JP2010085454A - Colored curable composition, color filter and method of producing the same, and pigment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition in a color from magenta to violet useful for a color filter and having excellent color purity, a high absorption coefficient and excellent pattern forming property. <P>SOLUTION: The colored curable composition includes at least one of compounds expressed by general formula (A) or (B) or tautomers thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored curable composition, a color filter, a method for producing the same, and a dye, and particularly contains a dye suitable for forming a color filter used for a liquid crystal display element or a solid-state imaging element, and the dye. The present invention relates to a colored curable composition, a color filter using the colored curable composition, and a method for producing the same.

  A pigment dispersion method is used as one of methods for producing a color filter used for a liquid crystal display device, a solid-state imaging device, or the like. There is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions by a pigment dispersion method. This method is stable against light and heat due to the use of pigments, and can be secured with sufficient positional accuracy because it is patterned by photolithography, making it suitable for the production of color filters for large screens and high-definition color displays. It has been widely used as a new method.

  In order to produce a color filter by the pigment dispersion method, a radiation-sensitive composition is applied on a substrate with a spin coater, a roll coater or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development. To obtain a colored pixel. By repeating this operation for the hue, a color filter can be produced.

  However, in recent years, color filters for solid-state imaging devices have been desired to have higher definition, and it is difficult to further improve resolution with conventional pigment dispersion systems, and color unevenness due to coarse pigment particles is difficult. Because of the problems such as the occurrence of the above, it is not suitable for applications requiring a fine pattern such as a solid-state imaging device.

In order to achieve the above high resolution, the use of a dye as a coloring material has been conventionally studied (for example, see Patent Document 1). However, the dye-containing curable composition has the following new problems.
(1) Dyes are generally inferior in light resistance and heat resistance compared to pigments.
(2) Since ordinary dyes have low solubility in an alkaline aqueous solution or an organic solvent (hereinafter also simply referred to as a solvent), it is difficult to obtain a liquid curable composition having a desired spectrum.
(3) The dye often exhibits an interaction with other components in the curable composition, and it is difficult to adjust the solubility (developability) of the cured part and the non-cured part.
(4) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added. For that purpose, the polymerizable compound (monomer), binder, photopolymerization initiator, etc. in the curable composition Other components must be reduced, and the curability of the composition, the heat resistance after curing, the developability of the (non-) cured portion, and the like are reduced.

  Because of these problems, it has heretofore been difficult to form a fine and thin colored pattern for a high-definition color filter. In addition, unlike a semiconductor manufacturing application or the like, in the case of a color filter manufacturing application for a solid-state imaging device, a thin film of 1 μm or less is required. Therefore, in order to obtain a desired absorption, it is necessary to add a large amount of a dye in the curable composition, resulting in the above-mentioned problems.

  In addition, colorants generally used for various purposes are required to have the following properties in common. That is, it has favorable absorption characteristics in terms of color reproducibility, fastness under the environmental conditions used, for example, good heat resistance, light resistance, moisture resistance, etc., has a large molar extinction coefficient and can be thinned. That is needed.

  For example, a dipyrromethene metal complex has a high molar extinction coefficient and favorable absorption characteristics in terms of color reproducibility (see Patent Document 2).

  On the other hand, particularly in the color filter of a solid-state imaging device, fine pattern formation is required, and it is difficult to adjust the solubility (developability) of the cured part and the non-cured part. In particular, exposure is performed through a fine pattern mask, followed by development with an alkali solution, and an unexposed portion is dissolved in an alkali developer to form a fine pattern. If the colored curable composition has poor solubility in an alkaline developer, the pattern formability deteriorates (colored matter remains in the unexposed area). In particular, a colored curable composition having a small concentration dependency of the alkaline liquid is required.

JP-A-6-75375 US Patent Application Publication No. 2008 / 0076044A1

The present invention is useful for primary color filters arranged in blue, green, and red, has a high light absorption coefficient that is excellent in color purity, can be thinned, and is excellent in pattern formation. An object of the present invention is to provide a colored curable composition.
Furthermore, the present invention provides a magenta to violet color filter that uses a colored curable composition, has excellent color purity, can be thinned, and has excellent fastness, and a method for producing the same. Objective.
Furthermore, the present invention provides a dye (pyromethene metal complex) that is useful for colored curable compositions useful for color filters and the like, has excellent absorption characteristics, has a high molar absorption coefficient, and can impart developability. With the goal.

As a result of detailed examination of various dyes, the present inventors have found that a dipyrromethene metal complex compound having a specific substituent has a good hue and a high extinction coefficient, is excellent in fastness, and is soluble in organic solvents. The present inventors have obtained knowledge that they are excellent and have excellent pattern formability (low concentration dependency of alkali developer), and the present invention has been achieved based on such knowledge.
Specific means for solving the above-described problems are as follows.

（式中、Ｒ_１〜Ｒ_６は各々独立に、水素原子、又は置換基を表し、Ｒ_７は、水素原子、ハロゲン原子、アルキル基、アリール基、又はヘテロ環基を表す。但し、Ｒ_１〜Ｒ_６のいずれかの置換基が２価の連結基となって、−（Ｌ）−ＳＯ_３ ⁻、又は−（Ｌ）−ＳＯ_３Ｍと結合している。Ｍは水素原子、又は電荷を中和するために必要な有機塩基又は金属原子を表す。Ｌは、アルキレン基、アラルキレン基、アリーレン基、又は、アルキレン基、アラルキレン基、アリーレン基、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｎ（Ｒａ）−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（Ｒｂ）−、−Ｎ（Ｒｂ）ＣＯ−、−Ｎ（Ｒｂ）ＣＯＯ−、−ＯＯＣＮ（Ｒｂ）−、−Ｎ（Ｒｂ）ＣＯＮ（Ｒｃ）−、−ＳＯ_２Ｎ（Ｒｂ）−、及び−Ｎ（Ｒｂ）ＳＯ_２−の群から選ばれる２価の基との組み合わせにより形成が可能な２価の基を表す。Ｒａは、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルスルホニル基、又はアリールスルホニル基を表し、Ｒｂ及びＲｃは、各々独立に、水素原子、アルキル基、アルケニル基、アリール基、又はヘテロ環基を表す。
Ｍａは、錯体を形成可能な金属、又は金属化合物を表す。Ｘ_１は、Ｍａの電荷を中和する為に必要な基を表し、Ｘ_２はＭａに結合可能な基を表す。ｐは０又は１を表す。一般式（Ｂ）において、Ｘ_１とＸ_２は、互いに結合して５員、６員、又は７員の環を形成していてもよい。）
＜２＞ 前記一般式（Ａ）が下記一般式（１−Ａ）であり、前記一般式（Ｂ）が下記一般式（１−Ｂ）であることを特徴とする＜１＞に記載の着色硬化性組成物。

（式中、Ｒ_２〜Ｒ_５は、各々独立に、水素原子、又は置換基を表す。Ｒ_７は、水素原子、ハロゲン原子、アルキル基、アリール基、又はヘテロ環基を表す。Ｒ_８及びＲ_９は、各々独立に、アルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アミノ基、アニリノ基、又はヘテロ環アミノ基を表す。但し、Ｒ_２〜Ｒ_５、Ｒ_８、及びＲ_９のいずれかの置換基が２価の連結基となって、−（Ｌ）−ＳＯ_３ ⁻、又は−（Ｌ）−ＳＯ_３Ｍが結合している。Ｍは水素原子、又は電荷を中和するために必要な有機塩基又は金属原子を表す。Ｌは、アルキレン基、アラルキレン基、アリーレン基、又は、アルキレン基、アラルキレン基、アリーレン基、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｎ（Ｒａ）−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（Ｒｂ）−、−Ｎ（Ｒｂ）ＣＯ−、−Ｎ（Ｒｂ）ＣＯＯ−、−ＯＯＣＮ（Ｒｂ）−、−Ｎ（Ｒｂ）ＣＯＮ（Ｒｃ）−、−ＳＯ_２Ｎ（Ｒｂ）−、及び−Ｎ（Ｒｂ）ＳＯ_２−の群から選ばれる２価の基との組み合わせにより形成が可能な２価の基を表す。Ｒａは、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルスルホニル基、又はアリールスルホニル基を表し、Ｒｂ及びＲｃは、各々独立に、水素原子、アルキル基、アルケニル基、アリール基、又はヘテロ環基を表す。
Ｍａは、錯体を形成可能な金属、又は金属化合物を表し、Ｘ₁は、Ｍａの電荷を中和する為に必要な基を表す。Ｘ_３及びＸ_４は、各々独立に、ＮＲ（Ｒは水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルスルホニル基、又はアリールスルホニル基を表す。ＲとＲ_８又はＲ_９とが互いに結合して５員、６員、又は７員の環を形成してもよい。）、酸素原子、又は硫黄原子を表し、Ｙ_１及びＹ_２は各々独立に、ＮＲ（Ｒは、水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルスルホニル基、又はアリールスルホニル基）、又は酸素原子を表し、Ｒ_８とＹ_１は、互いに結合して、５員、６員、又は７員の環を形成していてもよく、Ｒ_９とＹ_２とが互いに結合して５員、６員、又は７員の環を形成していてもよい。）
＜３＞ 前記Ｍａが、Ｆｅ、Ｚｎ、Ｃｏ、Ｖ＝Ｏ、又はＣｕであることを特徴とする＜１＞又は＜２＞に記載の着色硬化性組成物。
＜４＞ 前記Ｍａが、Ｚｎであることを特徴とする＜１＞〜＜３＞のいずれかに記載の着色硬化性組成物。
＜５＞ 下記一般式（Ｃ）で表される化合物、下記一般式（Ｄ）で表される化合物、及びそれらの互変異性体からなる群から選択される少なくとも１種を含有することを特徴とする着色硬化性組成物。

