JP2012237985A - Photosensitive resin composition, color filter, protective film, photospacer, substrate for liquid crystal display device, liquid crystal display device, and solid-state imaging element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has excellent polymerization curability when exposed to light and high exposure sensitivity and which is capable of forming a color pattern having excellent profile characteristics, a photospacer having excellent cross-sectional shape uniformity and excellent height uniformity, and a protective film having excellent uniformity and hardness even with a short heating time.SOLUTION: The photosensitive resin composition contains (A) an alkali-soluble resin that has a group having an acidic group and two or more polymerizable unsaturated groups different from each other in at least side chains, (B) a polymerizable compound and (C) a photopolymerization initiator.

Description

  The present invention relates to a photosensitive resin composition. The present invention also relates to a color filter, a protective film, a photospacer, and a substrate for a liquid crystal display device using the photosensitive resin composition. Furthermore, the present invention relates to a liquid crystal display device and a solid-state imaging device using the color filter.

  Liquid crystal display devices are widely used in display devices that display high-quality images. A display device substrate (for example, a color filter substrate, an active matrix substrate, or the like) has a structure in which structures such as a colored pattern and a protective film are formed on the substrate. Among these structures, a method of forming a coloring pattern, a protective film, and a photospacer by photolithography using a photosensitive resin composition has become the mainstream.

  Various studies have been made on the photosensitive resin composition so far, for example, a photopolymerization using a copolymer of an ethylenically unsaturated carboxylic acid or the like and an ethylenically unsaturated compound and a specific photopolymerization initiator. A resin composition is disclosed (for example, see Patent Document 1). Further, from an aliphatic cyclic hydrocarbon group-containing copolymer having a molecular structure in which a structural unit having an aliphatic cyclic hydrocarbon group having a specific structure, a structural unit having an acidic functional group, and a structural unit having a radical polymerizable group are linked. A curable resin is disclosed (for example, see Patent Document 2).

  As one of methods for producing a color filter used in a liquid crystal display device, a pigment dispersion method is widely used. As a pigment dispersion method, there is a method of producing a color filter by a photolithography method using a photosensitive resin composition in which a pigment is dispersed in various photosensitive resin compositions. This method is stable to light and heat because it contains a pigment, and is patterned by a photolithographic method, so that the positional accuracy is sufficiently ensured, and for the production of color filters used in liquid crystal display devices and the like. This is the preferred method.

  As a colorant used for producing a color filter, not only pigments but also coloring compounds other than pigments such as dyes are widely studied. Among these, as dyes, compounds having a wide variety of dye bases such as triarylmethane dyes, pyromethene dyes, pyrimidineazo dyes, pyrazole azo dyes, xanthene dyes, phthalocyanine dyes are known (for example, patents). Reference 3-5).

Use of a dye as a colorant is useful in that the hue and brightness of a display image when an image is displayed can be increased by the color purity of the dye itself and the vividness of the hue.
Further, it is disclosed that when a specific anthraquinone compound is used as a dye, a color filter excellent in contrast and the like can be obtained (see, for example, Patent Document 6).

  On the other hand, a photosensitive resin composition using a colorant such as a dye and a resin binder having a specific structure having an unsaturated group is also known to have improved solvent resistance (for example, see Patent Document 7). Although the resin binder having a specific structure greatly contributes to performance improvement such as imparting photolithographic properties and various resistances, it is not sufficient.

JP 2007-86565 A Japanese Patent Laid-Open No. 2002-293737 JP 2008-292970 A JP 2007-039478 A Japanese Patent No. 3387541 JP 2001-108815 A JP 2009-169231 A

When a pattern structure (eg, photo spacer, colored pattern, etc.) and a protective film are formed on a substrate using a conventional photosensitive resin composition, polymerization and curing may be insufficient only by exposure. In some cases, it may be necessary to perform high-temperature heat treatment after exposure and development.
This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a photosensitive resin composition that is excellent in polymerization curability at the time of exposure, so-called exposure sensitivity is high, spectral characteristics are excellent, adhesion is high, and liquid crystal is excellent in specific resistance. To do.
Furthermore, for example, it aims at providing the photosensitive resin composition which can form the photo spacer excellent in the uniformity of cross-sectional shape and height uniformity, and the protective film excellent in uniformity and hardness.
Another object of the present invention is to provide a substrate for a liquid crystal display device that can suppress display unevenness when used in a liquid crystal display device, and a liquid crystal display device in which display unevenness is suppressed.

（一般式（Ａ）中、Ｒは水素原子またはメチル基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ水素原子、ハロゲン原子、シアノ基、アルキル基またはアリール基である。）
（４）前記アルカリ可溶性樹脂が、下記一般式（Ａ）で表される繰り返し単位および下記一般式（Ｂ）で表される繰り返し単位を有する、（１）または（２）に記載の感光性樹脂組成物。
一般式（Ａ）

（一般式（Ａ）中、Ｒは水素原子またはメチル基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ水素原子、ハロゲン原子、シアノ基、アルキル基またはアリール基を表す。）
一般式（Ｂ）

（一般式（Ｂ）中、Ｒは水素原子またはメチル基を表す。）
（５）前記アルカリ可溶性樹脂が、下記一般式（Ａ）で表される繰り返し単位、下記一般式（Ｂ）で表される繰り返し単位および下記一般式（Ｃ）で表される繰り返し単位を有する、（１）または（２）に記載の感光性樹脂組成物。
一般式（Ａ）

（一般式（Ａ）中、Ｒは水素原子またはメチル基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ水素原子、ハロゲン原子、シアノ基、アルキル基またはアリール基を表す。）
一般式（Ｂ）

