JP2015059137A - Coloring composition, photosensitive coloring composition, color filter and method of producing the same, liquid crystal display device, organic electroluminescent element, and solid state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition having high color valency and excellent heat resistance, light resistance, and temporal stability, and provide a photosensitive coloring composition, a color filter and a production method thereof, a liquid crystal display device, an organic electroluminescent element, and a solid state image sensor, using the coloring composition.SOLUTION: A coloring composition comprises a compound represented by general formula (I) where P represents a phthalocyanine site, M represents a methine site, L represents a single bond or a linking group, and n represents an integer of 1-16.

Description

  The present invention relates to a coloring composition, a photosensitive coloring composition using the coloring composition, a color filter and a method for producing the same, a liquid crystal display device, an organic electroluminescence element (organic EL element), a solid-state imaging element, a dye, In particular, the present invention relates to a coloring composition containing a phthalocyanine dye and a methine dye as coloring components and its application.

  As a method for producing a color filter used for an image display device such as a liquid crystal display device or an organic EL display device, a solid-state image sensor, a dyeing method, a printing method, an electrodeposition method, or a pigment dispersion method is known.

  The dyeing method is a method for producing a color filter by dyeing a dyed substrate made of a natural resin such as gelatin, mulled or casein or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye. In dyeing methods, since dyes are used as coloring materials, there are problems with light resistance, heat resistance, moisture resistance, etc., and when large sizes are used, it is difficult to uniformly control dyeing and fixing properties, resulting in uneven color. It tends to occur, and has a problem that a dye-proof layer is required for dyeing and the process becomes complicated.

  In the electrodeposition method, a transparent electrode is formed in a predetermined pattern in advance, and a color filter is formed by ionizing a resin containing a pigment dissolved or dispersed in a solvent and applying a voltage to form a colored image in a pattern. It is a manufacturing method. In the electrodeposition method, in addition to the transparent electrode for display, a photolitho process including film formation and an etching process of a transparent electrode for forming a color filter is necessary. At that time, if an electrical short occurs, a line defect occurs and the yield decreases. Further, in principle, it is difficult to apply to a mosaic arrangement other than the stripe arrangement, and further, it is difficult to manage the transparent electrode.

  The printing method is a simple method for producing a color filter by printing such as offset printing using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin. However, it is difficult to filter because the usable ink has a high viscosity. In addition, defects due to dust, foreign matter, and gelled portions of the ink binder are likely to occur, and there are problems in position accuracy, line width accuracy, and planar smoothness associated with printing accuracy.

  The pigment dispersion method is a method for producing a color filter by a photolithography method using a photosensitive coloring composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat due to the use of pigments, and is patterned by a photolithographic method, so that sufficient positional accuracy can be secured and suitable for the production of color filters for large screens and high-definition color displays. It is a simple method.

  As a pigment dispersion method, a method using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is disclosed (for example, see Patent Document 1). However, in recent years, color filters for image display devices and solid-state image sensors have been demanded to have higher definition. In the conventional pigment dispersion method, pigments exist in the form of particles having a size. However, the resolution is not improved and color unevenness occurs due to coarse particles of the pigment, which is not suitable for applications requiring a fine pattern such as a solid-state imaging device.

  In order to achieve higher resolution of color filters, a technique using a dye as a coloring material has been studied, and a positive type using a naphthoquinonediazide compound or the like as a photosensitive coloring composition using a dye (for example, a patent) Two types of negative type (for example, see Patent Document 3) using a photopolymerization initiator (in combination with a polymerizable compound) as a photosensitive material have been proposed. However, these photosensitive coloring compositions have problems in terms of solvent solubility, and also have a problem that the heat resistance and light resistance of the dye are low.

  In view of the above, examples of the dye excellent in heat resistance and light resistance include phthalocyanine compounds and methine dyes. However, the solvent solubility is poor and there are practical problems, for example, it is difficult to produce a color filter by a coating method of a composition containing a phthalocyanine dye. If an attempt is made to improve the solvent solubility, the heat resistance and light resistance decrease. End up. Therefore, by including dyes excellent in solvent solubility, heat resistance, and light resistance, there is no dye precipitation, etc., and there is provided a dye-containing coloring composition or color filter that has excellent weather resistance to light and heat. Has not reached.

  On the other hand, as a phthalocyanine-based compound with improved solvent solubility, a long-chain alkyl group (for example, a functional group such as a long-chain alkyl group, an alkoxy group, an ester group, a polyether group, or a thioether group) is bonded to the benzene ring of phthalocyanine. And a sulfonic acid amide group (see, for example, Patent Document 5) have been proposed.

  As a phthalocyanine compound with improved solvent solubility, a compound in which a benzene ring of phthalocyanine is introduced with a heterocyclic group containing two or more nitrogen atoms as a substituent or one or more of nitrogen and sulfur atoms as a substituent is used. In addition, a dye-containing curable composition in which two or more nitrogen atoms or a heterocyclic compound containing one or more nitrogen and sulfur atoms is combined has been proposed (see, for example, Patent Document 6). Further, a phthalocyanine compound in which a phenoxy group having a specific substituent or an alkylene group in which a specific group is bonded via a sulfur atom or an oxygen atom is substituted on the benzene ring of phthalocyanine has been proposed (see, for example, Patent Document 7). ), A composition used in combination with an azo dye is known (for example, see Patent Document 8).

  As a methine compound, a compound in which a long-chain alkyl group (for example, see Patent Document 9) is introduced has been proposed.

On the other hand, a compound in which two coloring sites are linked by a covalent bond has been proposed. By connecting in this way, the feature that the absorption based on the two color development sites does not change can be obtained regardless of the use conditions. So far, for example, a compound in which a phthalocyanine compound and an azo compound are linked has been proposed (see, for example, Patent Document 10).

Japanese Patent Laid-Open No. 1-102469 JP-A-2-127602 JP-A-6-75375 JP-A-1-180865 Japanese Patent Laid-Open No. 3-195833 JP 2005-265995 A JP 2012-153814 A JP 2011-197670 A JP-A-2005-250420 JP 2013-76025 A

These phthalocyanine compounds in Patent Documents 4 to 8 are still not sufficiently soluble and have a low extinction coefficient. Particularly, when the film is formed, the extinction coefficient in the long wavelength region is lowered due to the association between phthalocyanine molecules. was there. Further, the light resistance was insufficient.
The methine compound in Patent Document 9 still has insufficient solubility, and particularly when it is formed into a film, there is a difficulty that absorption is reduced due to aggregation of the methine compound.
Moreover, in patent document 10, there existed a difficulty that light resistance was inadequate in the conventional connection type compound.

  As described above, in the conventional technique, the light absorption coefficient is lowered by heating by post-baking or the like, the heat resistance is insufficient, and the color value is inferior. Furthermore, the time-dependent stability and developability of the photosensitive coloring composition were insufficient.

  As described above, color filters for image display devices that require high definition, high brightness, and high color reproducibility, and color filters for solid-state imaging devices that require color unevenness and high color reproducibility, etc. Although coloring compositions containing dyes are useful for applications, in coloring compositions containing phthalocyanine compounds and methine compounds as dyes, the color density and hue of light and heat with respect to the solubility of dyes, etc. At present, stability (light resistance, heat resistance), spectral characteristics (such as hue and color purity suitable for color filters), and stability over time when used as a colored composition have not yet been satisfied. is there. Moreover, as a coloring composition, it is desired that developability is also favorable.

  The present invention has been made in view of the above, and a first object of the present invention is to provide a colored composition having a high color value and excellent heat resistance, light resistance, and stability over time. The second subject of the present invention is a photosensitive coloring composition having a spectral characteristic exhibiting a good hue and excellent in heat resistance and light resistance, a color filter using the same, a method for producing the same, and a liquid crystal display device Another object is to provide an organic electroluminescence device and a solid-state imaging device.

  Under such circumstances, the inventors of the present application have made extensive studies, and as a result, the phthalocyanine compound has a high color value by covalently linking the phthalocyanine moiety and the methine compound methine moiety, heat resistance, light resistance, and aging. The present inventors have found that it is excellent in stability and have completed the present invention.