（式中、Ｒ_２〜Ｒ_５は、各々独立に、水素原子、又は置換基を表す。Ｒ_７は、水素原子、ハロゲン原子、アルキル基、アリール基、又はヘテロ環基を表す。Ｒ_１０及びＲ_１１は、各々独立に、アルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アミノ基、アニリノ基、又はヘテロ環アミノ基を表す。但し、Ｒ_２〜Ｒ_５、Ｒ_１０、及びＲ_１１のいずれかの置換基が２価の連結基となって、−（Ｌ）−ＳＯ_３ ⁻、又は−（Ｌ）−ＳＯ_３Ｍが結合している。Ｍは水素原子、又は電荷を中和するために必要な有機塩基又は金属原子を表す。Ｌは、アルキレン基、アラルキレン基、アリーレン基、又は、アルキレン基、アラルキレン基、アリーレン基、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｎ（Ｒａ）−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（Ｒｂ）−、−Ｎ（Ｒｂ）ＣＯ−、−Ｎ（Ｒｂ）ＣＯＯ−、−ＯＯＣＮ（Ｒｂ）−、−Ｎ（Ｒｂ）ＣＯＮ（Ｒｃ）−、−ＳＯ_２Ｎ（Ｒｂ）−、及び−Ｎ（Ｒｂ）ＳＯ_２−の群から選ばれる２価の基との組み合わせにより形成が可能な２価の基を表す。Ｒａは、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルスルホニル基、又はアリールスルホニル基を表し、Ｒｂ及びＲｃは、各々独立に、水素原子、アルキル基、アルケニル基、アリール基、又はヘテロ環基を表す。Ｘ₁は、Ｚｎの電荷を中和する為に必要な基を表す。）
＜６＞ ＜１＞〜＜５＞のいずれかに記載の着色硬化性組成物を含むカラーフィルタ。
＜７＞ ＜１＞〜＜５＞のいずれかに記載の着色硬化性組成物を支持体上に塗布して層を形成する工程と、
前記支持体上に形成した着色硬化性組成物の層に対し、マスクを介して露光した後、現像してパターン像を形成する工程と、
を含むことを特徴とするカラーフィルタの製造方法。
＜８＞ 前記一般式（Ｃ）で表される化合物、前記一般式（Ｄ）で表される化合物、及びそれらの互変異性体からなる群から選択される色素。 <1> It contains at least one selected from the group consisting of a compound represented by the following general formula (A), a compound represented by the following general formula (B), and their tautomers. A colored curable composition.

(In the formula, R _{1 to} R ₆ each independently represents a hydrogen atom or a substituent, and R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, provided that R ₁ represents R _1. To R ₆ , which is a divalent linking group and bonded to — (L) —SO ₃ ^— or — (L) —SO ₃ M. M is a hydrogen atom or a charge .L represents an organic base or metal atom required to neutralize the represents an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, -O -, - S -, - SO 2 -, -N (Ra)-, -COO-, -OCO-, -CON (Rb)-, -N (Rb) CO-, -N (Rb) COO-, -OOCN (Rb)-, -N ( Rb) CON (Rc) -, - SO 2 N (Rb) -, and -N (Rb) SO ₂ - Represents a divalent group that can be formed by combining with a divalent group selected from the group, wherein Ra represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; Rb and Rc each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
Ma represents a metal or a metal compound capable of forming a complex. X ₁ represents a group necessary for neutralizing the charge of Ma, and X ₂ represents a group capable of binding to Ma. p represents 0 or 1; In the general formula (B), X ₁ and X ₂ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. )
<2> The coloring according to <1>, wherein the general formula (A) is the following general formula (1-A), and the general formula (B) is the following general formula (1-B). Curable composition.

(Wherein R _{2 to} R ₅ each independently represents a hydrogen atom or a substituent. R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₈ and R ₉ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group, provided that R _{2 to} R ₅ , A substituent of any one of R ₈ and R ₉ is a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M is bonded, where M is a hydrogen atom. Or an organic base or a metal atom necessary for neutralizing the charge, L is an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, -O-, -S-, _{-SO 2 -, - N (Ra} ) -, - C O -, - OCO -, - CON (Rb) -, - N (Rb) CO -, - N (Rb) COO -, - OOCN (Rb) -, - N (Rb) CON (Rc) -, - SO ₂ N (Rb) -, and -N (Rb) SO ₂ - .Ra representing a divalent combinable formed by a divalent group with group selected from the group consisting of an alkyl group, an alkenyl group, an aryl Represents a group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
Ma represents a metal or a metal compound capable of forming a complex, and X ₁ represents a group necessary for neutralizing the charge of Ma. X ₃ and X ₄ each independently represent NR (where R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. R and R ₈ or R ₉ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring), an oxygen atom, or a sulfur atom, and Y ₁ and Y ₂ are each independently NR (R Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or an oxygen atom, and R ₈ and Y ₁ are bonded to each other to represent 5 A 6-membered, 6-membered or 7-membered ring may be formed, and R ₉ and Y ₂ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. )
<3> The colored curable composition according to <1> or <2>, wherein Ma is Fe, Zn, Co, V═O, or Cu.
<4> The colored curable composition according to any one of <1> to <3>, wherein Ma is Zn.
<5> It contains at least one selected from the group consisting of a compound represented by the following general formula (C), a compound represented by the following general formula (D), and their tautomers. A colored curable composition.

(In the formula, R _{2 to} R ₅ each independently represents a hydrogen atom or a substituent. R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₁₀ and R ₁₁ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group, provided that R _{2 to} R ₅ , A substituent of any one of R ₁₀ and R ₁₁ becomes a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M is bonded, where M is a hydrogen atom. Or an organic base or metal atom necessary for neutralizing the charge, L is an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, -O-, -S-, _{-SO 2 -, - N (Ra} ) , -COO-, -OCO-, -CON (Rb)-, -N (Rb) CO-, -N (Rb) COO-, -OOCN (Rb)-, -N (Rb) CON (Rc)-, A divalent group that can be formed by a combination with a divalent group selected from the group of —SO ₂ N (Rb) — and —N (Rb) SO ₂ —, wherein Ra represents an alkyl group or an alkenyl group; , An aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. X ₁ represents a group necessary for neutralizing the charge of Zn.)
<6> A color filter comprising the colored curable composition according to any one of <1> to <5>.
<7> A step of coating the colored curable composition according to any one of <1> to <5> on a support to form a layer;
A step of forming a pattern image by exposing the layer of the colored curable composition formed on the support through a mask and developing the layer;
A method for producing a color filter, comprising:
<8> A dye selected from the group consisting of the compound represented by the general formula (C), the compound represented by the general formula (D), and tautomers thereof.

According to the present invention, it is useful for primary color filters arranged in blue, green and red, has excellent color purity, has a high extinction coefficient that can be thinned, has excellent fastness, and is soluble in organic solvents. And a colored curable composition containing a dipyrromethene metal complex having a specific substituent that has a small dependency on the concentration of an alkali developer and excellent pattern formation.
In addition, according to the present invention, it is possible to provide a color filter excellent in color purity, capable of being thinned, excellent in fastness, and having high resolution, and a method for manufacturing the same.

  Below, the coloring curable composition of this invention, a color filter, and the manufacturing method of a color filter are explained in full detail.

-Colored curable composition-
The colored curable composition of the present invention is selected from the group consisting of a compound represented by the following general formula (A), a compound represented by the following general formula (B), and a tautomer thereof as a colorant. Containing at least one of the above. UV-sensitive colored curable compositions are preferred.

In General Formula (A) and General Formula (B), R _{1 to} R ₆ each independently represent a hydrogen atom or a substituent, and R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or hetero. Represents a cyclic group. However, any substituent of R _{1 to} R ₆ is a divalent linking group, and is bonded to — (L) —SO ₃ ^— or — (L) —SO ₃ M. M represents a hydrogen atom or an organic base or metal atom necessary for neutralizing the electric charge. L represents an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO ₂ —, —N (Ra) —, —COO—, —OCO—. , -CON (Rb) -, - N (Rb) CO -, - N (Rb) COO -, - OOCN (Rb) -, - N (Rb) CON (Rc) -, - SO 2 N (Rb) - And a divalent group that can be formed by a combination with a divalent group selected from the group of —N (Rb) SO ₂ —. Ra represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. Or a heterocyclic group.
Ma represents a metal or a metal compound capable of forming a complex. X ₁ represents a group necessary for neutralizing the charge of Ma, and X ₂ represents a group capable of binding to Ma. p represents 0 or 1; In the general formula (B), X ₁ and X ₂ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.

The compounds represented by general formula (A) and general formula (B) will be described in detail.
Is either a divalent linking group of the substituents of _{R 1 ~R 6, - (L} ) -SO 3 - or, - (L) is SO ₃ M is bonded, the _R 1 to R ₆ for a description of any divalent _{group, - (L) -SO 3 -} , and - (L) -SO ₃ M hydrogen atom instead of being expressed by those substituted.