（一般式（Ｂ）中、Ｒは水素原子またはメチル基を表す。）
一般式（Ｃ）

（一般式（Ｃ）中、Ｒは水素原子またはメチル基を表し、Ｘは２価の連結基を表し、Ａｃは（メタ）アクリロイルオキシ基を表す。）
（６）前記一般式（Ａ）で表される繰り返し単位、前記一般式（Ｂ）で表される繰り返し単位および前記一般式（Ｃ）で表される繰り返し単位のいずれかにおいて、Ｒがメチル基である、（３）〜（５）のいずれか１項に記載の感光性樹脂組成物。
（７）前記一般式（Ａ）で表される繰り返し単位において、Ｒがメチル基であり、Ｒ¹〜Ｒ⁵がいずれも水素原子である、（３）〜（６）のいずれか１項に記載の感光性樹脂組成物。
（８）（１）〜（７）のいずれか１項に記載の感光性樹脂組成物を用いてなるカラーフィルタ、保護膜、フォトスペーサーまたは液晶表示装置用基板。
（９）（２）〜（７）のいずれか１項に記載の感光性樹脂組成物を、支持体に適用し着色層を形成する着色層形成工程と、該着色層に対してパターン様の露光をして、潜像を形成する露光工程と、前記潜像が形成された着色層を現像してパターンを形成する現像工程と、を有するカラーフィルタの製造方法。
（１０）（８）に記載のカラーフィルタ、（９）に記載のカラーフィルタの製造方法により製造されたカラーフィルタ、保護膜、または、フォトスペーサーを具備してなる液晶表示装置または固体撮像素子。
（１１）下記一般式（１−１）で表される繰り返し単位、下記一般式（２−１）で表される繰り返し単位および下記一般式（３−１）で表される繰り返し単位を有する樹脂。
一般式（１−１）

一般式（２−１）

一般式（３−１）

（一般式（３−１）中、Ｘは２価の連結基を表し、Ａｃは（メタ）アクリロイルオキシ基を表す。）
（１２）前記樹脂を構成する繰り返し単位の９０モル％以上が、前記一般式（１−１）で表される繰り返し単位、前記一般式（２−１）で表される繰り返し単位および前記一般式（３−１）で表される繰り返し単位のいずれかである、（１１）に記載の樹脂。
（１３）前記樹脂は、前記一般式（１−１）で表される繰り返し単位を４０〜８０モル％、前記一般式（２−１）で表される繰り返し単位１５〜３０モル％を、前記一般式（３−１）で表される繰り返し単位を１〜３０モル％含む、（１１）または（１２）に記載の樹脂。 Under such circumstances, as a result of intensive studies by the inventor of the present application, by adopting an alkali-soluble resin contained in the photosensitive resin composition having two or more different polymerizable unsaturated groups, photo It has been found that the photocrosslinking during patterning by the lithography method and the thermal crosslinking during the heat treatment at a high temperature after the development process proceed sequentially, so that the crosslinked structure becomes dense and the above problems can be solved.
Specific means for achieving the above object are as follows.
(1) Alkali-soluble resin (A), polymerizable compound (B), and photopolymerization initiator (C) having a group having an acidic group and two or more different polymerizable unsaturated groups at least in the side chain A photosensitive resin composition comprising:
(2) The photosensitive resin composition according to (1), further comprising a colorant.
(3) The photosensitive resin composition according to (1) or (2), wherein the alkali-soluble resin has a repeating unit represented by the following general formula (A).
Formula (A)

(In General Formula (A), R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group. is there.)
(4) The photosensitive resin according to (1) or (2), wherein the alkali-soluble resin has a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (B). Composition.
Formula (A)

(In the general formula (A), R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, respectively. Represents.)
General formula (B)

(In general formula (B), R represents a hydrogen atom or a methyl group.)
(5) The alkali-soluble resin has a repeating unit represented by the following general formula (A), a repeating unit represented by the following general formula (B), and a repeating unit represented by the following general formula (C). (1) or the photosensitive resin composition as described in (2).
Formula (A)

(In the general formula (A), R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, respectively. Represents.)
General formula (B)

(In general formula (B), R represents a hydrogen atom or a methyl group.)
General formula (C)

(In general formula (C), R represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Ac represents a (meth) acryloyloxy group.)
(6) In any one of the repeating unit represented by the general formula (A), the repeating unit represented by the general formula (B), and the repeating unit represented by the general formula (C), R is a methyl group The photosensitive resin composition according to any one of (3) to (5), wherein
(7) In any one of (3) to (6), in the repeating unit represented by the general formula (A), R is a methyl group, and R ^{1 to} R ⁵ are all hydrogen atoms. The photosensitive resin composition as described.
(8) A color filter, a protective film, a photospacer, or a substrate for a liquid crystal display device using the photosensitive resin composition according to any one of (1) to (7).
(9) A colored layer forming step of applying the photosensitive resin composition according to any one of (2) to (7) to a support to form a colored layer, and a pattern-like pattern with respect to the colored layer A method for producing a color filter, comprising: an exposure step of exposing to form a latent image; and a developing step of developing a colored layer on which the latent image is formed to form a pattern.
(10) A liquid crystal display device or a solid-state imaging device comprising a color filter according to (8), a color filter manufactured by the method for manufacturing a color filter according to (9), a protective film, or a photospacer.
(11) Resin having a repeating unit represented by the following general formula (1-1), a repeating unit represented by the following general formula (2-1), and a repeating unit represented by the following general formula (3-1) .
General formula (1-1)

General formula (2-1)

Formula (3-1)

(In General Formula (3-1), X represents a divalent linking group, and Ac represents a (meth) acryloyloxy group.)
(12) 90 mol% or more of the repeating units constituting the resin are a repeating unit represented by the general formula (1-1), a repeating unit represented by the general formula (2-1), and the general formula The resin according to (11), which is any one of the repeating units represented by (3-1).
(13) The resin contains 40 to 80 mol% of the repeating unit represented by the general formula (1-1) and 15 to 30 mol% of the repeating unit represented by the general formula (2-1). Resin as described in (11) or (12) which contains 1-30 mol% of repeating units represented by General formula (3-1).