（一般式（Ｉ）中、Ｐはフタロシアニン部位を表し、Ｍはメチン部位を表し、Ｌは単結合、または連結基を表す。ｎは１〜１６の整数を表す。）
＜２＞一般式（Ｉ）が、下記一般式（１）で表される、＜１＞に記載の着色組成物。

（一般式（１）において、Ｘは、それぞれ独立にハロゲン原子を表す。Ｒは、それぞれ独立に、水素原子または１価の置換基を表す。ただし、Ｒのうち、ｎ個は、−Ｌ−Ｍである。Ｍａは、Ｃｕ、Ｚｎ、Ｖ（＝Ｏ）、Ｍｇ、Ｎｉ、Ｔｉ（＝Ｏ）、Ｓｎ、またはＳｉを表す。ｍは、それぞれ独立に、０〜４の整数を表し、ｒは、それぞれ独立に、０〜４の整数を表す。但し、複数のｎのうち少なくとも１つは１以上である。複数のｍと複数のｒとの総和は１６である。）
＜３＞一般式（Ｉ）が、下記一般式（７）で表される、＜１＞または＜２＞に記載の着色組成物。

（一般式（７）中、Ｒ¹およびＲ²は、それぞれ独立に置換基を有してもよい３級アルキル基、または置換基を有してもよいアリール基を表し、Ｒ³は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。Ｚ¹およびＺ²は、それぞれ独立に、５員環もしくは６員環を形成するために必要な非金属原子を表す。Ｒ⁴およびＲ⁵は、それぞれ独立に、置換基を表す。ｎ１およびｎ２は、それぞれ独立に０〜２の整数である。但し、Ｒ¹〜Ｒ⁵の少なくとも一つは、−Ｌ−Ｐ−（Ｌ−Ｍ）_n-1である。）
＜４＞一般式（７）のＲ⁴またはＲ⁵が、−Ｌ−Ｐ−（Ｌ−Ｍ）_n-1である、＜３＞に記載の着色組成物。
＜５＞一般式（Ｉ）が、一般式（７’）で表される、＜１＞〜＜４＞のいずれかに記載の着色組成物。
一般式（７’）

（一般式（７’）中、Ｒ¹およびＲ²は、それぞれ独立に置換基を有してもよい３級アルキル基、または置換基を有してもよいアリール基を表し、ＺａおよびＺｂは、それぞれ独立に、窒素原子、または−Ｃ（Ｒ⁷）−を表し、Ｒ⁷は水素原子または置換基を表す。ＺｄおよびＺｅは、それぞれ独立に、窒素原子、または−Ｃ（Ｒ⁷）−を表す。Ｒ⁷は水素原子または置換基を表す。Ｒ⁴およびＲ⁵は、それぞれ独立に、置換基を表す。ｎ１およびｎ２は、０〜２の整数である。但し、Ｒ¹〜Ｒ²、Ｒ⁴〜Ｒ⁵の少なくとも一つは、−Ｌ−Ｐ−（Ｌ−Ｍ）_n-1である。）
＜６＞一般式（Ｉ）中のＬが、下記群Ａから選ばれる連結基、またはこれらの連結基を組み合わせてなる連結基である、＜１＞〜＜５＞のいずれかに記載の着色組成物。
群Ａ

＜７＞一般式（Ｉ）中のＬが、下記一般式（２）で表される、＜６＞に記載の着色組成物。
一般式（２）

（一般式（２）中、Ｌ¹は、酸素原子、または硫黄原子を表し、Ｌ²は、群Ａから選ばれる連結基、またはこれらの連結基を組み合わせてなる連結基を表す。＊は、Ｐとの結合部位を表し、＊＊はＭとの結合部位を表す。）
＜８＞一般式（Ｉ）中のＬが、スルホンアミド基を有する、＜１＞〜＜７＞のいずれかに記載の着色組成物。
＜９＞一般式（Ｉ）中のｎが、１〜４の整数を表す、＜１＞〜＜８＞のいずれかに記載の着色組成物。
＜１０＞＜１＞〜＜９＞のいずれかに記載の着色組成物、重合性化合物、および光重合開始剤を有する、感光性着色組成物。
＜１１＞光重合開始剤が、オキシム系化合物またはビイミダゾール系化合物である、＜１０＞に記載の感光性着色組成物。
＜１２＞＜１＞〜＜９＞のいずれかに記載の着色組成物、または＜１０＞または＜１１＞に記載の感光性着色組成物を用いた着色層を有するカラーフィルタ。
＜１３＞＜１＞〜＜９＞のいずれかに記載の着色組成物、または＜１０＞または＜１１＞に記載の感光性着色組成物を、基板上に適用し、着色層を形成する工程と、形成された着色層をパターン状に露光し、現像して着色領域を形成する工程と、を有するカラーフィルタの製造方法。
＜１４＞＜１２＞に記載のカラーフィルタ、または＜１３＞に記載のカラーフィルタの製造方法により作製されたカラーフィルタを有する液晶表示装置、有機エレクトロルミネッセンス素子または固体撮像素子。 Specifically, the above problem has been solved by the following means <1>, preferably <2> to <14>.
<1> A coloring composition containing a compound represented by the following general formula (I).

(In general formula (I), P represents a phthalocyanine moiety, M represents a methine moiety, L represents a single bond or a linking group, and n represents an integer of 1 to 16.)
<2> The colored composition according to <1>, wherein the general formula (I) is represented by the following general formula (1).

(In General Formula (1), each X independently represents a halogen atom. Each R independently represents a hydrogen atom or a monovalent substituent. However, among R, n represents -L-. M represents Ma, Cu, Zn, V (═O), Mg, Ni, Ti (═O), Sn, or Si, each m independently represents an integer of 0 to 4; Each independently represents an integer of 0 to 4. However, at least one of the plurality of n is 1 or more, and the sum of the plurality of m and the plurality of r is 16.)
<3> The colored composition according to <1> or <2>, in which the general formula (I) is represented by the following general formula (7).

(In General Formula (7), R ¹ and R ² each independently represent a tertiary alkyl group that may have a substituent, or an aryl group that may have a substituent, and R ³ represents a hydrogen atom. , A halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, Z ¹ and Z ² each independently form a 5-membered ring or a 6-membered ring. R ⁴ and R ⁵ each independently represents a substituent, and n 1 and n 2 are each independently an integer of 0 to 2, provided that R ^{1 to} R ⁵ At least one is -LP- (LM) _n-1 .)
<4> The colored composition according to <3>, wherein R ⁴ or R ^{5 in} the general formula (7) is -LP- (LM) _n-1 .
<5> The colored composition according to any one of <1> to <4>, in which the general formula (I) is represented by the general formula (7 ′).
General formula (7 ')

(In the general formula (7 ′), R ¹ and R ² each independently represent a tertiary alkyl group which may have a substituent or an aryl group which may have a substituent, and Za and Zb are Each independently represents a nitrogen atom or —C (R ⁷ ) —, R ⁷ represents a hydrogen atom or a substituent, and Zd and Ze each independently represent a nitrogen atom or —C (R ⁷ ) —. R ⁷ represents a hydrogen atom or a substituent, R ⁴ and R ⁵ each independently represents a substituent, and n1 and n2 are integers of 0 to 2, provided that R ^{1 to} R ² , R ^{4 to} R ⁵ is -LP- (LM) _n-1 .)
<6> The coloring according to any one of <1> to <5>, wherein L in the general formula (I) is a linking group selected from the following group A or a linking group formed by combining these linking groups. Composition.
Group A

<7> The colored composition according to <6>, wherein L in the general formula (I) is represented by the following general formula (2).
General formula (2)

(In General Formula (2), L ¹ represents an oxygen atom or a sulfur atom, and L ² represents a linking group selected from Group A or a linking group formed by combining these linking groups. The binding site to P is represented, and ** represents the binding site to M.)
<8> The colored composition according to any one of <1> to <7>, wherein L in the general formula (I) has a sulfonamide group.
<9> The colored composition according to any one of <1> to <8>, wherein n in the general formula (I) represents an integer of 1 to 4.
<10> Photosensitive coloring composition which has a coloring composition in any one of <1>-<9>, a polymeric compound, and a photoinitiator.
<11> The photosensitive coloring composition according to <10>, wherein the photopolymerization initiator is an oxime compound or a biimidazole compound.
<12> A color filter having a colored layer using the colored composition according to any one of <1> to <9> or the photosensitive colored composition according to <10> or <11>.
<13> A step of applying the colored composition according to any one of <1> to <9> or the photosensitive colored composition according to <10> or <11> on a substrate to form a colored layer. And a step of exposing the formed colored layer in a pattern and developing to form a colored region.
<14> A liquid crystal display device, an organic electroluminescence element, or a solid-state imaging device having the color filter according to <12> or the color filter produced by the method for producing a color filter according to <13>.

According to the present invention, it is possible to provide a coloring composition having a high color value and excellent heat resistance, light resistance, and stability over time.
In addition, according to the present invention, a photosensitive coloring composition having a spectral characteristic exhibiting a good hue and excellent in heat resistance and light resistance, a color filter using the same, a method for producing the same, and good image quality A liquid crystal display device, an organic electroluminescence element, and a solid-state imaging element can be provided.

  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 and an upper limit. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified.

In addition, "total solid content" described in this specification shows the sum total of the component remove | excluding the organic solvent from the composition of the coloring composition.
Further, in the present specification, “(meth) acryl” includes both acryl and methacryl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

  Hereinafter, the coloring composition, the photosensitive coloring composition, the color filter and the manufacturing method thereof, the liquid crystal display device, the organic electroluminescence element, and the solid-state imaging element of the present invention will be described in detail.

（一般式（Ｉ）中、Ｐはフタロシアニン部位を表し、Ｍはメチン部位を表し、Ｌは単結合、または連結基を表す。ｎは１〜１６の整数を表す。） <Coloring composition>
The coloring composition of the present invention contains a compound represented by the following general formula (I). Moreover, it is preferable that the coloring composition of this invention contains the organic solvent further as needed.

(In general formula (I), P represents a phthalocyanine moiety, M represents a methine moiety, L represents a single bond or a linking group, and n represents an integer of 1 to 16.)

Conventionally, when phthalocyanine dyes and methine dyes are applied to coloring compositions for color filters, not only spectral characteristics are insufficient, but phthalocyanine dyes and methine dyes are poorly soluble in organic solvents. In addition, heat resistance and light resistance may not be sufficient, and it has been difficult to produce a color filter using a coloring composition containing a phthalocyanine dye. In addition, when a colored composition containing a phthalocyanine dye and a methine dye is stored in a solution state, the solubility in an organic solvent is not sufficient, so that the dye precipitates when stored over time. It was poor.
In the present invention, by using the compound represented by the general formula (I) as the phthalocyanine dye and methine dye, the solubility in an organic solvent is improved, good spectral characteristics are obtained, and the color value is high. A colored composition having excellent heat resistance and light resistance and good stability over time can be obtained.