R _{1 to} R ₆ in the general formula (A) and the general formula (B) each independently represent a hydrogen atom or a substituent. Examples of the substituent for R _{1 to} R ₆ include a halogen atom (for example, Fluorine, chlorine, bromine), an alkyl group (preferably a C1-C48, more preferably a C1-C24 linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl) , Butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably having 2 to 48 carbon atoms, More preferably, it is an alkenyl group having 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably Is an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenyl or naphthyl, or a heterocyclic group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic ring having 1 to 18 carbon atoms). Groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), silyl groups (preferably A silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, , Methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy group, for example, cyclopentyloxy, cyclohexyloxy), aryloxy group (preferably having 6 to 48 carbon atoms, More preferably, it is an aryloxy group having 6 to 24 carbon atoms, such as phenoxy or 1-naphthoxy, and a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms). For example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t -Butyldimethylsilyloxy, diphenylmethylsilyloxy) An acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 2 carbon atoms). 48, more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as an ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group, such as cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (Preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably Or a carbamoyloxy group having 1 to 24 carbon atoms such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), sulfamoyloxy A group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy),

An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), an arylsulfonyloxy group (preferably Is an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably 1 to 48 carbon atoms, more preferably an acyl having 1 to 24 carbon atoms). Groups such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), alkoxycarbonyl groups (preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms, Methoxycarbonyl, D Xyloxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 24 carbon atoms) An aryloxycarbonyl group such as phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl -N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably having 3 carbon atoms) Hereinafter, more preferably an amino group having 24 or less carbon atoms, for example, amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino group (preferably having 6 carbon atoms). -32, more preferably 6-24 anilino groups, for example, anilino, N-methylanilino), heterocyclic amino groups (preferably C1-C32, more preferably 1-18 heterocyclic amino groups, 4-pyridylamino), a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamido, benzamido, tetradecanamido, pivaloylamido, cyclohexaneamido), ureido group (preferably Uray having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms Group, for example, ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as N-succinimide, N -Phthalimide), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxy Carbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), sulfonamide group Preferably it is a C1-C48, more preferably C1-C24 sulfonamide group, for example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (Preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), An azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms, for example, phenylazo, 3-pyrazolylazo), an alkylthio group (preferably having 1 to 48 carbon atoms, more preferably a carbon number); 1 to 24 alkylthio groups such as methylthio, ethylthio, octylthio , Cyclohexyl thio),

An arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms such as phenylthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). A heterocyclic thio group of, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms) A sulfinyl group such as dodecanesulfinyl), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably an arylsulfinyl group having 6 to 24 carbon atoms such as phenylsulfinyl), an alkylsulfonyl group (preferably having a carbon number) 1 to 48, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, For example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl groups (preferably having 6 to 48 carbon atoms, more preferably carbon numbers) An arylsulfonyl group having 6 to 24, for example, phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N- Dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably A phosphonyl group having 1 to 32 prime atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, and more preferably Is a phosphinoylamino group having 1 to 24 carbon atoms and represents, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

When the substituents of R _{1 to} R _{6 in} the general formula (A) and the general formula (B) are further substitutable groups, they are substituted with the groups described for the substituents of R _{1 to} R _6. If it is substituted with two or more substituents, these substituents may be the same or different. However, any substituent of R _{1 to} R ₆ is a divalent linking group, and is bonded to — (L) —SO ₃ ^— or — (L) —SO ₃ M.

When the substituents R _{1 to} R ₆ are divalent linking groups, a plurality of substituents may be linked to each other to form a new divalent linking group, such as an alkylene group or an aralkylene group. , Arylene group, divalent heterocyclic group, —O—, —S—, —C (═O) O—, —OC (═O) —, —C (═O) —, —OC (═O) N (Rd)-, -C (= O) N (Rd)-, -N (Rd) C (= O)-, -N (Rd) C (= O) O-, -N (Rd) C ( = O) N (Re) - , - C (= o) N (Rd) C (= O) -, - SO -, - SO 2 -, - SO 3 -, - SO 2 N (Rd) -, - N (Rd) SO ₂ —, —C (═O) N (Rd) SO ₂ —, —SO ₂ N (Rd) SO ₂ — and the like are combined to form a new divalent linkage. A group may be formed.

Rd and Re represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an alkyl group sulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, and the like. A group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an alkyl group sulfonyl group, an arylsulfonyl group, a carbamoyl group, and a sulfamoyl group may be substituted with the groups described above for the substituents of R _{1 to} R ₆ ; When substituted with two or more substituents, these substituents may be the same or different.

R _{7 in} general formula (A) and general formula (B) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the halogen atom, alkyl group, aryl group, or heterocyclic ring of R ₇ The group is synonymous with the halogen atom, the alkyl group, the aryl group, and the heterocyclic group described for the substituents of R _{1 to} R ₆ , and the preferred range is also the same.

M in the general formulas (A) and (B) represents a hydrogen atom or an organic base or metal atom necessary for neutralizing the charge. Examples of the organic base include alkylamines, anilines, 4 Secondary amines, guanidines, pyridines, quinolines and the like are preferable, and the metal is preferably an alkali metal. Ammonia is also preferred. M is most preferably a hydrogen atom.

The L in the general formula (A) or Formula (B), an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, -O -, - S -, - SO 2 -, - N (Ra)-, -COO-, -OCO-, -CON (Rb)-, -N (Rb) CO-, -N (Rb) COO-, -OOCN (Rb)-, -N (Rb) CON _{(Rc) -, - SO 2} N (Rb) -, - represents a divalent combination allows formation by a divalent group with a group selected from the group of - N (Rb) SO _2. Ra represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. Represents a heterocyclic group.

The alkylene group of L is preferably a linear, branched, or cyclic alkylene group having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, such as methylene, ethylene, propylene, butylene, Examples include cyclopropylene, cyclobutylene, and cyclohexylene. The aralkylene group of L is preferably an aralkylene group having 7 to 18 carbon atoms, more preferably 7 to 16 carbon atoms, and examples thereof include benzylene and phenethylene. The arylene group of L is preferably an arylene group having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and examples thereof include o-phenylene, m-phenylene, p-phenylene, 1,4-naphthylene and the like. If the alkylene group, aralkylene group, and arylene group of L can be further substituted, they may be substituted with the groups described for the substituents of R _{1 to} R ₆ , and may be substituted with two or more substituents. The substituents may be the same or different.

L is also an alkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO ₂ —, —N (Ra) —, —COO—, —OCO—, —CON (Rb) —, —N. (Rb) CO -, - N (Rb) COO -, - OOCN (Rb) -, - N (Rb) CON (Rc) -, - SO 2 N (Rb) -, and -N (Rb) SO ₂ - A divalent group formed by a combination with a divalent group selected from the group may be formed. _{However, -O -, - S -,} - SO 2 -, - N (Ra) -, - COO -, - OCO -, - CON (Rb) -, - N (Rb) CO -, - N (Rb) COO—, —OOCN (Rb) —, —N (Rb) CON (Rc) —, —SO ₂ N (Rb) —, or —N (Rb) SO ₂ — directly represents —SO ₃ ^— or — The SO ₃ M group is not bonded, and —SO ₃ ^— or —SO ₃ M is bonded via an alkylene group, an aralkylene group, or an arylene group.

The alkyl group, alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group of Ra are the alkyl group, alkenyl group, and aryl group described above for the substituents of R _{1 to} R _6. , A heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and a preferred range is also the same.
When an alkyl group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group of Ra is a substitutable group, the above-described substituents for R _{1 to} R ₆ are used. In the case where it is substituted with two or more substituents, these substituents may be the same or different.

The alkyl group, alkenyl group, aryl group, and heterocyclic group of Rb have the same meanings as the alkyl group, alkenyl group, aryl group, and heterocyclic group described for the substituents of R _{1 to} R ₆ , and the preferred ranges are also the same. is there.
When Rb is an alkyl group, alkenyl group, aryl group or heterocyclic group-substitutable group, it may be substituted with the group described for the substituents of R _{1 to} R ₆ and two or more substituents may be substituted. When substituted with a group, the substituents may be the same or different.

Ma in the general formula (A) and the general formula (B) represents a metal or a metal compound capable of forming a complex, and the metal and the metal compound of Ma include a divalent metal atom and a divalent metal oxide. A divalent metal hydroxide or a divalent metal chloride is included. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, in addition to Fe, such _{as, AlCl, InCl, FeCl, TiCl} 2, SnCl 2, SiCl 2, GeCl Also included are metal chlorides such as ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .

  Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex VO is preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferred, Fe, Zn, Co, or Cu is more preferred, and Zn is most preferred.

X ₁ in the general formulas (A) and (B) represents a group necessary for neutralizing the electric charge of Ma, and X ₂ represents a group capable of binding to Ma. p represents 0 or 1; X ₁ and X ₂ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.

X ₁ in the general formula (B) represents a group necessary for neutralizing the charge of Ma, and examples thereof include a halogen, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group.

X _{2 in} general formula (A) and general formula (B) may be any group as long as it is a group capable of binding to Ma, such as water, alcohols (for example, methanol, ethanol, propanol) and the like. Metal chelates ”[1] Takeichi Sakaguchi and Keihei Ueno (1995 Nanoedo), [2] (1996), [3] (1997), and the like.

P in general formula (A) and general formula (B) represents 0 or 1.
X ₁ and X ₂ in the general formula (A) and the general formula (B) may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma. The 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings may be composed of only carbon atoms, and form a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom. May be.

  The compounds represented by the general formula (A) and the general formula (B), or tautomers thereof, are preferably represented by the general formula (1-A) from the viewpoints of synthesis suitability, stability of the compound, fastness and the like. And a dipyrromethene metal complex represented by a compound represented by formula (1-B) or a tautomer thereof.