According to the present invention, it is excellent in polymerization curability at the time of exposure, so-called exposure sensitivity is high, a coloring pattern excellent in profile characteristics even in a short heat treatment time, a photo spacer excellent in uniformity in cross-sectional shape and uniformity in height, uniformity In addition, it has become possible to provide a photosensitive resin composition that can form a protective film having excellent hardness.
In addition, the present invention can provide a display device substrate capable of suppressing display unevenness when used in a display device, and a display device in which display unevenness is suppressed.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail, and the color filter, protective film, photospacer, display device substrate, and liquid crystal display device of the present invention using the same will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In this specification, (meth) acrylate is used in the meaning including both acrylate and methacrylate.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A) having a group having an acidic group and two or more different polymerizable unsaturated groups, a polymerizable compound (B), and a photopolymerization initiator ( C). The photosensitive resin composition of this invention can be further comprised using a coloring agent, an organic solvent, and various additives as needed.

In the following, the photosensitive resin composition of the present invention may be simply referred to as “the composition of the present invention” or “composition”.
In addition, unless otherwise specified, the alkyl group is an alkyl group having a substituent and an alkyl group having no substituent, and is a general term for a linear, branched, or cyclic alkyl group.

<Alkali-soluble resin (A)>
The alkali-soluble resin used in the present invention is characterized by having a group having an acidic group and two or more different polymerizable unsaturated groups.
The photosensitive resin composition of the present invention preferably contains the alkali-soluble resin (A) in a proportion of 10 to 50% by mass of the component excluding the solvent, and more preferably in a proportion of 15 to 45% by mass.
Examples of the acidic group include a carboxyl group, a sulfonic acid group, a hydroxy acid group, a salicylic acid group, and an acid ureido group, and a carboxyl group is more preferable. There may be only one kind of acidic group, or two or more kinds thereof may be contained.
The acidic group is preferably incorporated into the alkali-soluble resin as a repeating unit containing an acidic group. The repeating unit containing an acidic group is preferably contained in a proportion of 3 to 50 mol%, more preferably in a proportion of 10 to 40 mol%, and more preferably in a proportion of 15 to 35 mol%. More preferably it is included.
Examples of two or more different polymerizable unsaturated groups include ((meth) acryloyloxy group, vinyl group, cyclic unsaturated group, etc.), and include at least a (meth) acryloyloxy group and a vinyl group. preferable. Three or more polymerizable unsaturated groups may be used.
Two or more different polymerizable unsaturated groups are preferably incorporated into the alkali-soluble resin as repeating units each containing a polymerizable unsaturated group. The repeating unit containing a polymerizable unsaturated group is a total of repeating units containing a polymerizable unsaturated group, and is preferably 40 to 97 mol% and more preferably 50 to 90 mol% of the alkali-soluble resin. .
Furthermore, when two or more different polymerizable unsaturated groups include at least a repeating unit containing a (meth) acryloyloxy group and a repeating unit containing a vinyl group, the repeating unit containing a (meth) acryloyloxy group is 1 It is preferable that it is -30 mol% and the repeating unit containing a vinyl group is 40-80 mol%.

（一般式（Ａ）中、Ｒは水素原子またはメチル基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ水素原子、ハロゲン原子、シアノ基、アルキル基またはアリール基を表す。）
一般式（Ｂ）

（一般式（Ｂ）中、Ｒは水素原子またはメチル基を表す。）
一般式（Ｃ）

（一般式（Ｃ）中、Ｒは水素原子またはメチル基を表し、Ｘは２価の連結基を表し、Ａｃは（メタ）アクリロイルオキシ基を表す。） The alkali-soluble resin used in the present invention preferably has a repeating unit represented by the following general formula (A), and is represented by the repeating unit represented by the following general formula (A) and the following general formula (B). The repeating unit represented by the following general formula (A), the repeating unit represented by the following general formula (B), and the repeating unit represented by the following general formula (C) are more preferable. More preferably, it has.
Formula (A)

(In the general formula (A), R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, respectively. Represents.)
General formula (B)

(In general formula (B), R represents a hydrogen atom or a methyl group.)
General formula (C)

(In general formula (C), R represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Ac represents a (meth) acryloyloxy group.)

  R in the general formulas (A) to (C) is preferably a methyl group.

Specific examples of the halogen atom, alkyl group and aryl group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ include the following.

  Specific examples of the halogen atom include Cl, Br, and I. The alkyl group may be linear, branched, or cyclic, and includes a methyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, and the like, preferably having 1 to 7 carbon atoms. Examples of the aryl group include a phenyl group, a furyl group, and a naphthyl group.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each preferably a hydrogen atom, and more preferably all are hydrogen atoms.

X in the general formula (C) represents a divalent linking group, and is a linear, branched or cyclic, substituted or unsubstituted alkylene group, or the alkylene group, and —O—, —C (═O) — and A group consisting of a combination of at least one of —NH— is preferable. Examples of the substituent that the alkylene group may have include a hydroxyl group. As for carbon number of an alkylene group, 1-15 are preferable.
Ac in the general formula (C) is preferably a methacryloyloxy group.

  The alkali-soluble resin preferably has a repeating unit represented by the general formula (A) of 20 to 90 mol%, more preferably 40 to 80 mol%, preferably a repeating unit represented by the general formula (B). The repeating unit represented by the general formula (C) is preferably contained in an amount of 10 to 35 mol%, more preferably 15 to 30 mol%, and preferably 1 to 30 mol%.