The reason for such an effect is not necessarily clear, but is presumed to be due to the following action. That is,
Phthalocyanine dyes tend to aggregate due to their strong associative power, and crystal-grown phthalocyanine dyes are poorly soluble in organic solvents and have insufficient stability over time as colored compositions. Further, methine dyes are also likely to aggregate due to their strong associative power, and crystal-grown phthalocyanine dyes are poor in solubility in organic solvents and have insufficient stability over time as colored compositions. However, in the compound in which these two color development sites are linked, when the color development sites aggregate with each other, the color development sites on one side act as an action to sterically inhibit aggregation, resulting in stability over time. Estimated to be higher.

  Moreover, when producing a photosensitive coloring composition using the coloring composition of the present invention, it can be configured as a positive type when it contains a naphthoquinone diazide compound as the photosensitive compound, and is negative when it contains a photopolymerization initiator. Can be configured. In general, the negative type can further contain a polymerizable compound. Moreover, other components may be included as necessary.

（一般式（Ｉ）中、Ｐはフタロシアニン部位を表し、Ｍはメチン部位を表し、Ｌは単結合、または連結基を表す。ｎは１〜１６の整数を表す。） First, the compound represented by the general formula (I) contained in the colored composition of the present invention will be described in detail.

(In general formula (I), P represents a phthalocyanine moiety, M represents a methine moiety, L represents a single bond or a linking group, and n represents an integer of 1 to 16.)

  The phthalocyanine moiety exhibits a good hue as a cyan dye, and the methine moiety exhibits a favorable hue for a yellow color. The composition of the present invention provides a green color with a good hue. In addition, the solubility in an organic solvent at the time of preparing the colored composition is good, and when the colored composition is stored in a liquid state, or when the colored composition is in the state of a colored film on the substrate, the dye etc. over time Storage stability is good without precipitation, and heat resistance and light resistance are good. Furthermore, when a colored pattern (colored pixel) constituting the color filter is formed, the pattern formability is also excellent.

In general formula (I), L represents a single bond or a linking group.
Examples of the linking group represented by L include a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and An organic linking group consisting of 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may have a substituent. Specific examples of the organic linking group include a linking group selected from Group A below, or a linking group formed by combining these linking groups.

Group A

（Ａ−２）群 L preferably includes at least one selected from the following group (A-1) and at least one selected from the following group (A-2).
(A-1) group

(A-2) group

（一般式（２）中、Ｌ¹は、酸素原子、または硫黄原子を表し、Ｌ²は、前記群Ａから選ばれる連結基、またはこれらの連結基を組み合わせてなる連結基を表す。＊は、Ｐとの結合部位を表し、＊＊はＭとの結合部位を表す。）
一般式（２）中、Ｌ²は前記（Ａ−１）群から選択される１つまたは２つ以上の組み合わせであることが好ましい。 L is more preferably a linking group represented by the following general formula (2).
General formula (2)

(In General Formula (2), L ¹ represents an oxygen atom or a sulfur atom, and L ² represents a linking group selected from Group A or a linking group formed by combining these linking groups. , P represents a binding site, and ** represents a binding site to M.)
In general formula (2), L ² is preferably one or a combination of two or more selected from the group (A-1).

L ¹ represents an oxygen atom or a sulfur atom, preferably an oxygen atom.
L ² represents a linking group selected from the group A or a linking group formed by combining these linking groups, and preferably has a sulfonamide group.

Specifically, as L, the following linking groups are preferable.

  In general formula (I), n represents the integer of 1-16, the integer of 1-8 is preferable, the integer of 1-4 is more preferable, and 1 or 2 is more preferable.

（一般式（１）において、Ｘは、それぞれ独立にハロゲン原子を表す。Ｒは、それぞれ独立に、水素原子または１価の置換基を表す。ただし、Ｒのうち、ｎ個は、−Ｌ−Ｍである。Ｍａは、Ｃｕ、Ｚｎ、Ｖ（＝Ｏ）、Ｍｇ、Ｎｉ、Ｔｉ（＝Ｏ）、Ｓｎ、またはＳｉを表す。ｍは、それぞれ独立に、０〜４の整数を表し、ｒは、それぞれ独立に、０〜４の整数を表す。但し、複数のｎのうち少なくとも１つは１以上である。複数のｍと複数のｒとの総和は１６である。）
一般式（１）中、Ｌ、Ｍ、ｎは、一般式（Ｉ）中のＬ、Ｍと、ｎに対応する。 The general formula (I) is preferably represented by the following general formula (1).

(In General Formula (1), each X independently represents a halogen atom. Each R independently represents a hydrogen atom or a monovalent substituent. However, among R, n represents -L-. M represents Ma, Cu, Zn, V (═O), Mg, Ni, Ti (═O), Sn, or Si, each m independently represents an integer of 0 to 4; Each independently represents an integer of 0 to 4. However, at least one of the plurality of n is 1 or more, and the sum of the plurality of m and the plurality of r is 16.)
In general formula (1), L, M, and n correspond to L, M, and n in general formula (I).

  When the phthalocyanine moiety represented by the general formula (1) is a mixture of two or more types, m and r each mean an average value of the compounds in the mixture.

  In the phthalocyanine moiety in the present invention, the ratio of the absorption intensity at 550 nm to the absorption intensity at 650 nm (550 nm / 650 nm) is preferably in the range of 0 to 0.2, and preferably in the range of 0 to 0.1. Further preferred.

In the general formula (1), X represents a halogen atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. Further, when the substitution position of X is the α-position of the phthalocyanine skeleton, the absorption wavelength becomes longer and can be suitably used for a green filter.
m represents 0-4 independently, and 2-4 are preferable. 2-15 are preferable, as for the sum total of four m, 6-15 are more preferable, and 9-15 are especially preferable.

  Ma represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Mg, Sn, or Si, and Zn or Cu is preferable.

R represents a hydrogen atom or a monovalent substituent. However, at least 1 of R is -LM in general formula (I). Examples of the monovalent substituent include the substituent T described later. R is preferably a hydrogen atom, an alkyl group, an alkoxy group, a phenoxy group, an aryl group or an aryloxy group, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a phenoxy group, More preferred is a hydrogen atom.
r represents 0-4 independently, and 0-1 are preferable.

  In the general formula (1), the substitution position of R in the phthalocyanine skeleton may be either the α-position or the β-position of the phthalocyanine skeleton, but the α-position substitution product has a greater effect of suppressing molecular association and is colored. This is preferable in terms of increasing the extinction coefficient of the composition layer.

Examples of the substituent T described above are shown below.
An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 2 carbon atoms) 18 alkenyl groups such as vinyl group, allyl group and 3-buten-1-yl group), aryl groups (preferably aryl groups having 6 to 24 carbon atoms such as phenyl group and naphthyl group), heterocyclic ring Group (preferably a heterocyclic group having 1 to 18 carbon atoms such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2- Limidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl Group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, Methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group) An aryloxy group (preferably having 6 to 2 carbon atoms) An aryloxy group of, for example, phenoxy group, 1-naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazole-5-oxy group, 2- Tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably carbon number) 2 to 24 acyloxy groups, for example, acetoxy group, pivaloyloxy group, 2-ethylhexanoyloxy group, 2-methylpropanoyloxy group, octanoyloxy group, butanoyloxy group, 2-methylbutanoyloxy group, Benzoyloxy group, dodecanoyloxy group), al A alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms such as ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, or cycloalkyloxycarbonyloxy group such as cyclohexyloxy A carbonyloxy group), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms) For example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably A sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), alkylsulfonyloxy group (preferably alkyl having 1 to 24 carbon atoms) A sulfonyloxy group, for example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, for example, a phenylsulfonyloxy group) An acyl group (preferably an acyl group having 1 to 24 carbon atoms, such as formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group),

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methyl; A cyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group), a carbamoyl group (preferably a carbamoyl group having 1 to 24 carbon atoms, such as a carbamoyl group) Group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl N, N-dicyclohexylcarbamoyl group), an amino group (preferably an amino group having 24 or less carbon atoms, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, 2- Ethylhexylamino group, cyclohexylamino group), anilino group (preferably 6-24 anilino group, for example, anilino group, N-methylanilino group), heterocyclic amino group (preferably 1-18 heterocyclic amino group) For example, 4-pyridylamino group), carbonamide group (preferably 2-24 carbonamide groups, for example, acetamido group, benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group), ureido group (preferably carbon A ureido group of 1 to 24, such as a ureido group, N, N-dimethyl group; Id group, N-phenylureido group), imide group (preferably an imide group having 24 or less carbon atoms, for example, N-succinimide group, N-phthalimide group), alkoxycarbonylamino group (preferably having 2 to 24 carbon atoms). Alkoxycarbonylamino group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 7 carbon atoms) 24 aryloxycarbonylamino group, for example, phenoxycarbonylamino group), sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, such as methanesulfonamide group, butanesulfonamide group, benze Sulfonamide group, hexadecane sulfonamide group, cyclohexane sulfonamide group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group having 1 to 24 carbon atoms, for example, phenylazo group, 3-pyrazolylazo group), alkylthio group (preferably 1 to 1 carbon atom) 24 alkylthio groups, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio groups (preferably arylthio groups having 6 to 24 carbon atoms, for example, phenylthio group), heterocyclic thio groups (preferably A heterocyclic thio group having 1 to 18 carbon atoms, for example, 2-benzothiazolylthio , 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), arylsulfinyl group (preferably 6 to 24 carbon atoms). Arylsulfinyl group such as phenylsulfinyl group, alkylsulfonyl group (preferably alkylsulfonyl group having 1 to 24 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group) Group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, for example, phenyls Sulfonyl group, 1-naphthylsulfonyl group), sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group) N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphospho Nyl group, phenylphosphonyl group), phosphinoylamino group (preferably a phosphinoylamino group having 1 to 24 carbon atoms, for example, diethoxyphosphinoylamino group, dioctyloxyphosphinoylamino group). .