In general formulas (1-A) and (1-B), R _{2 to} R ₅ each independently represents a hydrogen atom or a substituent. R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₈ and R ₉ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group. However, any substituent of R _{2 to} R ₅ , R ₈ , and R ₉ becomes a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M is bonded. is doing. M represents a hydrogen atom or an organic base or metal atom necessary for neutralizing the electric charge. L represents an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO ₂ —, —N (Ra) —, —COO—, —OCO—. , -CON (Rb) -, - N (Rb) CO -, - N (Rb) COO -, - OOCN (Rb) -, - N (Rb) CON (Rc) -, - SO 2 N (Rb) - And a divalent group that can be formed by a combination with a divalent group selected from the group of —N (Rb) SO ₂ —. Ra represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. Or a heterocyclic group.
Ma represents a metal or a metal compound capable of forming a complex, and X ₁ represents a group necessary for neutralizing the charge of Ma. X ₃ and X ₄ each independently represent NR (where R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. R and R ₈ or R ₉ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring), an oxygen atom, or a sulfur atom, and Y ₁ and Y ₂ are each independently NR (R Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or an oxygen atom, and R ₈ and Y ₁ are bonded to each other to represent 5 A 6-membered, 6-membered or 7-membered ring may be formed, and R ₉ and Y ₂ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring.

Next, general formula (1-A) and general formula (1-B) will be described in detail.
R _{2 to} R ₅ , R ₇ , M, L, Ma, and X ₁ in the general formula (1-A) and the general formula (1-B) are described in the general formula (A) and the general formula (B). The preferred range is also the same.

Formula (1-A) and the general formula (1-B) _{R 8} and _{R 9} in becomes a divalent linking ^{_{group, - (L) -SO 3 -}} , or - (L) _-SO 3 M And the divalent linking group of R ₈ and R ₉ is described by the substitution of a hydrogen atom in place of — (L) —SO ₃ ^— or — (L) —SO ₃ M. .

R ₈ and R ₉ in general formula (1-A) and general formula (1-B) are each independently an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group. Represents an anilino group or a heterocyclic amino group.

The preferred range of the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group, anilino group, and heterocyclic amino group of R ₈ and R ₉ is the substitution of R _{1 to} R ₆ . It is the same as that explained in the group.

The alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group, anilino group, and heterocyclic amino group of R ₈ and R ₉ are further substituted with the substituents of R _{1 to} R ₆ . In the case of substitution with two or more substituents, these substituents may be the same or different.

When the substituents of R ₈ and R ₉ are divalent linking groups, a plurality of substituents may be linked to each other to form a new divalent linking group. For example, an alkylene group or an aralkylene group , Arylene group, divalent heterocyclic group, —O—, —S—, —C (═O) O—, —OC (═O) —, —C (═O), —OC (═O) N (Rd)-, -C (= O) N (Rd)-, -N (Rd) C (= O)-, -N (Rd) C (= O) O-, -N (Rd) C (= _{O) N (Re) -,} - SO -, - SO 2 -, - SO 3 -, - SO 2 N (Rd) -, - N (Rd) SO 2 -, - C (= O) N (Rd) A plurality of divalent linking groups such as SO ₂ — and —SO ₂ N (Rd) SO ₂ — may be bonded to form a new divalent linking group.

Rd and Re represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an alkyl group sulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, and the like. A group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an alkyl group sulfonyl group, an arylsulfonyl group, a carbamoyl group, and a sulfamoyl group may be substituted with the groups described above for the substituents of R _{1 to} R ₆ ; When substituted with two or more substituents, these substituents may be the same or different.

X ₃ and X ₄ in general formula (1-A) and general formula (1-B) are each independently NR (where R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, Represents an alkylsulfonyl group or an arylsulfonyl group, and R and R ₈ or R ₉ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring), oxygen atom or sulfur atom; And the preferred range of the alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group of R is the alkyl group or alkenyl group described above for the substituents of R _{1 to} R _6. , Aryl group, heterocyclic group, acyl group, alkylsulfonyl group and arylsulfonyl group.

When R is a substitutable group, it may be substituted with the groups described for the substituents of R _{1 to} R ₆ , and when it is substituted with two or more substituents, The substituents may be the same or different.

X ₃ and X ₄ are preferably NR (R is a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group) or an oxygen atom, and from the viewpoints of suitability for synthesis, stability of the compound, and the like, an oxygen atom Is most preferred.

Y ₁ and Y ₂ in general formula (1-A) and general formula (1-B) are each independently NR (where R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group). , An alkylsulfonyl group, an arylsulfonyl group), or an oxygen atom, and R in NR has the same meaning as explained for R in X ₃ and X ₄ above.

R ₈ and Y ₁ in General Formula (1-A) and General Formula (1-B) may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ₉ And Y ₂ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring.
Ma represents a metal or a metal compound capable of forming a complex, and X ₁ represents a group necessary for neutralizing the charge of Ma.

  The general formula (1-A) is more preferably represented by the following general formula (C) or a tautomer thereof from the viewpoints of suitability for synthesis, stability of the compound, solubility in organic solvents, and the like. 1-B) is more preferably represented by the following general formula (D) or a tautomer thereof.

In general formula (C) and general formula (D), R < ₂ > -R < ₅ > represents a hydrogen atom or a substituent each independently. R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₁₀ and R ₁₁ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group. However, any substituent of R _{2 to} R ₅ , R ₁₀ and R ₁₁ becomes a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M is bonded. is doing. M represents a hydrogen atom or an organic base or metal atom necessary for neutralizing the electric charge. L represents an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, —O—, —S—, —SO ₂ —, —N (Ra) —, —COO—, —OCO—. , -CON (Rb) -, - N (Rb) CO -, - N (Rb) COO -, - OOCN (Rb) -, - N (Rb) CON (Rc) -, - SO 2 N (Rb) - , N (Rb) SO ₂ — represents a divalent group that can be formed in combination with a divalent group selected from the group of Ra represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Represents. X ₁ represents a group necessary for neutralizing the charge of Zn.

In general formula (C) and general formula (D), R _{2 to} R ₅ , R ₇ , M, L, and X ₁ are the general formula (A), general formula (B), and general formula (1-A). , And those of general formula (1-B), and the preferred ranges are also the same.
R ₁₀ and R ₁₁ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group. However, any substituent of R _{2 to} R ₅ , R ₁₀ and R ₁₁ becomes a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M is bonded. is doing.

Formula (C) and _{R 10} and _{R 11} in the general formula (D) is a divalent linking ^{_{group, - (L) -SO 3 -}} , or - (L) bonded to -SO ₃ M The divalent linking group of R ₁₀ and R ₁₁ will be described by the substitution of a hydrogen atom in place of — (L) —SO ₃ ^— or — (L) —SO ₃ M.

R ₁₀ and R ₁₁ in general formula (C) and general formula (D) are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group, anilino group, Or represents a heterocyclic amino group.
The alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group, anilino group, or heterocyclic amino group of R ₁₀ and R ₁₁ are further substituted as described above for R _{1 to} R _6. When substituted with two or more substituents, these substituents may be the same or different.
R ₁₀ and R ₁₁ are each independently preferably an alkyl group or an aryl group from the viewpoints of synthesis suitability and stability of the compound.

When the substituents of R ₁₀ and R ₁₁ are divalent linking groups, a plurality of substituents may be linked to each other to form a new divalent linking group. For example, an alkylene group or an aralkylene group , Arylene group, divalent heterocyclic group, —O—, —S—, —C (═O) O—, —OC (═O) —, —C (═O), —OC (═O) N (Rd)-, -C (= O) N (Re)-, -N (Rd) C (= O)-, -N (Rd) C (= O) O-, -N (Rd) C (= _{O) N (Re) -,} - SO -, - SO 2 -, - SO 3 -, - SO 2 N (Rd) -, - N (Rd) SO 2 -, - C (= O) N (Rd) A plurality of divalent linking groups such as SO ₂ — and —SO ₂ N (Rd) SO ₂ — may be bonded to form a new divalent linking group.

Rd and Re represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an alkyl group sulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, etc., and these alkyl groups, aryl groups , A heterocyclic group, an acyl group, an alkoxycarbonyl group, an alkyl group sulfonyl group, an arylsulfonyl group, a carbamoyl group, and a sulfamoyl group may be substituted with the groups described above for the substituents of R _{1 to} R _6. When it is substituted with more than one substituent, these substituents may be the same or different.

The tautomers of the compounds represented by general formula (1-A), general formula (1-B), general formula (C), and general formula (D) will be described.
The tautomers of the compounds represented by general formula (1-A), general formula (1-B), general formula (C), and general formula (D) are one hydrogen atom in the molecule. Any compound may be used as long as it has a structure that can be formed by the movement of, for example, a structure of the following general formula (a) to general formula (f).

X ₅ in the above formulas (a) to (f) is a group capable of binding to Ma, and a is 0 or 1. Each other substituent is synonymous with those of general formula (1-A), general formula (1-B), general formula (C), and general formula (D).

Next, the preferable range of the compound according to the present invention will be described.
Preferably, the general formula (A) is represented by the general formula (1-A), the general formula (B) is represented by the general formula (1-B), and more preferably, the general formula (C) or the general formula, respectively. It is represented by (D).

  L in general formula (1-A), general formula (1-B), general formula (C), and general formula (D) is preferably an alkylene group.