The repeating unit represented by the general formula (A) is preferably a repeating unit represented by the following general formula (A-1).
Formula (A-1)

The repeating unit represented by the general formula (B) is preferably a repeating unit represented by the following general formula (B-1).
Formula (B-1)

（一般式（３−１）中、Ｘは２価の連結基を表し、Ａｃは（メタ）アクリロイルオキシ基を表す。）
一般式（３−１）におけるＸは、直鎖、分岐または環状の、置換または無置換のアルキレン基または、該アルキレン基と、−Ｏ−、−Ｃ（＝Ｏ）−および−ＮＨ−の少なくとも1種以上との組み合わせからなる基が好ましい。アルキレン基が有していてもよい置換基としては、例えば、水酸基が挙げられる。アルキレン基の炭素数は、１〜１５が好ましい。
一般式（３−１）におけるＡｃは、メタクリロイルオキシ基が好ましい。 The repeating unit represented by the general formula (C) is preferably a repeating unit represented by the following general formula (C-1).

(In General Formula (3-1), X represents a divalent linking group, and Ac represents a (meth) acryloyloxy group.)
X in the general formula (3-1) is a linear, branched or cyclic, substituted or unsubstituted alkylene group, or at least one of the alkylene group, -O-, -C (= O)-, and -NH-. A group consisting of a combination with one or more species is preferred. Examples of the substituent that the alkylene group may have include a hydroxyl group. As for carbon number of an alkylene group, 1-15 are preferable.
Ac in the general formula (3-1) is preferably a methacryloyloxy group.

（一般式（Ｄ）中、Ｒは水素原子またはメチル基を表し、Ａは有機基を表す。）
Ｒはメチル基が好ましい。
Ａは、直鎖、分岐または環状の、置換または無置換のアルキレン基が好ましい。アルキレン基としては、炭素数１〜２０が好ましい。また、置換基としては水酸基が好ましい。 Furthermore, the alkali-soluble polymer used in the present invention may contain other repeating units without departing from the spirit of the present invention. The other repeating unit is preferably 0 to 30 mol%, more preferably 0 to 20 mol%, and further preferably 0 to 10 mol% of the alkali-soluble polymer.
Such other repeating unit is preferably a repeating unit represented by the following general formula (D).
Formula (D)

(In general formula (D), R represents a hydrogen atom or a methyl group, and A represents an organic group.)
R is preferably a methyl group.
A is preferably a linear, branched or cyclic, substituted or unsubstituted alkylene group. As an alkylene group, C1-C20 is preferable. The substituent is preferably a hydroxyl group.

  It is preferable that the alkali-soluble resin used in the present invention does not substantially contain a repeating unit other than the repeating units represented by the general formulas (A) to (D). “Substantially free” means impurities and the like, and is usually 1 mol% or less.

The molecular weight of the alkali-soluble resin used in the present invention is not specifically defined, the weight-average molecular weight, preferably from 1000～2X10 ^5, more preferably 2000～1X10 ^5, is 5000～X10 ⁴ More preferably.

（一般式I中、Ｒは水素原子またはメチル基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ水素原子、ハロゲン原子、シアノ基、アルキル基またはアリール基である。） The alkali-soluble resin used in the present invention is preferably synthesized by polymerizing at least a monomer represented by the following general formula I.
Formula I

(In general formula I, R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group. )

（一般式II中、Ｒは水素原子またはメチル基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ水素原子、ハロゲン原子、シアノ基、アルキル基またはアリール基である。）
一般式III

（一般式II中、Ｒは水素原子またはメチル基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵は、それぞれ水素原子、ハロゲン原子、シアノ基、アルキル基またはアリール基を表し、Ｒ⁶は、炭素数２〜８のアルキレン基を表す。） The alkali-soluble resin used in the present invention is also preferably synthesized via the following general formula II or general formula III, and more preferably synthesized via the general formula II.
Formula II

(In General Formula II, R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ^4, and R ⁵ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group. )
Formula III

(In the general formula II, R represents a hydrogen atom or a methyl group, R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, respectively. R ⁶ represents an alkylene group having 2 to 8 carbon atoms.)

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formulas I to III have the same meanings as in the general formulas (A) to (C), respectively. The preferred range is also synonymous.

  The monomer represented by the general formula I is synthesized by esterifying an alcohol having an unsaturated group described below with an acryl group or a methacryl group.

  Representative compounds are allyl alcohol, 2-methylallyl alcohol, crotyl alcohol, 3-chloro-2-propen-1-ol, 3-phenyl-2-propen-1-ol, 3,3-diphenyl-2 -Propen-1-ol, 3-bromo-3-phenyl-2-propen-1-ol, 2-methyl-3-phenyl-2-propen-1-ol, 2-methyl-3,3-diphenyl-2 -Propen-1-ol, 2-ethyl-1,3-diphenyl-2-propen-1-ol, 2,3-diphenyl-2-propen-1-ol, 1,2,3-triphenyl-2- Propen-1-ol, 2,3,3-triphenyl-2-propen-1-ol, 1,3-diphenyl-2-propen-1-ol, 1,1,3-triphenyl-2-propene- 1 All, 1,1,3,3-tetraphenyl-2-propen-1-ol, 1-phenyl-2-propen-1-ol, 1,2-diphenyl-2-propen-1-ol, 1-phenyl 2-methyl-2-propen-1-ol, 1-cyclohexyl-2-propen-1-ol, 2-benzyl-2-propen-1-ol, 1-carboxy-2-propen-1-ol, 1 -Cyano-2-propen-1-ol, 3-cyclopentyl-2-propen-1-ol, 3-bromo-2-propen-1-ol, 2-methyl-3-chloro-2-propen-1-ol 2-methyl-3-bromo-2-propen-1-ol, 2-chloro-3-phenyl-2-propen-1-ol (2-chlorocinnamyl alcohol), 2-bromo-3-phenyl 2-propen-1-ol (2-bromocinnamyl alcohol), 2-fluoro-3-phenyl-2-propen-1-ol (2-fluorocinnamyl alcohol), 2-cyano-3-phenyl-2- Propen-1-ol (2-cyanocinnamyl alcohol), 2-chloro-2-propen-1-ol (2-chloroallyl alcohol), 2-bromo-2-propen-1-ol (2-bromoallyl alcohol) ), 2-bromo-3,3-difluoro-2-propen-1-ol, 2-chloro-3,3-difluoro-2-propen-1-ol, 2-fluoro-3-chloro-2-propene- Examples include 1-ol, 2,3-dibromo-2-propen-1-ol, and 2-chloro-3-methyl-2-propen-1-ol.