  Further, the substituent T is an alkaline aqueous solution solubilized part, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonimide group, a phenolic hydroxyl group, an acetoacetamide group, for the purpose of improving developability with respect to an alkaline developer. Substituents such as acetoacetate groups and substituents such as alkyl groups, alkyloxy groups, alkylthio groups, aryloxy groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups and the like in which these groups are substituted are preferably used. .

  When the above-described substituent T is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different. However, the substituent in the present invention preferably has a mass per molecule of 500 or less.

  The molecular weight of the phthalocyanine moiety is preferably 1500 to 3500, more preferably 1750 to 2500.

The phthalocyanine moiety can be synthesized according to the methods described in “Phthalocyanine as a functional dye, published by IPC Corporation”, “Phthalocyanine—Chemistry and Function—issued by IPC Corporation”, and the like.
The phthalocyanine moiety in the present invention can be synthesized, for example, by subjecting an optionally substituted phthalonitrile to condensation cyclization in the presence of a metal source. At that time, a phthalocyanine compound into which various substituents are introduced can be synthesized by mixing a plurality of phthalonitriles. Even when single phthalonitrile is used as a raw material, there are a maximum of four types of cyclized isomers.
As a raw material for the phthalocyanine moiety, phthalonitrile is preferable in that it does not require a high temperature during production, but is not particularly limited, and is generally known as a raw material for phthalocyanine, for example, By using phthalic acid, phthalic anhydride, or phthalimide, which may be substituted, phthalocyanines into which various substituents are introduced can be synthesized.

（一般式（７）中、Ｒ¹およびＲ²は、それぞれ独立に置換基を有してもよい３級アルキル基、または置換基を有してもよいアリール基を表し、Ｒ³は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。Ｚ¹およびＺ²は、それぞれ独立に、５員環もしくは６員環を形成するために必要な非金属原子を表す。Ｒ⁴およびＲ⁵は、それぞれ独立に、置換基を表す。ｎ１およびｎ２は、０〜２の整数である。但し、Ｒ¹〜Ｒ⁵の少なくとも一つは、−Ｌ−Ｐ−（Ｌ−Ｍ）_n-1である。）
一般式（７）中、Ｐ、Ｌ、Ｍ、ｎは、一般式（Ｉ）中のＰ、Ｌ、Ｍ、ｎとそれぞれ同義であり、好ましい範囲も同様である。 The general formula (I) is preferably represented by the following general formula (7).

(In General Formula (7), R ¹ and R ² each independently represent a tertiary alkyl group that may have a substituent, or an aryl group that may have a substituent, and R ³ represents a hydrogen atom. , A halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, Z ¹ and Z ² each independently form a 5-membered ring or a 6-membered ring. R ⁴ and R ⁵ each independently represents a substituent, and n 1 and n ² are each an integer of 0 to 2, provided that at least one of R ^{1 to} R ⁵ Is -LP- (LM) _n-1 .)
In general formula (7), P, L, M, and n are synonymous with P, L, M, and n in general formula (I), respectively, and their preferable ranges are also the same.

The tertiary alkyl group which may have a substituent represented by R ¹ and R ² is preferably a tertiary alkyl group which may have a substituent having 4 to 48 carbon atoms. The tertiary alkyl group may be a substituted or unsubstituted tertiary or cyclic or chain tertiary alkyl group. Examples of the tertiary alkyl group include a t-butyl group, a t-amyl group, a t-octyl group, an adamantyl group, a 1-methylcyclopropyl group, a 1-methylcyclohexyl group, and 1-benzylcyclopropyl.

The aryl group which may have a substituent represented by R ¹ and R ² is preferably an aryl group which may have a substituent having 6 to 48 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the substituent that the tertiary alkyl group and aryl group represented by R ¹ and R ² may have include a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 48 carbon atoms). More preferably, it is an alkyl group of 1 to 18, and the alkyl group may be linear, branched, or cyclic, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl group (preferably having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms) An alkenyl group such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably carbon An aryl group having 6 to 48 prime numbers, more preferably 6 to 12 aryl groups such as phenyl and naphthyl, and a heterocyclic group (preferably 1 to 32 carbon atoms, more preferably 1 to 12 heterocyclic groups such as 2 -Thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably having 3 to 38 carbon atoms, More preferably, it is a silyl group having 3 to 12, for example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably having a carbon number) 1 to 48, more preferably 1 to 12 alkoxy groups such as methoxy, ethoxy, 1-butyl Xoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups (for example, cyclopentyloxy, cyclohexyloxy)), aryloxy groups (preferably having 6 to 48 carbon atoms, more preferably 6 to 12 carbon atoms) An aryloxy group, for example, phenoxy, 1-naphthoxy, a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1-12, for example, 1-phenyltetrazole-5-oxy 2-tetrahydropyranyloxy), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 12, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy Group (preferably having 2 to 48 carbon atoms) Preferably, it is an acyloxy group having 2 to 12, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 12 carbon atoms, For example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group (for example, cyclohexyloxycarbonyloxy)), aryloxycarbonyloxy group (preferably 7-32 carbon atoms, more preferably 7-18 aryls) An oxycarbonyloxy group such as phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms such as N, N-dimethylcarba Moyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably 1 to 12 sulfamoyloxy) A group such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 12 carbon atoms, For example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 12 carbon atoms, such as phenylsulfonyloxy),

An acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms, such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 carbon atoms) 48, more preferably 2 to 12 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), aryloxycarbonyl groups (preferably having 7 to 32 carbon atoms, more preferably 7 to 12 aryloxycarbonyl groups such as phenoxycarbonyl, carbamoyl groups (preferably having 1 to 48 carbon atoms, more preferably 1 to 12 carbamoyl groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl -N Octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably having 32 or less carbon atoms, more preferably Is an amino group having 12 or less, for example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably having 6 to 32 carbon atoms, more preferably 6-12 anilino group, for example, anilino, N-methylanilino), a heterocyclic amino group (preferably a C1-C32, more preferably 1-12 heterocyclic amino group, for example, 4-pyridylamino), Carboxamide group (preferably 2 to 48 carbon atoms, more preferred Is a carbonamide group having 2 to 12 carbon atoms, for example, acetamido, benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide), ureido group (preferably having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms, for example, ureido N, N-dimethylureido, N-phenylureido), an imide group (preferably an imide group having 20 or less carbon atoms, more preferably 12 or less, such as N-succinimide and N-phthalimide), an alkoxycarbonylamino group ( An alkoxycarbonylamino group having preferably 2 to 48 carbon atoms, more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino. B), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 48 carbon atoms, More preferably, it is a sulfonamide group of 1 to 12, for example, methanesulfonamide, butanesulfonamide, octanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably having 1 carbon atom) -48, more preferably 1-12 sulfamoylamino groups such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), azo groups (preferably having 1 carbon atom) ~ 48, more preferably 1-24. In zone group, e.g., phenylazo, 3-pyrazolyl azo),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably 6 to 6 carbon atoms). 12 arylthio groups such as phenylthio), heterocyclic thio groups (preferably having 1 to 32 carbon atoms, more preferably 1 to 12 heterocyclic thio groups such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1-12, for example, dodecanesulfinyl), an arylsulfinyl group (preferably having 6 to 32 carbon atoms, More preferably 6-12 arylsulfinyl groups, for example Phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 12, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, Hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably 6-48 carbon atoms, more preferably 6-12 arylsulfonyl groups such as phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl groups (preferably Is a sulfamoyl group having 32 or less carbon atoms, more preferably 16 or less, such as sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, -Ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms such as phenoxyphosphonyl, octyl Oxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 12 carbon atoms such as diethoxyphosphinoylamino, dioctyloxyphosphino Ilamino).

When the tertiary alkyl group optionally having substituents represented by R ¹ and R ² and the aryl group optionally having substituents are substituted with two or more substituents, The substituents may be the same or different.

R ³ in the general formula (7), a hydrogen atom, a halogen atom, an optionally substituted alkyl group or substituted represents an even aryl group, a halogen atom R ^3,, a substituent The alkyl group which may have and the aryl group which may have a substituent represent a group having the same meaning as the halogen atom, alkyl group and aryl group described for the substituent in R ¹ and R ² above. The alkyl group which may have a substituent represented by R ³ and the aryl group which may have a substituent may have a substituent represented by R ¹ and R ² above. Examples of the substituent of the alkyl group which may have a substituent and the substituent of the aryl group which may have a substituent include those substituted with two or more substituents. May be the same or different.

Z ¹ and Z ² in the general formula (7) each independently form a 5-membered or 6-membered ring together with the nitrogen atom adjacent to Z ¹ or Z ² and the carbon atom bonded thereto in the general formula (7). Represents a group of nonmetallic atoms necessary for the purpose. Examples of the nonmetallic atom group include a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom.

Specifically, Z ¹ and Z ² are preferably —N═CR ^z —. Z ¹ and Z ² preferably represent the same nonmetallic atom. R ^z represents a hydrogen atom or a substituent, and the substituent is synonymous with the substituent described in the above R ¹ , and the preferred range is also the same.