Formula (A) or Formula (B) in the ^- (L) -SO ₃ -, or - (L) as the position -SO ₃ M are attached and _{R 1} or _{R 6} is a divalent linking group is preferably bonded is, the formula (1-a) and formula (1-B) in the ^- (L) -SO ₃ -, or - (L) as positions -SO ₃ M is bonded it is preferred _{that R 8} or _{R 9} is bound to a divalent linking group, more preferably the general formula (C) and the general formula (D) in the ^- (L) -SO ₃ -, or - (L) as the position -SO ₃ M is _bonded, it is preferred _{that R 10} or _{R 11} are bonded a divalent linking group.

Any group of R _{1 to} R _{6 in} the general formula (A) and the general formula (B) is a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M As the divalent linking group when bonded to the alkylene group, an alkylene group, an aralkylene group, an arylene group, a divalent heterocyclic group, an alkylene group, an aralkylene group, an arylene group, -O-, -S-,- C (= O) O-, -OC (= O)-, -C (= O), -OC (= O) N (Rd)-, -C (= O) N (Re)-, -N ( Rd) C (═O) —, —N (Rd) C (═O) O—, —N (Rd) C (═O) N (Re) —, —SO—, —SO ₂ —, —SO ₂ N (Rd) -, or -N (Rd) SO ₂ - ₂ divalent linking group is preferably formed of capital. More preferred are an alkylene group, an aralkylene group and an arylene group.

In the general formula (1-A) and the general formula (1-B), any one of R _{2 to} R _5, R ₈ and R ₉ becomes a divalent linking group, and — (L) —SO ₃ ^— Or a divalent linking group when-(L) SO ₃ M is bonded to an alkylene group, an aralkylene group, an arylene group, a divalent heterocyclic group, an alkylene group, an aralkylene group, or an arylene group , -O-, -S-, -C (= O) O-, -OC (= O)-, -C (= O), -OC (= O) N (Rd)-, -C (= O ) N (Re)-, -N (Rd) C (= O)-, -N (Rd) C (= O) O-, -N (Rd) C (= O) N (Re)-, -SO A divalent linking group formed with —, —SO ₂ —, —SO ₂ N (Rd) —, or —N (Rd) SO ₂ — is preferable. More preferred are an alkylene group, an aralkylene group and an arylene group.

Formula (C) and the general formula _{(D) R 2 ~R 5,} R 10 in, and any of the groups for _{R 11} is a divalent linking group - (L) -SO ₃ ^-, or - (L) As the divalent linking group to which —SO ₃ M is bonded, an alkylene group, an aralkylene group, an arylene group, a divalent heterocyclic group, an alkylene group, an aralkylene group, or an arylene group, and —O— , -S-, -C (= O) O-, -OC (= O)-, -C (= O), -OC (= O) N (Rd)-, -C (= O) N (Re ) -, - N (Rd) C (= O) -, N (Rd) C (= O) O -, - N (Rd) C (= O) N (Re) -, - SO -, - SO 2 A divalent linking group formed with —, —SO ₂ N (Rd) —, or —N (Rd) SO ₂ — is preferable. More preferred are an alkylene group, an aralkylene group and an arylene group.

  The preferred ranges of the substituents of the general formula (A), the general formula (B), the general formula (1-A), the general formula (1-B), the general formula (C), and the general formula (D) are as follows The combination of the preferred range of each substituent and the preferred range of the general formula is more preferably higher.

R ₁ and R ₆ in general formula (A) and general formula (B) are preferably each independently an alkyl group, aryl group, heterocyclic group, general formula (1-A) and general formula (1-B). ) -Y ₁ -C (═X ₃ ) —R ₈ , or a group represented by —Y ₂ —C (═X ₄ ) —R ₉ , General Formula (C) and General In formula (D), it is a group represented by —NH—C (═O) —R ₁₀ or —NH—C (═O) —R ₁₁ .
More preferably, R ₁ and R ₆ are groups represented by —Y ₁ —C (═X ₃ ) —R ₈ in the general formula (1-A) and the general formula (1-B), or — A group represented by Y ₂ —C (═X ₄ ) —R ₉ , —NH—C (═O) —R ₁₀ in formula (C) and formula (D), or —NH—C ( = O) -R ₁₁ represents a group.
Most preferred is a group represented by —NH—C (═O) —R ₁₀ or —NH—C (═O) —R ₁₁ in formulas (C) and (D).

Formula (A), Formula (B), formula (1-A), the general formula (1-B), Formula (C), and in the general formula (D), _{R 2,} and _{R 5} is Preferably, each independently, an alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, carboxyl group, acyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclic thio group, alkyl Sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, sulfamoyl group, more preferably perfluoroalkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl Group, cyano group, carboxyl group, acyl group, carbamoyl group, alkylsulfonyl group, aryl A sulfonyl group, a heterocyclic sulfonyl group, and a sulfamoyl group, more preferably a perfluoroalkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a carboxyl group, an acyl group, and a carbamoyl group. An alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group, and most preferably a perfluoroalkyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a carbamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In general formula (A), general formula (B), general formula (1-A), general formula (1-B), general formula (C), and general formula (D), R ₃ and R ₄ are Preferably each independently an alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, cyano group, carbamoyl group, more preferably an alkyl group, aryl group, heterocyclic group, cyano group, Most preferably, they are an alkyl group, an aryl group, and a heterocyclic group.

R ₇ in general formula (A), general formula (B), general formula (1-A), general formula (1-B), general formula (C), and general formula (D) is preferably hydrogen. An atom, a halogen atom, an alkyl group, an aryl group, and a heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, and still more preferably a hydrogen atom, an alkyl group, and an aryl group. Most preferably, it is a hydrogen atom.

  In general formula (B), general formula (1-B), and general formula (D), M is preferably a hydrogen atom, a trialkylamine having 3 to 14 carbon atoms, or a quaternary having 4 to 20 carbon atoms. Ammoniums, guanidines having 3 to 14 carbon atoms, and alkali metals, more preferably trialkylamines having 3 to 9 carbon atoms, quaternary ammonium salts having 4 to 8 carbon atoms, or alkali metals Further, alkali metals are more preferable.

X ₂ in the general formula (A) and the general formula (B) is preferably water, alcohols (for example, methanol, ethanol, propanol) or the like, and further “metal chelate” [1] Takeichi Sakaguchi / Keihei Ueno (1995 Nanedou), [2] (1996), [3] (1997), etc., more preferably water or alcohols, most preferably p is 0.

  Ma in the general formula (A), the general formula (B), the general formula (1-A), and the general formula (1-B) is preferably Fe, Zn, Co, or Cu, and more preferably. Zn, Co, and Cu, and most preferably Zn.

X ₁ in the general formula (B), the general formula (1-B), and the general formula (D) is preferably a halogen atom, a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group, and more preferably, A chlorine atom, a carboxylic acid group, and a sulfonic acid group.

R ₈ and R ₉ in general formula (1-A) and general formula (1-B) are preferably each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, amino group, anilino A group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, and an anilino group, still more preferably an alkyl group, an aryl group, and a heterocyclic group, most preferably , An alkyl group and an aryl group.

X ₃ and X ₄ in general formula (1-A) and general formula (1-B) are preferably each independently NR (where R is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, Represents an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a sulfur atom, and an oxygen atom, more preferably —NH—, a sulfur atom, and an oxygen atom, and most preferably an oxygen atom.

Y ₁ and Y ₂ in general formula (1-A) and general formula (1-B) are preferably each independently NR (where R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic ring) Group, acyl group, alkylsulfonyl group, arylsulfonyl group), more preferably NR (R is a hydrogen atom, alkyl group), and most preferably —NH— group.

R ₁₀ and R ₁₁ in general formula (C) and general formula (D) are preferably each independently an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group or an aryl group. .

  Next, for the compounds represented by general formula (A), general formula (B), general formula (1-A), general formula (1-B), general formula (C), and general formula (D), respectively. Specific examples are shown below, but the present invention is not limited thereto.

The compounds represented by the general formula (A), the general formula (B), the general formula (C), and the general formula (D) are synthesized by the method described in US Patent Application Publication No. 2008 / 0076044A1. can do.
The method for synthesizing the dipyrromethene-based metal complex compound in the present invention will be described in detail with reference to the following reaction scheme A, taking the synthesis of A-3 as an example compound as an example.

Reaction scheme A

(Synthesis Example 1)
Synthesis of [Exemplary Compound A-3] (Synthesis of Intermediate B)
50 ml of N-methylpyrrolidone (NMP) was added to 17.4 g (0.05 mol) of intermediate A synthesized according to the method described in JP-A-10-316654, and the mixture was cooled to 5 ° C. and stirred. To this solution, 7.62 g (0.06 mol) of 2-chloropropionyl chloride was added dropwise. After completion of the dropwise addition, this reaction solution was poured into 800 ml of water with stirring to precipitate crystals. The crystals were filtered and washed with water. The crystals were then dispersed in 250 ml of acetonitrile, stirred for 2 hours and filtered. As a result, 16.5 g (yield: 75.2%) of intermediate B was obtained.

(Synthesis of Intermediate C)
50 ml of NMP was added to 13.0 g (0.03 mol) of the intermediate B obtained by the above method and 8.0 g (0.045 mol) of sodium 3-mercaptopropanesulfonate, followed by stirring under a nitrogen stream. To this dispersion, 5.5 g (0.036 mol) of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise. After completion of the dropwise addition, the reaction was completed by stirring at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into 700 ml of saturated brine and 500 ml of ethyl acetate with stirring. The brine was removed and the ethyl acetate solution was washed with saturated brine and dried over anhydrous sodium sulfate. Ethyl acetate was concentrated under reduced pressure, and 500 ml of acetonitrile was added to the residue to precipitate crystals. The crystals were filtered and dried. As a result, 16.9 g (yield: 97.1%) of Intermediate C was obtained.