  The acidic group may be any vinyl-based compound containing an acidic group that can be copolymerized with a monomer having an unsaturated group represented by the general formula I. For example, “Polymer Data Handbook [ Fundamentals] ”Baifukan (1986) and the like. Specifically, acrylic acid, α and / or β-substituted acrylic acid (for example, α-acetoxy, α-acetoxymethyl, α- (2-amino) methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, α-chloro-β-methoxy, α, β-dichloro, etc.), methacrylic acid, itaconic acid, Itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid) , 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half ester, maleic acid half amides, vinyl benzene carboxylic acids, vinyl benzene sulfonic acids, vinyl sulfonic acid, vinyl phosphonic acid Vinyl or dicarboxylic acids half esters derivatives of allyl, and ester derivatives of these carboxylic acids or sulfonic acids, compounds containing acidic group in the substituent of the amide derivatives.

  The alkali-soluble resin used in the present invention includes at least a monomer represented by the general formula I and a monomer having at least an acidic group as shown in the general formulas II and III, and, if necessary, a hydroxyalkyl (meth) acrylate. A copolymer having the unsaturated group can be obtained by copolymerizing.

  Examples of the alkyl group of the hydroxyalkyl (meth) acrylate include an ethylene group, a propylene group, and a butylene group. Monomers used to introduce this structural unit include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxy Examples include butyl methacrylate.

  The (meth) acrylate-containing compound that reacts with the acidic group and / or the hydroxy group of the hydroxyalkyl (meth) acrylate may have a (meth) acrylate having an epoxy group or a (meth) acryloylalkyl isocyanate which may have a substituent, (Meth) acrylic acid chloride and the like.

  As the (meth) acrylate having an epoxy group, for example, a compound represented by the following structural formula (1) and a compound represented by the following structural formula (2) are preferable.

However, in said structural formula (1), R < ¹ > represents a hydrogen atom or a methyl group. L ¹ represents an organic group. L ¹ is a linear, branched or cyclic, substituted or unsubstituted alkylene group or a combination of the alkylene group and at least one of —O—, —C (═O) — and —NH—. And an alkylene group is more preferable. Examples of the substituent that the alkylene group may have include a hydroxyl group. 1-15 are preferable and, as for carbon number of an alkylene group, 1-4 are more preferable.

In the Structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group. L ² is a linear, branched or cyclic, substituted or unsubstituted alkylene group or a combination of the alkylene group and at least one of —O—, —C (═O) — and —NH—. And an alkylene group is more preferable. Examples of the substituent that the alkylene group may have include a hydroxyl group. 1-15 are preferable and, as for carbon number of an alkylene group, 1-4 are more preferable.

Of the compound represented by the structural formula (1) and the compound represented by the structural formula (2), the compound represented by the structural formula (1) is more preferable. In the structural formulas (1) and (2), it is more preferable that L ¹ and L ² are each independently an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) or a structural formula (2), For example, the following exemplary compounds (1)-(10) are mentioned.

  The (meth) acryloyl alkyl isocyanate compound which may have a substituent is a compound in which a (meth) acryloyl group is bonded to an isocyanate group (—NCO) via an alkylene group having 2 to 6 carbon atoms. Examples of 2-acryloyl ethyl isocyanate and 2-methacryloyl ethyl isocyanate. 2-Methacryloylethyl isocyanate is commercially available from “Karenz MOI” manufactured by Showa Denko K.K.

  Acrylic acid chloride and methacrylic acid chloride as a (meth) acrylic acid chloride compound are commercially available as manufactured by Tokyo Chemical Industry Co., Ltd.

  The alkali-soluble resin of the present invention may further be copolymerized with other monomers.

―Other monomers―
The other monomer is not particularly limited, and examples of the monomer containing a group having a branched and / or alicyclic structure include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (Meth) acrylamides etc. are mentioned, (meth) acrylates, vinyl esters, and (meth) acrylamides are preferable, and (meth) acrylates are more preferable. A specific example of the monomer is (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo-2,2,1-heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, and (meth) acrylic. Acid-3-methyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-1-adamantyl, (meth) acrylic acid-3-ethyladamantyl, (meth) acrylic acid-3-methyl-5-ethyl -1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid octahydro- 4,7-mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, (meth) acrylic acid-1-men , Tricyclodecyl (meth) acrylate, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3,1,1] heptyl, (meth) acrylic acid-3,7,7 -Trimethyl-4-hydroxy-bicyclo [4,1,0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fuentyl (meth) acrylate, (meth) acrylic acid-2,2 , 5-trimethylcyclohexyl and the like. Among these (meth) acrylic esters, cyclohexyl methacrylate, (nor) bornyl (meth) acrylic acid, isobornyl (meth) acrylate, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl , Futileyl methacrylate, 1-menthyl methacrylate, tricyclodecyl (meth) acrylate, etc., cyclohexyl methacrylate, (nor) bornyl methacrylate, isobornyl (meth) acrylate, (meth) acrylic acid-2-adamantyl Is particularly preferred.