R ⁴ and R ⁵ in the general formula (7) each independently represent a substituent. A substituent is synonymous with the monovalent substituent of R in General formula (1), and its preferable range is also the same.
n1 and n2 are each independently an integer of 0 to 2, and 1 is preferable.

At least one of R ^{1 to} R ⁵ in the general formula (7) is -LP- (LM) _n-1 , and R ⁴ or R ⁵ is -LP- (LM) _n. It is preferably _-1 . A plurality of L and M may be the same or different.

（一般式（７’）中、Ｒ¹およびＲ²は、それぞれ独立に置換基を有してもよい３級アルキル基、または置換基を有してもよいアリール基を表し、ＺａおよびＺｂは、それぞれ独立に、窒素原子、または−Ｃ（Ｒ⁷）−を表し、Ｒ⁷は置換基を表す。ＺｄおよびＺｅは、それぞれ独立に、窒素原子、または−Ｃ（Ｒ⁷）−を表す。Ｒ⁷は水素原子または置換基を表す。Ｒ⁴およびＲ⁵は、それぞれ独立に、置換基を表す。ｎ１およびｎ２は、０〜２の整数である。但し、Ｒ¹〜Ｒ²、Ｒ⁴〜Ｒ⁵の少なくとも一つは、−Ｌ−Ｐ−（Ｌ−Ｍ）_n-1である。）
一般式（７’）中、Ｐ、Ｌ、Ｍ、ｎは、一般式（Ｉ）中のＰ、Ｌ、Ｍ、ｎとそれぞれ同義であり、好ましい範囲も同様である。 The general formula (I) is preferably represented by the following general formula (7 ′) from the viewpoints of hue, fastness, molar extinction coefficient, and the like.
General formula (7 ')

(In the general formula (7 ′), R ¹ and R ² each independently represent a tertiary alkyl group which may have a substituent or an aryl group which may have a substituent, and Za and Zb are Each independently represents a nitrogen atom or —C (R ⁷ ) —, R ⁷ represents a substituent, and Zd and Ze each independently represent a nitrogen atom or —C (R ⁷ ) —. R ⁷ represents a hydrogen atom or a substituent, R ⁴ and R ⁵ each independently represents a substituent, n1 and n2 are integers of 0 to 2, provided that R ^{1 to} R ² , R ⁴ at least one to R ⁵ is -L-P- (L-M) n-1.)
In general formula (7 ′), P, L, M, and n have the same meanings as P, L, M, and n in general formula (I), respectively, and the preferred ranges are also the same.

R ¹ and R ² in the general formula (7 ') has the same meaning as R ¹ and R ² in the general formula (1), and preferred ranges are also the same.
Za and Zb in the general formula (7 ′) each independently represent a nitrogen atom or —C (R ⁷ ) — (regardless of the right and left of the bond). R ⁷ represents a hydrogen atom or a substituent. The substituent represented by R ⁷ has the same meaning as the substituent described for R ¹ , and the preferred range is also the same. In addition, when the substituent represented by R ⁷ is a further substitutable group, it may be substituted with the above substituent. When R ⁷ is substituted with two or more substituents, these substituents may be the same or different.

Zd and Ze in the general formula (7 ′) each independently represent a nitrogen atom or —C (R ⁷ ) — (regardless of whether the bond is left or right), and R ⁷ represents a hydrogen atom or a substituent. The substituent represented by R ⁷ has the same meaning as the substituent described for R ¹ , and the preferred range is also the same. When the substituent represented by R ⁷ is a further substitutable group, it may be substituted with the above substituent. When R ⁷ is substituted with two or more substituents, these substituents may be the same or different.

R ⁴ and R ⁵ in formula (7 ′) each independently represent a substituent. R ⁴ is preferably bonded to Zb and R ⁵ is preferably bonded to Ze. A substituent is synonymous with the monovalent substituent of R in General formula (1), and its preferable range is also the same.
N1 and n2 in the general formula (7 ′) are each independently an integer of 0 to 2, and 1 is preferable.

At least one of R ^{1 to} R ² and R ^{4 to} R ^{5 in} the general formula (7 ′) is —LP— (LM) _n−1 , and R ⁴ is —LP— (L -M) _n-1 is preferred. A plurality of L and M may be the same or different.

（一般式（３）において、Ｘは、それぞれ独立にハロゲン原子を表す。Ｒは、それぞれ独立に、水素原子または１価の置換基を表す。ただし、Ｒの少なくとも１つは、Ｌとの結合部位である。Ｍａは、Ｃｕ、Ｚｎ、Ｖ（＝Ｏ）、Ｍｇ、Ｎｉ、Ｔｉ（＝Ｏ）、Ｓｎ、またはＳｉを表す。ｍは、それぞれ独立に、０〜４の整数を表し、ｒは、それぞれ独立に、０〜４の整数を表す。但し、複数のｍのうち少なくとも１つは１以上である。複数のｍと複数のｒとの総和は１６である。Ｒ¹およびＲ²は、それぞれ独立に置換基を有してもよい３級アルキル基、または置換基を有してもよいアリール基を表し、Ｒ³は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、または置換基を有してもよいアリール基を表す。Ｚ¹およびＺ²は、それぞれ独立に、５員環もしくは６員環を形成するために必要な非金属原子を表す。Ｒ⁵は、置換基を表す。ｎ２は０〜２の整数である。ｎは１〜１６の整数を表す。Ｌは、単結合、または連結基を表す。） The general formula (I) is preferably represented by the following general formula (3).
General formula (3)

(In General Formula (3), each X independently represents a halogen atom. Each R independently represents a hydrogen atom or a monovalent substituent. However, at least one of R is a bond to L. Ma represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Sn, or Si, each m independently represents an integer of 0 to 4, r Each independently represents an integer of 0 to 4. However, at least one of the plurality of m is 1 or more, and the sum of the plurality of m and the plurality of r is 16. R ¹ and R ² Each independently represents a tertiary alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ³ represents a hydrogen atom, a halogen atom or an alkyl which may have a substituent. Represents an aryl group which may have a group or a substituent, and Z ¹ and Z ² each represents Each independently represents a nonmetallic atom necessary for forming a 5-membered ring or a 6-membered ring, R ⁵ represents a substituent, n2 is an integer of 0 to 2, and n is an integer of 1 to 16. L represents a single bond or a linking group.)

In General formula (3), X, R, Ma, r, and m are synonymous with X, R, Ma, r, and m in General formula (1), respectively, and their preferable ranges are also the same.
In the general formula ^{(3), R 1 ~R 3} , R 5, Z 1 ~Z 2, n2 is the general formula (7) in the ^{R 1 ~R 3, R 5,} Z 1 ~Z 2, n2 respectively synonymous The preferred range is also the same.
In General formula (3), L and n are synonymous with L and n in General formula (I), respectively, and their preferable ranges are also the same.

（一般式（４）において、Ｘは、それぞれ独立にハロゲン原子を表す。Ｒは、それぞれ独立に、水素原子または１価の置換基を表す。ただし、Ｒの少なくとも１つは、Ｌとの結合部位である。Ｍａは、Ｃｕ、Ｚｎ、Ｖ（＝Ｏ）、Ｍｇ、Ｎｉ、Ｔｉ（＝Ｏ）、Ｓｎ、またはＳｉを表す。ｍは、それぞれ独立に、０〜４の整数を表し、ｒは、それぞれ独立に、０〜４の整数を表す。但し、複数のｍのうち少なくとも１つは１以上である。複数のｍと複数のｒとの総和は１６である。Ｒ¹およびＲ²は、それぞれ独立に置換基を有してもよい３級アルキル基、または置換基を有してもよいアリール基を表し、ＺａおよびＺｂは、それぞれ独立に、窒素原子、または−Ｃ（Ｒ⁴）−を表し、Ｒ⁴は水素原子または置換基を表す。ＺｄおよびＺｅは、それぞれ独立に、窒素原子、または−Ｃ（Ｒ⁷）−を表す。Ｒ⁷は水素原子または置換基を表す。Ｒ⁵は、置換基を表す。ｎ２は、０〜２の整数である。ｎは１〜１６の整数を表す。Ｌは、単結合、または連結基を表す。） The general formula (I) is preferably represented by the following general formula (4).
General formula (4)

(In General Formula (4), each X independently represents a halogen atom. Each R independently represents a hydrogen atom or a monovalent substituent, provided that at least one of R is a bond to L. Ma represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Sn, or Si, each m independently represents an integer of 0 to 4, r Each independently represents an integer of 0 to 4. However, at least one of the plurality of m is 1 or more, and the sum of the plurality of m and the plurality of r is 16. R ¹ and R ² Each independently represents a tertiary alkyl group which may have a substituent or an aryl group which may have a substituent, and Za and Zb each independently represent a nitrogen atom or —C (R ⁴ ) - represents, .Zd and Ze R ⁴ represents a hydrogen atom or a substituent, it To be independent, a nitrogen atom or ^{-C (R 7), - .R} 7 representing a is .R ⁵ represents a hydrogen atom or a substituent, .N2 representing the substituent is an integer of 0 to 2 .n Represents an integer of 1 to 16. L represents a single bond or a linking group.