(Synthesis of Intermediate D)
100 ml of NMP was added to 34.9 g (0.1 mol) of Intermediate A synthesized according to the method described in JP-A-10-316654, and the mixture was cooled to 10 ° C. and stirred. To this solution, 14.5 g (0.12 mol) of pivaloyl chloride was added dropwise. After completion of the dropwise addition, the reaction was completed by stirring for 2 hours at room temperature. The reaction solution was poured into 1000 ml of water with stirring to precipitate crystals. The crystals were filtered, washed with water and dried. To this crystal, 500 ml of acetonitrile was added, heated to 50 ° C. and stirred for 1 hour. The dispersion was cooled to room temperature, filtered and dried. As a result, 36.2 g (yield: 83.7%) of Intermediate D was obtained.

(Synthesis of Intermediate E)
100 ml of dimethylformamide (DMF) was cooled to 5 ° C. and stirred, and 19.3 g of phosphorus oxychloride was added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. to 10 ° C. for 1 hour, and then a solution prepared by dissolving 36.2 g (0.084 mol) of the intermediate D obtained by the above method in 100 ml of DMF was added dropwise. After stirring at 10 ° C. to 15 ° C. for 1 hour, 19.3 g of phosphorus oxychloride was further reduced. After completion of the dropwise addition, the reaction was completed by stirring for 2 hours at 10 to 15 ° C. After completion of the reaction, this reaction solution was poured into 1000 ml of water with stirring. Next, an aqueous solution in which 40 g of sodium hydroxide was dissolved in 300 ml of water was added dropwise to this aqueous solution until the pH reached 7. After completion of the dropwise addition, the resulting crystals were stirred for 2 hours at room temperature, filtered, washed with water and dried. 40.0 g of a dimethylaminomethylene derivative of Intermediate D was obtained. To 40.0 g of this dimethylaminomethylene, 150 ml of ethyl acetate, 30 ml of methanol and 200 ml of water were added and stirred at room temperature. To this solution, 8.5 g of potassium carbonate was added and heated to 35 ° C. to 40 ° C. and stirred for 2 hours. After completion of the reaction, 35% aqueous hydrochloric acid was added to the reaction solution until the pH reached 3-4. Next, the ethyl acetate layer was washed with saturated brine and then dried over anhydrous sodium sulfate. The ethyl acetate was concentrated to dryness under reduced pressure. Crystals were precipitated by adding 100 ml of acetonitrile to the residue, filtered and dried. 36.6 g (yield: 95.0%) of Intermediate E was obtained.

(Synthesis of Intermediate F)
50 ml of acetic anhydride and 3.5 g of trifluoroacetic acid were added to 4.61 g (0.01 mol) of the intermediate E obtained by the above method, and the mixture was cooled to 5 ° C. to 10 ° C. and stirred. To this solution, 5.81 g (0.01 mol) of Intermediate E obtained by the above method was slowly added in several portions. After completion of the addition, the reaction was completed by stirring at room temperature for 2 hours. After completion of the reaction, this reaction solution was slowly added dropwise to an aqueous solution in which 84 g of sodium bicarbonate was dissolved in 1000 ml of water. The precipitated crystals were filtered, washed with water and dried. A mixed solvent of 50 ml of acetonitrile and 25 ml of ethyl acetate was added to the crystals and dispersed at room temperature, followed by stirring for 2 hours. The crystals were filtered and dried. 7.88 g (yield: 77.0%) of intermediate F was obtained.
Λmax in the ethyl acetate solution was 507.1 nm, and the molar extinction coefficient (ε) was 55600.

(Synthesis of Exemplified Compound A-3)
To 1.18 g of zinc acetate dihydrate, 150 ml of 2-propanol was added and stirred at room temperature. To this dispersion, 5.0 g (0.0049 mol) of Intermediate F obtained by the above method was added. After completion of the addition, the reaction was completed by stirring at room temperature for 3 hours. To this solution, 100 ml of acetonitrile was slowly added dropwise and stirred for 4 hours. The crystals were filtered, washed with acetonitrile and dried. 4.25g (yield: 81.6%) of exemplary compound A-3 was obtained.
Λmax of Example Compound A-3 in an ethyl acetate solution was 535.0 nm, and the molar extinction coefficient (ε) was 140800.

  The compounds represented by the general formula (A), the general formula (B), the general formula (C), and the general formula (D) are synthesized by the method described in US Patent Application Publication No. 2008 / 0076044A1. can do.

  In the present invention, the content in the at least one colored curable composition selected from the compounds represented by the general formula (A) and the general formula (B) and the tautomers thereof is the molecular weight and the mole, respectively. Although it varies depending on the extinction coefficient, it is preferably 0.5 to 80% by mass, more preferably 0.5 to 60% by mass, and most preferably 0.5 to 50% by mass with respect to the total solid component of the colored curable composition. preferable.

  The colored curable composition and color filter of the present invention include compounds represented by the general formula (A), the general formula (B), the general formula (C), and the general formula (D), respectively, Besides tautomers, phthalocyanine compounds (for example, phthalocyanine compounds described in US Patent Application Publication No. 2008 / 0076044A1), triarylmethane-based colorants having an absorption maximum at 550 nm to 650 nm, for example, -Eye Acid Blue 7 (C.I. Acid Blue 7), C.I. Acid Blue 83 (C.I. Acid Blue 83), C.I. Acid Blue 90 (C.I. Acid Blue 90), C.I.・ Solvent Blue 38 (CI Solvent Blue 38), C.I. Acid Violet 7 (C.I.Acid Violet17), CI Acid Violet 49 (C.I.Acid Violet49), CI Acid Green 3 (C.I.Acid Green3), etc. can be used.

  Furthermore, a xanthene dye having an absorption maximum at 500 nm to 600 nm, such as C.I. Acid Red 289, can be used.

  The content of the phthalocyanine-based colorant and the triarylmethane-based colorant can be used as long as the effects of the present invention are not impaired. It is preferable that it is 5 mass%-50 mass%.

In order to produce a blue filter array, it is preferable to use a mixture of the metal complex according to the present invention and at least one phthalocyanine-based colorant.
At this time, each mixing ratio varies depending on each molar extinction coefficient, required spectral characteristics, film thickness, etc., but in general, the content ratio (total content of the metal complex of the present invention): (phthalocyanine) System colorant) = 10: 1 to 1:20. Preferably it is used in the range of 5: 1 to 1:10.

<Binder>
The colored curable composition of the present invention preferably contains at least one binder. The binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, etc., and methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer. There are polymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful.
In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

  In addition, a monomer having a hydrophilic group may be copolymerized, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylolacrylamide. Secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) Examples include acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Other monomers having a hydrophilic group include tetrahydrofurfuryl group, phosphoric acid moiety, phosphate ester moiety, quaternary ammonium salt moiety, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt moiety, morpholinoethyl group, etc. Monomers are also useful.

In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful.
Examples of the polymer having these polymerizable groups include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
In order to increase the strength of the cured coating, alcohol-soluble nylon, polyether of 2,2-bis (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.

Among the various binders, the binder is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS-resist-106 (Osaka Organic Chemical). Kogyo Co., Ltd.), Cyclomer P-series and the like are preferable.

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

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

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

The binder preferably has a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ × 10 ^4. The polymer is particularly preferred.
10 mass%-90 mass% are preferable with respect to the total solid of the colored curable composition of this invention, and the usage-amount of the said binder in the colored curable composition of this invention is 20 mass%-80 mass%. Is more preferable, and 30% by mass to 70% by mass is particularly preferable.

<Crosslinking agent>
The colored curable composition of the present invention contains at least one selected from a compound represented by the general formula (A) or the general formula (B) and a tautomer thereof as a colorant, and is compared with the conventional one. In addition, it has a higher extinction coefficient that can be made thinner and has a high extinction coefficient, and can be made to have excellent fastness properties. It is also possible to configure so as to obtain a deposited film.

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

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

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

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

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

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

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

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

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

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

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

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

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

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

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

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

  When the crosslinking agent is contained, the content of the crosslinking agent (a) to (c) in the colorant-containing curable composition varies depending on the material, but with respect to the total solid content (mass) of the composition, 1-70 mass% is preferable, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable. When the content is within the above range, it is possible to maintain a sufficient degree of cure and elution of the unexposed area, and prevent the degree of cure of the exposed area from being insufficient or significantly reducing the elution of the unexposed area. be able to.

<Polymerizable monomer>
The colored curable composition of the present invention can be suitably constituted by containing at least one polymerizable monomer. The polymerizable monomer is mainly contained when the colored curable composition is constituted as a negative type.
In addition, it can contain in the positive type | system | group containing the below-mentioned naphthoquinone diazide compound with the below-mentioned photoinitiator, and in this case, the hardening degree of the pattern formed can be promoted more. Hereinafter, the polymerizable monomer will be described.

  The polymerizable monomer is preferably a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with (meth) acrylic acid, and mixtures thereof.

  Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The content of the polymerizable monomer in the colored curable composition is preferably 0.1% by mass to 90% by mass, and 1.0% by mass to 80% by mass with respect to the solid content in the colored curable composition. Is more preferable, and 2.0 mass%-70 mass% is especially preferable.

<Radiation sensitive compounds>
The colored curable composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound. A radiation-sensitive compound is a compound capable of causing a chemical reaction such as radical generation, acid generation, and base generation for UV light having a wavelength of 400 nm or less. However, the above-described binder is subjected to a reaction such as crosslinking, polymerization, or decomposition of an acidic group. It is used for the purpose of insolubilizing the coating film with an alkali developer by causing polymerization of polymerizable monomers and oligomers coexisting in the coating film, crosslinking of the crosslinking agent, and the like.