In addition, monomers having a (meth) acrylic acid ester, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, hydrocarbon alkenyl group, etc. that do not have a branched and / or alicyclic structure can also be used. .
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned. There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  As content rate of the other monomer in the said resin, it is preferable that molar composition ratio is 0-30 mol%, It is more preferable that it is 0-20 mol%, It is 0-10 mol% Is more preferable.

  Specific examples of the alkali-soluble resin used in the present invention include compounds represented by the following compounds P-1 to P-18.

<(B) Polymerizable compound>
The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition, as disclosed in JP-A-2006-23696. Examples include the components described in paragraph numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

In addition, a urethane-added polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. JP-A-51-37193, JP-B-2-32293, JP-B-2-16765 And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) 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 obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK Oligo UA-7200 (above, Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M Preferred examples include -402, TO-1382 (manufactured by Toagosei Co., Ltd.), and V # 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
These polymerizable compounds can be used alone or in combination of two or more.

  The content of the polymerizable compound in the total solid content of the photosensitive resin composition (the total content in the case of 2 or more types) is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass. Preferably, 20% by mass to 60% by mass is particularly preferable.

<(C) Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound. A compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable. In addition, a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.

Specifically, for example, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide), benzophenone compounds, acetophenone compounds, and derivatives thereof.
Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.

  Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, WO 2005/080337, WO 2006/018933, JP The compounds described in JP 2007-210991 A, JP 2007-231000 A, JP 2007-2699779 A, JP 2009-191061 A, and International Publication No. 2009/131189 can be used.

  Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  In the present invention, a compound represented by the following general formula (III) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

In general formula (III), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ is —R, —OR, —COR, —SR, —CONRR. 'Or -CN, and R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.

In the general formula (III), when X ¹ , X ² , and X ³ represent a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X ³ are Examples of the alkyl group in the case of representing an alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2 -Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl , Monofluoromethyl, difluoromethyl , Trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Especially, it is preferable that all of X < ¹ >, X < ² > and X < ³ > represent a hydrogen atom, or X < ¹ > represents an alkyl group and X < ² > and X < ³ > both represent a hydrogen atom.

In the general formula (III), examples of the alkyl group represented by R and R ′ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, and tertiary amyl. , Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxy Examples include ethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R ² and R ^{3 including} R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—. Br is a particularly preferred embodiment.

(C) Among the photopolymerization initiators, in the general formula (III), X ¹ , X ² and X ³ are all hydrogen atoms; R ¹ is an alkyl group, particularly a methyl group; Those in which R ² is an alkyl group, particularly a methyl group; those in which R ³ is an alkyl group, particularly an ethyl group, are particularly suitable as a photopolymerization initiator.

  Accordingly, preferred specific examples of the photopolymerization initiator represented by the general formula (III) include compounds A to F exemplified below. However, the present invention is not limited by the following compounds.

  The photopolymerization initiator represented by the general formula (III) can be synthesized, for example, by the method described in JP-A-2005-220097.

  The compound represented by the general formula (III) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  In the present invention, a compound represented by the following general formula (II) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

In general formula (II), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0-5. X ²² represents a monovalent substituent, and when n is an integer of 2 to 4, a plurality of X ²² may be the same or different.

The monovalent substituent represented by R ²² is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ²² include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylsulfonyl group which may have a substituent, Examples include an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or a trifluoromethyl group. , Etc.

  The aryl group that may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.

R ²² is more preferably an unsubstituted or substituted acyl group from the viewpoint of high sensitivity, and specifically, an unsubstituted or substituted acetyl group, propionyl group, benzoyl group, toluyl group. Groups are preferred.
As said substituent, the group represented by the following structural formula is mentioned, for example, Among these, any of (d-1) (d-4) and (d-5) is preferable.

The divalent linking group represented by A ²² may have a C 1-12 alkylene which may have a substituent, a cyclohexylene which may have a substituent, or a substituent. Alkynylene is mentioned.
Examples of the substituent that can be introduced into these groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Examples include aryloxy groups such as a tolyloxy group, alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.

Among them, the A ²² is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring due to heating. Alkylene group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, An alkylene group substituted with a styryl group) is preferred.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, Ar is a phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m. -, P-cumenyl group, mesityl group and the like. Among them, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy such as methoxy group, ethoxy group and tert-butoxy group. Groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acetoxy groups, propionyloxy groups, acyloxy groups such as benzoyloxy groups, acetyl groups, Benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylamino group, cyclohexylamino group and other alkylamino groups, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino groups, Fe Arylamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group, a hydroxy group, a carboxy group, and the like.

  In the general formula (III), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

Examples of the monovalent substituent represented by X ²² include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, and a substituent A good arylthiooxy group, a halogen atom and the like can be mentioned.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl. Group, 2-ethylhexyl group, phenacyl group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable. For example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quarterphenyl group, o-, m-, and p-tolyl groups, xylyl groups, and the like.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a benzyloxy group. .

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, etc. are mentioned.

  The alkylthiooxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, an isopropylthiooxy group, a butylthiooxy group Group, isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, 2-ethylhexyl Examples include a thiooxy group, a decylthiooxy group, a dodecylthiooxy group, an octadecylthiooxy group, and a benzylthiooxy group.

  The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, such as a phenylthiooxy group, a 1-naphthylthiooxy group, a 2-naphthylthiooxy group, 2 -Chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-cyano Phenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanyl Phenylthiooxy group, 4-phenylsulfanylphenyl There is thiooxyacids group, and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group. Etc.

  Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.

Among these, X ²² has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of solvent solubility and improvement in absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio which may have a substituent An oxy group, an arylthiooxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent, or a substituent on N A good amide group is preferable, and an alkyl group which may have a substituent is more preferable.