In General formula (4), X, R, Ma, r, and m are synonymous with X, R, Ma, r, and m in General formula (1), respectively, and their preferable ranges are also the same.
In the general formula ^{(4), R 1, R} 2, R 5, Za~Ze, n2 have the general formula R ¹ in ^{(7 '), R 2,} R 5, Za~Ze, n2 and have the same meanings, The preferable range is also the same.
In General formula (4), L and n are synonymous with L and n in General formula (I), respectively, and their preferable ranges are also the same.

  Hereinafter, although the specific example of a compound represented with general formula (I) is given, it cannot be overemphasized that this invention is not limited to these.

  There is no restriction | limiting in particular as a synthesis example of the compound represented by general formula (I), It can synthesize | combine by a well-known synthesis method. For example, as shown in the following scheme, a compound corresponding to L in the general formula (I) (M-1 in the following scheme) and a compound corresponding to M in the general formula (I) (M-2 in the following scheme) After the reaction, the compound represented by the general formula (I) can be efficiently synthesized by bonding the phthalocyanine moiety. For example, the compound 1 can be synthesized according to the following scheme.

The content of the compound represented by the general formula (I) (and a conventionally known dye to be used in combination as needed) in the coloring composition can satisfy the spectral characteristics, and the smaller the dye ratio, the lower the sensitivity and It is preferable from the viewpoint of developability.
As content in the coloring composition of the compound represented by general formula (I), 1-70 mass% is preferable with respect to the total solid of a coloring composition, and 3-50 mass% is more preferable. By setting it as this range, coloring power and pattern formation property can be compatible.

  In the coloring composition of this invention, the compound represented by general formula (I) can be used individually as a dye, or multiple types can be used together. Furthermore, conventionally well-known dye can also be used together with the compound represented by general formula (I).

  The conventionally known dye is not particularly limited as long as it is a dye that dissolves in a required amount in an organic solvent, and can be appropriately selected according to the required spectral absorption. Examples of the dye species include acidic dyes, basic dyes, disperse dyes, reactants of acidic dyes with basic compounds, and reactants of basic dyes with acid compounds that are soluble in organic solvents.

  These dyes have a spectrum desirable as a color filter and must be dissolved in a concentration necessary for a solution containing an organic solvent or an alkali-soluble resin, which will be described later, so as not to cause precipitation or aggregation with time. These dyes include C.I. described in the Color Index. I. It can select suitably from Solvent Color etc. In addition, it is possible to select a dye having suitable solvent solubility and spectrum from known oil-soluble dyes, acid dyes, disperse dyes, reactive dyes, direct dyes and the like.

  Judgment of the solubility of the dye in the organic solvent can be made by whether or not 1% or more of the dye is dissolved in the organic solvent at 25 ° C. by weight. However, even if it is below this range, this is not the case when the solubility is increased by using the mixture, and even if the solubility is less than 1%, it can be used depending on the amount added.

Further, the coloring composition of the present invention may contain a dye compound or a pigment compound having another structure and a dispersion thereof as a coloring component.
The dye compound may have any structure as long as it does not affect the hue of the colored image. For example, the dye compound may be monomethine, azo (for example, Solvent Yellow 162), anthraquinone (for example, JP 2001-10881 anthraquinone compounds), phthalocyanine series (for example, phthalocyanine compounds described in US 2008/0076044), xanthene series (for example, CI Acid Red 289 (CIAcid.Red)). 289)), triarylmethane series (for example, CI Acid Blue 7), CI Acid Blue 83, CI Acid Blue 90, CI Eye・ Solvent Blue 38 (CISolvent Blue38), Sea Acid Violet 7 (CIAcid Violet17), CI 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 pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 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 Disazo condensation compound pigments such as Brown 23, Pigment Yellow 13, Pigment Yellow 83, or Disazo Compound Pigments such as Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15, Pigment Blue 56 Or triarylcarbonium compound pigments such as Pigment Blue 61, dioxazine compound pigments such as Pigment Violet 23 or Pigment Violet 37, aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, pigment red 264, pigment red 272, pigment orange 71, or diketopyrrolopyrrole compound pigment such as pigment orange 73, thioindigo compound pigment such as pigment red 88, pigment yellow 139, pigment orange 66 Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Oren 40, or pyranthrone compound pigments such as Pigment Red 216 or isoviolanthrone compound pigments, such as Pigment Violet 31, and the like.

Among these, it is preferable to use the following yellow dye.

  When a dye or a pigment is blended as a dispersion, it can be adjusted according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.

  A dye or a pigment can be used as long as the effects of the present invention are not impaired. When it has dye or a pigment, it is preferable that content of dye or a pigment is 0.5 mass%-70 mass% with respect to the total solid of a coloring composition. The dye or pigment is preferably added to the coloring 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. The amount of the compound other than the compound represented by the general formula (I) is preferably 30% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less based on the total dye compound. Further preferred.

[Organic solvent]
The coloring 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 coexisting component and the applicability when a colored composition is prepared, and in particular, the solubility, applicability, and safety of the binder. It is preferable to select in consideration of the properties.

  As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons are used. Specific examples include those described in paragraphs [0161] to [0162] of JP2012-032754A. Is done.

  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 composition is preferably such that the total solid concentration of the composition is 10% by mass to 80% by mass, and more preferably 15% by mass to 60% by mass.

<Photosensitive coloring composition>
The photosensitive coloring composition of this invention has the coloring composition of this invention, a polymeric compound, and a photoinitiator. The photosensitive coloring composition of this invention can be comprised using another component as needed.

  As content in the photosensitive coloring composition of the compound represented by General formula (1), although it changes with molecular weights and its light absorption coefficient, it is 1 mass%-with respect to the total solid of photosensitive coloring composition. 70 mass% is preferable and 10 mass%-50 mass% are more preferable. When the content of the compound represented by the general formula (1) is within the above range, it is advantageous in that a good color density can be obtained and the patterning of the pixel becomes good.

[Polymerizable compound]
The photosensitive coloring 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 any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and (co) polymers thereof. Specific examples of the polymerizable compound can be referred to the descriptions in paragraphs 0042 to 0049 of JP2013-182215A, the contents of which are incorporated herein.

  A commercially available product may be used as the polymerizable compound. Examples thereof include Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate).

  The content of the polymerizable compound in the total solid content of the photosensitive coloring composition is not particularly limited, and is preferably 10% by mass to 80% by mass and more preferably 15% by mass from the viewpoint of more effectively obtaining the effects of the present invention. % To 75% by mass is more preferable, and 20% to 60% by mass is particularly preferable. Only one type of polymerizable compound may be used, or two or more types may be used. When there are two or more kinds of polymerizable compounds, the total is preferably in the above range.

[Photopolymerization initiator]
The photosensitive coloring composition of the present invention contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize a 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 or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, and JP-A No. 2001-233842. These oxime compounds are mentioned.
As specific examples of the oxime compound, the description in paragraph 0053 of JP2013-182215A can be referred to, and the contents thereof are incorporated in the present specification.

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

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

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

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

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

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

In the general formula (b), R ¹⁰¹ represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl. Represents a group, a heterocyclic thiocarbonyl group, a heteroarylthiocarbonyl group or —CO—CO—Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

^R102 represents an alkyl group, an aryl group or a heterocyclic group, and these may be substituted.
R ¹⁰³ and R ¹⁰⁴ each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.

R ^{105 to} R ¹¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, a heteroaryloyl group, an alkylthio group, an aryloylthio group, or a heteroaryloyl group. , Alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, nitro group, amino group, sulfonic acid group, hydroxy group, carboxylic acid group, amide group, carbamoyl Represents a group or a cyano group.
One or two of R ^{105 to} R ¹¹¹ are electron-withdrawing substituents, that is, a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group or an arylcarbonyl group, which has a much higher curability. Since a photosensitive coloring composition is obtained, it is preferable.

  Specific examples of the compound having a fluorene structure represented by the general formula (b) are given below. However, it is not limited to these compounds. Ac represents an acetyl group.

  The compound having a fluorene structure represented by the general formula (b) can be synthesized, for example, according to the synthesis method described in JP-A-2008-292970.

  As specific examples of the biimidazole compound, the description in paragraphs 0061 to 0070 of JP2013-182213A can be referred to, and the contents thereof are incorporated in the present specification.

  Moreover, you may use an alpha acylamino compound as a photoinitiator. The α-acylamino compound may be a commercially available product, such as Irgacure 369 (manufactured by BASF).

  In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph [0079] of JP-A No. 2004-295116 are used in the photosensitive coloring composition of the present invention. Also good.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content of the photopolymerization initiator in the photosensitive coloring composition is 3% by mass to 20% by mass with respect to the total solid content of the photosensitive coloring composition from the viewpoint of obtaining the effect of the present invention more effectively. Preferably, 4 mass%-19 mass% are more preferable, and 5 mass%-18 mass% are especially preferable. When there are two or more photopolymerization initiators, the total is preferably in the above range.

[Alkali-soluble binder]
It is preferable that the photosensitive coloring composition of the present invention contains an alkali-soluble binder. The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

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

  In addition to the above, as the alkali-soluble binder in the present invention, the description in paragraphs 0079 to 0082 of JP2013-182215A can be referred to, and the contents thereof are incorporated in the present specification.

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

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.), Cyclomer P Series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable. A copolymer of benzyl methacrylate / methacrylic acid (85/15 [mass ratio]) is also preferable.

（式（Ｘ）において、Ｒ¹は、水素原子またはメチル基を表し、Ｒ²は炭素数２〜１０のアルキレン基を表し、Ｒ³は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。） Moreover, the alkali-soluble binder may contain a structural unit derived from an ethylenically unsaturated monomer represented by the following formula (X).
Formula (X)

(In Formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group R ² is preferably 2-3. Although the carbon number of the alkyl group of R ³ is 1 to 20, more preferably 1 to 10, alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group.