  In particular, when the colored curable composition is composed of a negative type, it preferably contains a photopolymerization initiator, and when it constitutes a positive type, it preferably contains a naphthoquinonediazide compound. .

(Photopolymerization initiator)
Next, the photopolymerization initiator contained when the colored curable composition of the present invention is a negative composition will be described.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
In addition, you may further contain in the positive type | system | group containing said naphthoquinone diazide compound, In this case, the pattern hardening degree formed can be promoted more.
Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound, and Examples thereof include cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of active halogen compounds such as halomethyloxadiazole include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl-5, and the like. -Styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like.

  Examples of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphth-1-yl)-described in JP-A-53-133428. Examples include 4,6-bis (halomethyl) -s-triazine compounds and 4- (p-aminophenyl) -2,6-bis (halomethyl) -s-triazine compounds.

  Other examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy-naphtho-) -Yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4 -(2-methoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- (2- Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (6- Toxi-naphth-2-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-bis ( Ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (bird Chloromethyl) -s-triazine, 4- [pN, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6- Bis (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- [p N- (p-methoxyphenyl) carbonylaminophenyl] 2,6-bis (trichloromethyl) -s-triazine, 4- [m-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (Trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [m -Chloro-pN, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-bis (ethoxycarbonyl) Methyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-bis (ethoxycarboni) Methyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine,

4- [o-chloro-pN, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N- Bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-bis (chloroethyl) aminophenyl] -2,6-bis (Trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [o-fluoro -PN, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) amino Phenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s- Triazine, 4- [m-fluoro-pN, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonyl) Methylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- (o-butyl) Mo-pN-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-bis (Trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- (m-bromo-p- N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s -Triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- (o -Bromo-pN-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-bis ( Trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine and the like.

  Others, TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, PANCHIM T series, T-OMS , T-BMP, TR, TB, Irgacure series, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocur series Darocur 1173, 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenyl Acetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4 , 5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- ( 2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-di E imidazoline dimer, benzoin isopropyl ether and the like are also useful.

  Particularly preferably, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( And oxime-O-acyl compounds such as 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

In addition to the photopolymerization initiator, other known photopolymerization initiators can be used in combination with the photosensitive colored curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triallylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / Triha And lomethyl-s-triazine compounds.

  The content of the photopolymerization initiator in the colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, and 1 to 20% by mass with respect to the polymerizable monomer solid content. Is particularly preferred. When the content is within the above range, the polymerization proceeds well and good film strength can be obtained.

A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethyl Amino) phenyl-p-methylstyryl ketone Examples include benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in JP-B 51-48516, and tinuvin 1130, 400. .

  In addition to the above, it is preferable to add a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

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

  When the colored curable composition of the present invention is constituted as a positive type, the alkali-soluble phenol resin and the crosslinking agent are usually about 2 to 50% by mass and about 2 to 30% by mass, respectively, in the organic solvent. It is preferable to dissolve at a ratio. Each content of the naphthoquinone diazide compound, the compound represented by the general formula (A) and the general formula (B), and one or more compounds (pigments) selected from the tautomers thereof is usually as described above. It is preferable to add at a ratio of about 2% by mass to 30% by mass and 2% by mass to 50% by mass with respect to the solution in which the binder and the crosslinking agent are dissolved.

<Solvent>
In preparing the colored curable composition of the present invention, a solvent can generally be contained. The solvent used is not particularly limited as long as it satisfies the solubility of each component of the composition and the applicability of the photosensitive colored curable composition. Is preferably selected in consideration of
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as ethyl (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, -2-oxypropionic acid alkyl esters such as ethyl oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion) Acid methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydro , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate Propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among the above, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

<Various additives>
In the colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

  In the case of promoting the alkali solubility of the area to be developed and removed (for example, the uncured portion in the case of a negative type) and further improving the developability of the photosensitive colored curable composition of the present invention. An organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be added to the composition. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

The colored curable composition of the present invention is used for forming a colored pixel such as a color filter used in a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), printing ink, inkjet ink, and It can be suitably used as a production application for paints and the like. In particular, it can be suitably used for forming colored pixels for solid-state imaging devices such as CCDs and CMOSs.
The colored curable composition of the present invention is particularly suitable for forming a color filter for a solid-state imaging device in which a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required.
Specifically, when the pixel pattern size (side length of the pixel pattern viewed from the substrate normal direction) constituting the color filter is 2 μm or less (for example, 0.5 to 2.0 μm), the amount of colorant increases. In addition, since the hue is blue, the line width sensitivity is deteriorated and the DOF margin is narrowed. As a result, the pattern formability is easily impaired. This is particularly noticeable when the pixel pattern size is 1.0 to 1.7 μm (further 1.2 to 1.5 μm). In addition, in the case of a thin film having a thickness of 1 μm or less, the amount of components that contribute to photolithographic properties excluding the colorant in the film is relatively reduced, and the amount of other components is further reduced by the increase in the amount of colorant. Sensitivity is increased and the pattern is easily peeled off in the low exposure area. In this case, heat sagging is likely to occur when heat treatment such as post-baking is performed. These are particularly remarkable when the film thickness is 0.005 μm to 0.9 μm (further 0.1 μm to 0.7 μm).
On the other hand, when the colored curable composition of the present invention is used, a color filter having a good cross-sectional profile can be produced with excellent pattern formation even with a pixel pattern size of 2 μm or less as described above.

-Color filter and manufacturing method thereof-
The color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described colored curable composition of the present invention is used. The color filter of the present invention forms a radiation-sensitive composition layer by applying the colored curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, etc. A negative or positive colored pattern (resist pattern) image can be formed by developing with a developer after exposure through the pattern.
The exposure light source applicable to the curable composition of the present invention is not particularly limited as long as it is a light source having a wavelength of 400 nm or less. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, Lamp light sources such as high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, Ar ion lasers (364 nm, 351 nm, 10 mW to 1 W), Kr ion lasers (356 nm, 351 nm, 10 mW to 1 W), As a solid-state laser, a combination of Nd: YAG (YVO 4) and SHG crystal × 2 times (355 nm, 5 mW to 1 W), a combination of a waveguide wavelength conversion element and AlGaAs, a combination of a waveguide wavelength conversion element and AlGaInP, and an AlGaAs semiconductor ( 300nm-350nm, 5mW-100mW), As other pulse lasers, N2 laser (337 nm, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 to 250 mJ) and the like can be used. When only a specific wavelength is used, an optical filter can also be used.
Furthermore, ultraviolet rays such as ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), i-line (wavelength 365 nm) can be used. An exposure light source that is particularly preferable from the viewpoint of cost and exposure energy is ultraviolet light, and in particular, i-line.
Furthermore, the formed pattern can be provided with a curing step for further curing by heating and / or exposure as necessary. As light or radiation used at this time, radiation such as i-line is particularly preferably used.

  In the production of the color filter of the present invention, in the case of the negative type, the image forming step (and the curing step if necessary) is repeated according to the desired number of colors, and in the case of the positive type, the image is obtained. By repeating the forming process and the post-baking process according to the desired number of colors, a color filter configured with a desired number of hues can be manufactured.

  As the above support, for example, soda 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, photoelectric conversion element substrates used for imaging elements, etc. A silicon substrate, a complementary metal oxide semiconductor (CMOS), etc. are mentioned. These supports may be formed with black stripes that separate pixels.

  In addition, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the support.

  As a developer used in the method for producing a color filter of the present invention, a region to be developed and removed of the colored curable composition of the present invention (an uncured portion in the case of a negative type) is dissolved, while other regions ( In the case of the negative type, any material can be used as long as it has a composition that does not dissolve the cured portion). Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution so dissolved is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS device having more than 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

[Example 1]
1) Preparation of resist solution-Propylene glycol monomethyl ether acetate (PGMEA) 5.20 parts-Cyclohexanone 52.6 parts-Binder: (benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate) copolymer (molar ratio) = 60:20:20) 41% EL solution
30.5 parts ・ Dipentaerythritol hexaacrylate 10.2 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.006 parts ・ Fluorosurfactant 0.80 parts ・ Photopolymerization initiator TAZ-107 (Midori Chemical Co., Ltd.) 0.58 parts) was mixed and dissolved to prepare a resist solution.

2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes).
Next, the resist solution of 1) above was applied onto a cleaned glass substrate using a spin coater so as to have a film thickness of 2.0 μm, and dried by heating at 220 ° C. for 1 hour to obtain a cured film (undercoat layer). .

3) Preparation of colored resist solution (colored curable composition [negative type]) A compound having the following composition was mixed and dissolved to prepare a colored curable composition X-1.
<Colored curable fat composition X-1>
・ Ethyl lactate 20 parts ・ Methyl isobutyl ketone 60 parts ・ Exemplary compound (A-1) 4.18 parts ・ KARAYAD DPHA (manufactured by Nippon Kayaku Co., Ltd., polymerizable compound) 12.80 parts ・ Photopolymerization initiator (CGI-242 ( Ciba Specialty Chemicals)
2.00 parts-Surfactant (F-781 manufactured by Dainippon Ink Co., Ltd.) 0.02 parts

4) Coating, exposure, and development of colored resist solution (colored curable composition [negative type]) The glass substrate with an undercoat layer obtained in 2) above for the colored curable composition X-1 prepared in 3) above On the undercoat layer, a spin coater was applied so that the dry film thickness of the coating film was 1.0 μm, thereby forming a photocurable coating film. Then, a heat treatment (pre-baking) was performed for 120 seconds using a 100 ° C. hot plate to obtain a magenta to violet colored filter.

Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 500 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 2 mm. After the exposure, a 60% CD-2000 (produced by Fujifilm Electronics Materials) developer and a 6% CD-2000 developer obtained by diluting 60% CD-2000 developer 10 times with water, Development was performed at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed.
As described above, a pattern suitable for a colored color filter was obtained.

5) Evaluation The storage stability of the colored resist solution prepared above and the spectral characteristics of the coating film coated on the glass substrate using the colored resist solution were evaluated. Further, developability when using a 60% CD-2000 developer and developability when using a developer diluted to 6% were evaluated. The evaluation results are shown in Table 1.

-Storage stability-
After the colored resist solution was stored at room temperature for one month, the degree of visual precipitation of foreign matters was visually evaluated according to the following criteria.
<Criteria>
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

-Transmittance evaluation-
The transmission spectrum of the color filter obtained as described above was measured, and the transmittance at 450 nm was evaluated. The larger the transmittance, the greater the amount of blue light transmitted, and the better the magenta or violet dye that can be used for the blue color filter.
<Criteria>
The transmittance at 450 nm when the transmittance at the maximum absorption wavelength of each dye was corrected (normalized) to 5% was determined.
○: 450 nm transmittance ≧ 90%
Δ: 80% ≦ 450 nm transmittance <90%
×: 450 nm transmittance <80%

-Evaluation of developability-
The absorbance at 550 nm in the unexposed area when 60% CD-2000 was used as the developer and the absorbance at 550 nm in the unexposed area when the developer diluted to 6% was used were evaluated. That is, in a color filter using a colored curable composition having good developability, no colored matter remains in the unexposed area, and as a result of excellent alkali developability, the absorbance at 550 nm is low.
<Criteria>
○: Absorbance at 550 nm <0.01
Δ: 0.01 ≦ 550 nm absorbance <0.1
×: 0.1 ≦ 550 nm absorbance

[Examples 2 to 41]
The same procedure as in Example 1 was conducted except that in the preparation of the 3) colored resist solution of Example 1, Exemplified Compound A-1 was replaced by equimolar amounts with the Exemplified Compounds in Tables 1 and 2 below. The results are shown in Tables 1 and 2.

[Comparative Examples 1-4]
In the preparation of the 3) colored resist solution of Example 1, everything was carried out in the same manner as in Example 1 except that equimolar amount of Exemplified Compound A-1 was replaced with the compound shown in Table 2 below. The results are shown in Table 2.

  From the results of Tables 1 and 2, the colored curable composition using the colorant in the present invention has excellent storability in the resist solution, and the coating film has spectral characteristics (color separation). The film was suitable for an excellent color filter. It was also found that there was no dependency on the concentration of the developer and the pattern forming property (developability) was excellent.

[Example 42 to Example 82]
-Application, exposure and development of resist solution (image formation)-
1) Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, on this silicon wafer, the resist solution prepared in 1) of Example 1 was applied to a dry film thickness of 1.0 μm, and further dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. Thus, a silicon wafer substrate with an undercoat layer was obtained.

On the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in 1), the colored curable composition used in Examples 1-41 is set so that the dry thickness of each coating film becomes 0.8 μm. To form a photocurable coating film. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), an exposure dose of 100 mJ / cm in the range of 100 to 2500 mJ / cm ² through an island pattern mask having a pattern of 1.2 μm square at a wavelength of 365 nm. Irradiation was carried out while changing by ² cm ² . Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.), and 60% CD-2000 ( Using Fujifilm Electronics Materials Co., Ltd., paddle development was performed at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer substrate.

-Formation of color filters-
The silicon wafer substrate on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center from the ejection nozzle. It was supplied as a shower and rinsed, and then spray-dried to obtain a color filter.

  The formed pattern image showed a favorable profile with a square cross section suitable for an image sensor.

[Example 83]
1) Preparation of colored curable composition [positive type] 30 parts of ethyl lactate (EL) 3.0 parts of the following resin P-1 1.8 parts of the following naphthoquinone diazide compound N-1 Crosslinking agent: hexamethoxymethylol 0.6 parts of melamine fluoride, photoacid generator: TAZ-107 (manufactured by Midori Chemical Co., Ltd.) 1.2 parts, fluorosurfactant (F-475, manufactured by DIC Corporation) 0.0005 part, dye: examples Compound A-3 (compound of the present invention) 0.3 part or more was mixed and dissolved to obtain a colored curable composition [positive type].

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

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

3) Synthesis of naphthoquinonediazide compound (N-1) Trispamine PA (Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinonediazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask and triethylamine 24.24 at room temperature. 44 g was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the reaction solution was poured into a large amount of water while stirring. Precipitated naphthoquinonediazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain photosensitive compound N-1.

  As a result of evaluating the colored curable composition [positive type] obtained above by the same method as in Example 1, it was found that the colored curable composition [positive type] was excellent in storage stability and transmittance.

Claims (8)

A coloring comprising at least one selected from the group consisting of a compound represented by the following general formula (A), a compound represented by the following general formula (B), and a tautomer thereof Curable composition.

(In the formula, R _{1 to} R ₆ each independently represents a hydrogen atom or a substituent, and R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, provided that R ₁ represents R _1. To R ₆ , which is a divalent linking group and bonded to — (L) —SO ₃ ^— or — (L) —SO ₃ M. M is a hydrogen atom or a charge .L represents an organic base or metal atom required to neutralize the represents an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, -O -, - S -, - SO 2 -, -N (Ra)-, -COO-, -OCO-, -CON (Rb)-, -N (Rb) CO-, -N (Rb) COO-, -OOCN (Rb)-, -N ( Rb) CON (Rc) -, - SO 2 N (Rb) -, and -N (Rb) SO ₂ - Represents a divalent group that can be formed by combining with a divalent group selected from the group, wherein Ra represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; Rb and Rc each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
Ma represents a metal or a metal compound capable of forming a complex. X ₁ represents a group necessary for neutralizing the charge of Ma, and X ₂ represents a group capable of binding to Ma. p represents 0 or 1; In the general formula (B), X ₁ and X ₂ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. ) The colored curable composition according to claim 1, wherein the general formula (A) is the following general formula (1-A), and the general formula (B) is the following general formula (1-B). object.

(Wherein R _{2 to} R ₅ each independently represents a hydrogen atom or a substituent. R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₈ and R ₉ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group, provided that R _{2 to} R ₅ , A substituent of any one of R ₈ and R ₉ is a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M is bonded, where M is a hydrogen atom. Or an organic base or a metal atom necessary for neutralizing the charge, L is an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, -O-, -S-, _{-SO 2 -, - N (Ra} ) -, - C O -, - OCO -, - CON (Rb) -, - N (Rb) CO -, - N (Rb) COO -, - OOCN (Rb) -, - N (Rb) CON (Rc) -, - SO ₂ N (Rb) -, and -N (Rb) SO ₂ - .Ra representing a divalent combinable formed by a divalent group with group selected from the group consisting of an alkyl group, an alkenyl group, an aryl Represents a group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
Ma represents a metal or a metal compound capable of forming a complex, and X ₁ represents a group necessary for neutralizing the charge of Ma. X ₃ and X ₄ each independently represent NR (where R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. R and R ₈ or R ₉ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring), an oxygen atom, or a sulfur atom, and Y ₁ and Y ₂ are each independently NR (R Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or an oxygen atom, and R ₈ and Y ₁ are bonded to each other to represent 5 A 6-membered, 6-membered or 7-membered ring may be formed, and R ₉ and Y ₂ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. )   The colored curable composition according to claim 1, wherein Ma is Fe, Zn, Co, V═O, or Cu.   The colored curable composition according to claim 1, wherein Ma is Zn. A coloring comprising at least one selected from the group consisting of a compound represented by the following general formula (C), a compound represented by the following general formula (D), and a tautomer thereof Curable composition.

(In the formula, R _{2 to} R ₅ each independently represents a hydrogen atom or a substituent. R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₁₀ and R ₁₁ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an anilino group, or a heterocyclic amino group, provided that R _{2 to} R ₅ , A substituent of any one of R ₁₀ and R ₁₁ becomes a divalent linking group, and — (L) —SO ₃ ^— or — (L) —SO ₃ M is bonded, where M is a hydrogen atom. Or an organic base or metal atom necessary for neutralizing the charge, L is an alkylene group, an aralkylene group, an arylene group, or an alkylene group, an aralkylene group, an arylene group, -O-, -S-, _{-SO 2 -, - N (Ra} ) , -COO-, -OCO-, -CON (Rb)-, -N (Rb) CO-, -N (Rb) COO-, -OOCN (Rb)-, -N (Rb) CON (Rc)-, A divalent group that can be formed by a combination with a divalent group selected from the group of —SO ₂ N (Rb) — and —N (Rb) SO ₂ —, wherein Ra represents an alkyl group or an alkenyl group; , An aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and Rb and Rc each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. X ₁ represents a group necessary for neutralizing the charge of Zn.)   The color filter containing the colored curable composition as described in any one of Claims 1-5. Applying the colored curable composition according to any one of claims 1 to 5 on a support to form a layer;
A step of forming a pattern image by exposing the layer of the colored curable composition formed on the support through a mask and developing the layer;
A method for producing a color filter, comprising:   The pigment | dye selected from the group which consists of the compound represented by the said general formula (C), the compound represented by the said general formula (D), and those tautomers.