Moreover, although n in general formula (III) represents the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of a synthesis | combination, and the integer of 0-2 is more preferable.
In formula (III), if X ²² there are a plurality, the plurality of X ²² may be the same or may be different.

  Specific examples of the oxime photopolymerization initiator represented by the general formula (III) are shown below.

  The compound represented by the general formula (III) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5'-tetraphenyl Imidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  A photoinitiator can be used 1 type or in combination of 2 or more types. When using 2 or more types, multiple types of compounds represented by general formula (III) may be used, and multiple types of compounds represented by general formula (II) may be used. Moreover, you may use at least 1 sort (s) from the compound represented by general formula (II) and (III), respectively. In addition, at least one compound represented by the general formulas (II) and (III) and an oxime compound other than the compounds represented by the general formulas (II) and (III) or photopolymerization other than the oxime compound are started. An agent may be used. Moreover, you may use a sensitizer together.

  The total content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to the total solid content in the photosensitive resin composition. More preferably, 1% by mass to 5% by mass is most preferable. Within this range, the sensitivity during exposure is high and the color characteristics are also good.

<Sensitizer>
A sensitizer can also be added to the photosensitive resin composition of the present invention. Typical sensitizers used in the present invention include Krivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)]. Specific examples include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10. -Dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.

<Multifunctional thiol compound>
The photosensitive resin composition of the present invention may contain a polyfunctional thiol compound.
The photosensitive resin composition of the present invention includes a polyfunctional thiol compound to increase sensitivity, suppress ion elution caused by a coloring material such as a dye, and the like. When the resin composition is used, image quality deterioration such as crosstalk can be prevented, and clear and high-quality display is possible. In addition, since the color filter using the photosensitive resin composition of the present invention can have an appropriate taper in the pattern shape, there is no disconnection of the transparent electrode even when the transparent electrode is provided, and the colored pixels in pattern development No protrusion is generated, and the linearity of the pattern is good. By providing a color filter using the photosensitive resin composition of the present invention, a high-quality liquid crystal display device can be obtained.

  In the present invention, the “polyfunctional thiol compound” means a compound having two or more thiol groups in the molecule. As the polyfunctional thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1500 is preferable, and 150 to 1000 is more preferable. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, and more preferably 2 to 6 thiol groups. In addition, these compounds are preferably used as a system that is used auxiliary when the radical polymerizable monomer is polymerized. Specifically, the addition amount of the polyfunctional thiol compound is 1 to 20% by mass relative to the total solid content of the composition, or less than the addition amount of the radical polymerizable monomer contained at the same time. It is preferable to make it an addition amount.

  In the present invention, the (B) polyfunctional thiol compound is preferably a compound having two or more groups represented by the following general formula (2).

（一般式（２）中、Ｒは水素原子、またはアルキル基を表し、Ａは−ＣＯ−、または−ＣＨ₂−を表す。）

(In General Formula (2), R represents a hydrogen atom or an alkyl group, and A represents —CO— or —CH ₂ —.)

(B) As a polyfunctional thiol compound, the compound which has 2-6 the group represented by General formula (2) is preferable, and the compound which has 2-4 is more preferable.
The alkyl group for R in the general formula (2) is a linear, branched, or cyclic alkyl group, and the carbon number is preferably 1 to 16, more preferably 1 to 10. . Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and 2-ethylhexyl group. And a methyl group, an ethyl group, a propyl group, and an i-propyl group are preferable.
R is particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or an i-propyl group, and most preferably a methyl group or an ethyl group.

  In the present invention, the (B) polyfunctional thiol compound is particularly preferably a compound represented by the following general formula (1) having a plurality of the general formula (2).

（一般式（１）中、Ｒは水素原子、またはアルキル基を表し、Ａは−ＣＯ−、または−ＣＨ₂−を表す。Ｌはｎ価の連結基を表し、ｎは２〜６の整数を表す。）

(In General Formula (1), R represents a hydrogen atom or an alkyl group, A represents —CO— or —CH ₂ —, L represents an n-valent linking group, and n represents an integer of 2 to 6. Represents.)

The alkyl group in R in General formula (1) is synonymous with R in the said General formula (1), and its preferable range is also the same. n is preferably from 2 to 4.
As L which is an n-valent linking group in the general formula (1), for example, a divalent linking group such as — (CH ₂ ) m— (m is 2 to 6), a trimethylolpropane residue, — (CH ₂ ) Trivalent linking group such as isocyanur ring having 3 p- (p is 2 to 6), pentavalent linking group such as tetravalent linking group such as pentaerythritol residue, dipentaerythritol residue And hexavalent linking groups.

  (B) Specific examples of the polyfunctional thiol compound include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). Nate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Multifunctional thiol compound suitable for And the like as.

  The content of the polyfunctional thiol compound is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total solid content in the photosensitive resin composition. When the content of the polyfunctional thiol compound is within this range, the sensitivity of the photosensitive resin composition is good, the storage stability is good, the pixel adhesion in the obtained color filter is good, and there is no pattern defect. A photosensitive resin composition having good electrical characteristics when used in a liquid crystal display device can be provided.

(Coloring agent)
The colorant may be any of a pigment, a dye, or a mixed system of a pigment and a dye.

<Pigment>
As the pigment, various conventionally known inorganic pigments or organic pigments can be used, but it is preferable to use organic pigments from the viewpoint of reliability. In the present invention, examples of the organic pigment include organic pigments described in paragraph [0093] of JP2009-256572A.
In particular,
C. I. Pigment Red 177, 224, 242, 254, 255, 264,
C. I. Pigment Yellow 138, 139, 150, 180, 185,
C. I. Pigment Orange 36, 38, 71,
C. I. Pigment Green 7, 36, 58,
C. I. Pigment Blue 15: 6,
C. I. Pigment Violet 23
Is preferable from the viewpoint of color reproducibility, but the present invention is not limited thereto. These organic pigments can be used alone or in various combinations in order to increase color purity.
As the pigment, a pigment having an average primary particle size of 10 nm to 30 nm is preferable. A photosensitive resin composition excellent in hue and contrast is obtained in the above embodiment.