The alkali-soluble binder 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.

  When the photosensitive coloring composition has an alkali-soluble binder, the content of the alkali-soluble binder in the photosensitive coloring composition is 10% by mass to 80% by mass with respect to the total solid content of the photosensitive coloring composition. It is preferably 20% by mass to 60% by mass. Only one type of alkali-soluble binder may be used, or two or more types may be used. When there are two or more types of alkali-soluble binders, the total is preferably in the above range.

[Crosslinking agent]
By supplementarily using a crosslinking agent in the photosensitive coloring composition of the present invention, the hardness of the colored cured film when the photosensitive coloring composition is cured can be further increased.
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. Of these, polyfunctional epoxy resins are preferred.
For details such as specific examples of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.

[Surfactant]
The photosensitive coloring composition of the present invention may contain a surfactant. The surfactant may be any of nonionic, cationic, or anionic, and a fluorine-containing surfactant is preferable. Specifically, JP-A-2-54202 is exemplified.
As a commercial product, Megafac F781-F (manufactured by Dainippon Ink & Chemicals, Inc.) or the like can be used.
When the photosensitive coloring composition has a surfactant, the content of the surfactant in the photosensitive coloring composition is 0.0001% by mass to 0.5% with respect to the total solid content of the photosensitive coloring composition. Mass% is preferred. Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.

[Organic solvent]
The photosensitive coloring 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.
As an organic solvent, it is synonymous with the organic solvent which may be contained in the said coloring composition, and its preferable range is also the same.

[Other ingredients]
The photosensitive coloring composition of the present invention may further contain various additives such as a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a sensitizer and a light stabilizer, as necessary. .

<Method for preparing photosensitive coloring composition>
The photosensitive coloring composition of this invention is prepared by mixing each component mentioned above and arbitrary components as needed.
In preparing the photosensitive coloring composition, the components constituting the photosensitive coloring composition may be blended together, or may be blended sequentially 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 photosensitive coloring 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 photosensitive coloring composition of the present invention can form a colored cured film having excellent hue and good contrast, it can be used for liquid crystal display devices (LCD) and solid-state imaging devices (for example, CCD, CMOS, etc.). It can be suitably used for forming colored pixels such as a color filter used for printing and for producing printing ink, inkjet ink, paint, and the like. 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 produced using the above-described coloring composition of the present invention or the above-described photosensitive coloring composition of the present invention. For example, the color filter of the present invention is formed on a substrate and a substrate. And a colored region containing the photosensitive coloring composition. 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 can be formed by any method as long as it can form a cured colored region (colored pattern) by applying the colored composition or the photosensitive colored composition of the present invention on a substrate. Preferably, it is manufactured using the photosensitive coloring composition of the present invention.
Moreover, when manufacturing the color filter for solid-state image sensors using the photosensitive coloring composition of this invention, the manufacturing method described in Paragraph [0359]-[0371] of Unexamined-Japanese-Patent No. 2011-252065. Can also be adopted.

In the method for producing a color filter of the present invention, a colored layer (also referred to as a photosensitive colored composition layer) is formed by applying (preferably coating) the above-described colored composition or photosensitive colored composition on a substrate. A coloring layer forming step (hereinafter also referred to as step A) and a step (B) of curing the photosensitive coloring composition layer formed in step (A). In the curing step (B), a pattern is exposed (preferably through a mask) to form a latent image, and an uncured portion of the colored layer after the exposure on which the latent image is formed is developed with a developer. Development step of forming a colored region (colored pattern) by developing and removing.
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 photosensitive coloring composition of the present invention is applied on a substrate directly or via another layer by a desired coating method, and then the photosensitive coloring composition. A coating film (photosensitive coloring composition layer) is formed, and then pre-curing (pre-baking) is performed as necessary, and the photosensitive coloring 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 using the photosensitive coloring 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 photosensitive coloring composition of this invention is applied to a board | 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 photosensitive coloring 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 photosensitive coloring 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.
Moreover, as solid content of the photosensitive coloring composition used at an application | coating process, it is 10%-20% normally, Preferably it is 13%-18%.

When forming the coating film by the photosensitive coloring 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 step A, a pre-bake treatment is usually 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.
Moreover, the thickness of the photosensitive coloring composition layer formed with the photosensitive coloring 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 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 photosensitive coloring composition layer is a film thickness after prebaking.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, the film (photosensitive coloring composition layer) made of the photosensitive coloring 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.

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 photosensitive coloring composition layer exposed as described above can be heated.
The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the photosensitive coloring composition layer.

Subsequently, the photosensitive coloring 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 (photosensitive coloring composition layer) of the photosensitive coloring composition in the uncured portion, but does not dissolve 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 solvents described above that can be used in preparing the photosensitive coloring composition of the present invention.
Examples of the alkaline aqueous solution include tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate, ammonia Alkaline compounds such as water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, An alkaline aqueous solution dissolved so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. 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, post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a photosensitive coloring composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). 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.
In addition, whenever formation, exposure, and development of a monochromatic photosensitive coloring composition layer are completed (for each color), the above-described step (C) and / or step (D) may be performed, or a desired Step (C) and / or step (D) may be performed collectively after the formation, exposure, and development of all the photosensitive coloring composition layers having the number of colors are completed.

  Moreover, the coloring composition of this invention or the photosensitive coloring composition is applicable also to the manufacturing method of a color filter including a dry etching process. As an example of such a production method, a step of forming a colored layer using the photosensitive coloring composition of the present invention, a step of forming a photoresist layer on the colored layer, a photoresist layer by exposing and developing. Examples include a manufacturing method including a step of patterning to obtain a resist pattern and a step of dry etching the colored layer using the resist pattern as an etching mask. When the photosensitive coloring composition of the present invention is used in a method for producing a color filter including a dry etching process, it may be a photocurable composition or a thermosetting composition. In the case of a thermosetting composition, a thermosetting agent can be used. As the thermosetting agent, a compound having two or more epoxy groups in one molecule is preferable.

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

<Liquid crystal display device>
The liquid crystal display element and the solid-state image sensor of the present invention have 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.

<Solid-state imaging device>
The photosensitive coloring composition of this invention can be preferably used also for a solid-state image sensor use. The configuration of the solid-state imaging device is a configuration provided with a color filter manufactured using the photosensitive coloring composition of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. The following configurations are listed.

The substrate has a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc., and the photodiodes are arranged on the photodiodes and the transfer electrodes. It has a light-shielding film made of tungsten or the like that is open only in the light-receiving part, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. In addition, the solid-state image sensor color filter of the present invention is included.
Further, a configuration having a light collecting means (for example, a micro lens, etc., the same applies hereinafter) on the device protective layer and below the color filter (on the side close to the support), a structure having the light collecting means on the color filter, etc. It may be.

  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.

-Exemplified Compound No. Synthesis of 1

In a dimethylformamide solution of the raw material M-1 (4 parts by mass) and the raw material M-2 (7 parts by mass), the mixture is cooled to 10 ° C. or less, and triethylamine (1.2 parts by mass) is added dropwise. Reacted for hours. The reaction solution was extracted with ethyl acetate (200 parts by mass) and 1N hydrochloric acid (200 parts by mass). The organic layer was separated, concentrated, and purified by silica gel chromatography to obtain 10 parts by mass of raw material M-3.
Subsequently, the obtained raw material M-3 (10 parts by mass), tetrachlorophthalonitrile (8 parts by mass), zinc acetate (4 parts by mass), n-pentanol (100 parts by mass), diazabicycloundecene (DBU) ) (1 part by mass) of the reaction solution at 100 ° C. for 6 hours, taken out, and purified by silica gel chromatography (eluent, ethyl acetate) to obtain 2.4 parts by mass of the target compound No. 1. It was.

Example 1
<Production of green film>
-Preparation of photosensitive coloring composition (coating liquid) 101-
The component in the following composition was mixed and the photosensitive coloring composition 101 was prepared.

<Composition>
-Compound represented by the general formula (1) ... 32.4 parts-The following (T-1) ... 54 parts by mass-The following (U-1 ) ... 135.5 parts by mass (solid content conversion value: 54.2 parts by mass)
・ The following (V-3) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9 parts by mass ・ The following (X-1) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 493 parts by mass ・ The following (X -2) ················ 246 parts by mass · Following (Z-1) ·········· 0.18 parts by mass

-Preparation of photosensitive coloring composition (coating liquid) 102-104-
The photosensitive coloring composition (coating liquid) 102 was a yellow colored product (Y-3) except that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) was in an amount within the range of 0.95 to 1.05. Was prepared in the same manner as the photosensitive coloring composition 101 described above.
The photosensitive coloring composition (coating liquid) 103 comprises a cyan dye (C-1) and a yellow dye (Y-3), with an absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) of 0.95 to 1.05. It was prepared in the same manner as the photosensitive coloring composition 101 except that an amount falling within the above range was added.
The photosensitive coloring composition (coating liquid) 104 was prepared in the same manner as the photosensitive coloring composition 101 except that 32.4 parts of a cyan dye (C-2) was added.

Below, the detail of each component used for preparation of the photosensitive coloring composition is shown.
(T-1) Polymerizable compound: Kayalad DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
(U-1) Binder resin: benzyl methacrylate / methacrylic acid (85/15 [mass ratio] copolymer (weight average molecular weight: 12,000) in propylene glycol monomethyl ether acetate solution (solid content: 40.0 mass%) Value (100mgKOH / g)

(V-3) Photopolymerization initiator: an oxime compound having the following structure (Et represents an ethyl group, and Ac represents an acetyl group)

(X-1) Solvent: Propylene glycol monomethyl ether acetate (X-2) Solvent: Ethyl 3-ethoxypropionate (Z-1) Surfactant: Megafac F781-F (manufactured by Dainippon Ink & Chemicals, Inc.)
(Y-3) 10.0 parts of the following yellow dye dissolved in 90.0 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.)

(C-1) Phthalocyanine dye (described in WO2011 / 105603)

(C-2) Cyan dye (Et represents an ethyl group)

<Evaluation>
[Light resistance]
The photosensitive coloring composition prepared above is applied onto a glass substrate using a spin coater so that the film thickness (after pre-baking) is 2.0 μm, and pre-baked at 80 ° C. for 120 seconds to form a colored layer. Formed. Then, the glass substrate on which the colored layer was formed was irradiated with 200,000 lux for 10 hours (equivalent to 2 million lux · h) using a xenon lamp. Thereafter, using a chromaticity meter (MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.), the chromaticity change in the colored layer before and after irradiation, that is, ΔE ^* ab value was measured. The obtained ΔE ^* ab value was used as an index indicating the degree of light resistance and evaluated based on the following evaluation criteria. A smaller ΔE ^* ab value indicates better light resistance.
-Evaluation criteria-
A: ΔE ^* ab value was 5 or less.
B: The ΔE ^* ab value was more than 5 and less than 10.
C: The ΔE ^* ab value was 10 or more.

[Heat-resistant]
The photosensitive coloring composition prepared above is applied onto a glass substrate using a spin coater so that the film thickness (after pre-baking) is 2.0 μm, and pre-baked at 80 ° C. for 120 seconds to form a colored layer. Formed. And the glass substrate in which the colored layer was formed was put into the heated oven, and it heated at the preset temperature of 230 degreeC for 1 hour. Thereafter, using a chromaticity meter (MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.), the chromaticity change in the colored layer before and after heating, that is, ΔE ^* ab value was measured. The obtained ΔE ^* ab value was used as an index indicating the degree of heat resistance and evaluated based on the following evaluation criteria. A smaller ΔE ^* ab value indicates better heat resistance.
-Evaluation criteria-
A: ΔE ^* ab value was 5 or less.
B: The ΔE ^* ab value was more than 5 and less than 10.
C: The ΔE ^* ab value was 10 or more.

[Stability over time]
The coating solution is allowed to stand at 5 ° C. for 2 weeks, and the photosensitive coloring composition after the lapse of 2 weeks is applied on a glass substrate using a spin coater so that the film thickness (after pre-baking) is 2.0 μm. Then, a colored layer was formed by pre-baking at 80 ° C. for 120 seconds. The surface state of the colored film was visually observed and evaluated according to the following evaluation criteria. In the sample having low storage stability when time passes, the phthalocyanine compound precipitates over time, which causes generation of “pops”.
-Evaluation criteria-
A: No irregularities are observed on the coating film.
B: No irregularities are observed on the coating film, but turbidity (roughness) is visible.
C: Unevenness is observed on the coating film.

As shown in Table 1, the light resistance and heat resistance of the examples containing the compound represented by the general formula (I) are improved compared to the comparative example not containing the compound represented by the general formula (I). It was excellent in stability over time.
The photosensitive coloring composition 101 containing only the compound represented by the general formula (I) is a compound other than the compound represented by the general formula (I) and the compound represented by the general formula (I). It turns out that light resistance and temporal stability are more excellent than the photosensitive coloring composition 102 containing a dye.

(Example 2)
A photosensitive coloring composition 101 is applied by spin coating on glass (# 1737; made by Corning Inc.), and then a volatile component is volatilized at 100 ° C. for 3 minutes to form a coloring composition. A material film was formed. After cooling, the colored composition film was exposed to i-line (wavelength 365 nm) for exposure. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 500 mJ / cm ² . Next, post baking was performed at 180 ° C. for 20 minutes to obtain a green composition film 201 having a thickness of 2 μm. Using a microspectrophotometer OSP-SP200 manufactured by Olympus Corporation and measuring the chromaticity with a C light source, x = 0.30 and y = 0.57.

  In addition, except that the ratio of the compound represented by the general formula (1) and the yellow colored substance (Y-3) was adjusted to x = 0.30 and y = 0.57, the green composition film 201 and Similarly, a green composition film 202 was obtained.

  In addition, green composition films 301 and 302 were obtained in the same manner as the green composition film 201 except that the photosensitive coloring compositions 103 to 104 were used as comparative examples.

<Evaluation>
[contrast]
When the green composition film is sandwiched between two polarizing films, the luminance value when the polarization axes of the two polarizing films are parallel and perpendicular is measured using a color luminance meter (manufactured by Topcon Corporation, model number: BM-5A) was measured, and the brightness when the polarization axes of the two polarizing films were parallel was divided by the brightness when vertical, and the obtained value was obtained as contrast.
The higher the contrast, the better the performance as a color filter for a liquid crystal display.

[Luminance]
The luminance was measured using a microspectrophotometer OSP-SP200 manufactured by Olympus Corporation and evaluated based on the Y value. The higher the Y value, the better the performance as a color filter for a liquid crystal display.

As shown in Table 2, the Example using the photosensitive coloring composition of the present invention has a higher Y value (luminance) and excellent color purity than the Comparative Example not using the photosensitive coloring composition of the present invention. The hue was also good and an excellent contrast was obtained.
Moreover, the composition film | membrane 201 using the photosensitive coloring composition 101 containing only the compound represented by general formula (I) is represented by the compound represented by general formula (I), and general formula (I). It can be seen that the contrast and the luminance are superior to those of the composition film 202 using the photosensitive coloring composition 102 containing a dye other than the above compound.

Claims (14)

The coloring composition containing the compound represented by the following general formula (I).

(In general formula (I), P represents a phthalocyanine moiety, M represents a methine moiety, L represents a single bond or a linking group, and n represents an integer of 1 to 16.) The coloring composition according to claim 1, wherein the general formula (I) is represented by the following general formula (1).

(In General Formula (1), each X independently represents a halogen atom. Each R independently represents a hydrogen atom or a monovalent substituent. However, among R, n represents -L-. M represents Ma, Cu, Zn, V (═O), Mg, Ni, Ti (═O), Sn, or Si, each m independently represents an integer of 0 to 4; Each independently represents an integer of 0 to 4. However, at least one of the plurality of n is 1 or more, and the sum of the plurality of m and the plurality of r is 16.) The coloring composition according to claim 1 or 2 in which general formula (I) is denoted by the following general formula (7).

(In General Formula (7), R ¹ and R ² each independently represent a tertiary alkyl group that may have a substituent, or an aryl group that may have a substituent, and R ³ represents a hydrogen atom. , A halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, Z ¹ and Z ² each independently form a 5-membered ring or a 6-membered ring. R ⁴ and R ⁵ each independently represents a substituent, and n 1 and n 2 are each independently an integer of 0 to 2, provided that R ^{1 to} R ⁵ At least one is -LP- (LM) _n-1 .) R ⁴ or R ⁵ in the general formula (7), -L-P- a _{(L-M) n-1} , the coloring composition of claim 3. The coloring composition according to any one of claims 1 to 4, wherein the general formula (I) is represented by the general formula (7 ').
General formula (7 ')

(In the general formula (7 ′), R ¹ and R ² each independently represent a tertiary alkyl group which may have a substituent or an aryl group which may have a substituent, and Za and Zb are Each independently represents a nitrogen atom or —C (R ⁷ ) —, R ⁷ represents a hydrogen atom or a substituent, and Zd and Ze each independently represent a nitrogen atom or —C (R ⁷ ) —. R ⁷ represents a hydrogen atom or a substituent, R ⁴ and R ⁵ each independently represents a substituent, and n1 and n2 are integers of 0 to 2, provided that R ^{1 to} R ² , R ^{4 to} R ⁵ is -LP- (LM) _n-1 .) The coloring composition according to any one of claims 1 to 5, wherein L in the general formula (I) is a linking group selected from the following group A or a linking group obtained by combining these linking groups.
Group A

The coloring composition according to claim 6, wherein L in the general formula (I) is represented by the following general formula (2).
General formula (2)

(In General Formula (2), L ¹ represents an oxygen atom or a sulfur atom, and L ² represents a linking group selected from Group A or a linking group formed by combining these linking groups. , P represents a binding site, and ** represents a binding site to M.) The coloring composition of any one of Claims 1-7 in which L in general formula (I) has a sulfonamide group. The coloring composition of any one of Claims 1-8 in which n in general formula (I) represents the integer of 1-4. The photosensitive coloring composition which has a coloring composition of any one of Claims 1-9, a polymeric compound, and a photoinitiator. The photosensitive coloring composition of Claim 10 whose photoinitiator is an oxime type compound or a biimidazole type compound. The color filter which has a colored layer using the coloring composition of any one of Claims 1-9, or the photosensitive coloring composition of Claim 10 or 11. The coloring composition according to any one of claims 1 to 9, or the photosensitive coloring composition according to claim 10 or 11, is applied on a substrate to form a colored layer, and A step of exposing the colored layer in a pattern and developing to form a colored region. A liquid crystal display device, an organic electroluminescence element, or a solid-state imaging device having the color filter according to claim 12 or the color filter produced by the method for producing a color filter according to claim 13.