  When a pigment is used, the content of the pigment in the photosensitive resin composition of the present invention is preferably 0.5 to 50% by mass, and 1 to 30% by mass with respect to the total solid content of the composition. Is more preferable. When the pigment content is within the above range, it is effective to ensure excellent color characteristics.

(dye)
Examples of the dye that may be contained in the photosensitive resin composition of the present invention include methine series, pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, dipyrromethene metal complex compounds, pyra. Zorotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, squarylium, phthalocyanine, benzopyran, indigo, and the like.

  Specific examples of the dye that may be contained in the photosensitive resin composition of the present invention include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, and JP-A-6. No. 11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, No. 333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316. JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-2777. No. 1, JP-A-8-146215, JP-A-11-343437, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222 JP-A-2002-14223, JP-A-8-302224, JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, JP-A-6-230210, etc. It is the described dye.

  Suitable dyes that may be included in the photosensitive resin composition of the present invention include the following.

(Methine series)

(Dipyrromethene metal complex compound)
The dipyrromethene metal complex compound in which the compound represented by formula (I) is coordinated to a metal atom or a metal compound will be described in detail.

（一般式（Ｉ）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、およびＲ⁶は、各々独立に、水素原子、または１価の置換基を表し、Ｒ⁷は水素原子、ハロゲン原子、アルキル基、アリール基、またはヘテロ環基を表す。）

(In the general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ is a hydrogen atom, Represents a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

  Examples of the monovalent substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, straight chain, branched chain, Or a cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, for example, vinyl Group, allyl group, 3-buten-1-yl group), aryl group (preferably having 6 to 48 carbon atoms, more preferably carbon number) An aryl group having from 24 to 24, for example, a phenyl group, a naphthyl group, a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group, such as a 2-thienyl group, 4 -Pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably carbon number) 3 to 38, more preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), hydroxyl group, cyano group A nitro group or an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, For example, if it is a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a tert-butoxy group, a dodecyloxy group, or a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group ), An aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group and 1-naphthoxy group), a heterocyclic oxy group (preferably having a carbon number of 1 to 32, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group and 2-tetrahydropyranyloxy group, silyloxy group (preferably having 1 to 32 carbon atoms, and more). Preferably it is a C1-C18 silyloxy group, for example, a trimethylsilyloxy group, a tert-butyl group. Tildimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodeca group. Noyloxy group), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, If it is an alkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, Phenoxycarbonyloxy group), carbamoyloxy group (preferably carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group) N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms, For example, an N, N-diethylsulfamoyloxy group, an N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms). For example, methylsulfonyloxy group, hexadecylsulfonyloxy Group, cyclohexylsulfonyloxy group), arylsulfonyloxy group (preferably arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenylsulfonyloxy group), acyl group (preferably carbon An acyl group having 1 to 48, more preferably 1 to 24 carbon atoms, such as a formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), an alkoxycarbonyl group (preferably carbon An alkoxycarbonyl group having 2 to 48, more preferably 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, or 2,6-di-tert-butyl-4 -Methylcyclohexyloxycarbonyl Group), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyl group), carbamoyl group (preferably having 1 to 48 carbon atoms, More preferably, it is a carbamoyl group having 1 to 24 carbon atoms, such as carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Amino group, methylamino group, N, N-dibutylamino group, tetradecylamino , 2-ethylhexylamino group, cyclohexylamino group), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24, for example, anilino group, N-methylanilino group), a heterocyclic amino group (Preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 4-pyridylamino group), a carbonamide group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms. An amide group, for example, an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably a C1-C32, more preferably a C1-C24 ureido group, Ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably Is an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as an N-succinimide group or an N-phthalimide group, or an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably 2 carbon atoms). To 24 alkoxycarbonylamino groups, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably carbon An aryloxycarbonylamino group having 7 to 32, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonylamino group, and a sulfonamide group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Sulfonamide Group, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably carbon number) 1 to 24 sulfamoylamino groups such as N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group, azo group (preferably having 1 to 32 carbon atoms) Preferably an azo group having 1 to 24 carbon atoms, such as a phenylazo group or a 3-pyrazolylazo group), an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, Methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably Or an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 18 carbon atoms). A ring thio group, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). An alkylsulfinyl group such as dodecanesulfinyl group), 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 a phenylsulfinyl group), an alkylsulfonyl group (preferably Is an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Tylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 6 carbon atoms) 48, more preferably an arylsulfonyl group having 6 to 24 carbon atoms, such as a phenylsulfonyl group or a 1-naphthylsulfonyl group, a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms). Sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo Group A sulfonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a phenoxyphosphonyl group, an octyloxyphosphonyl group, a phenylphosphonyl group), a phosphinoylamino group (preferably Is a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, diethoxyphosphinoylamino group, dioctyloxyphosphinoylamino group).

  When the above-described monovalent group is a group that can be further substituted, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

In the general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5, 6 or 7 members. The ring may be formed. In addition, as a ring formed, there is a saturated ring or an unsaturated ring. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they may be substituted with any of the substituents R, and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
In the general formula (I), when R ⁷ is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges are the halogen atom, alkyl group, R ^{1 to} R ⁶ described above, This is the same as the preferred range of the aryl group or heterocyclic group.

In the general formula (I), R ¹ and R ⁶ are preferably alkylamino group, arylamino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, and sulfonamido group. An amide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.

In the general formula (I), as R ² and R ⁵ , among the above, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group Preferred are alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoyl. A sulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In general formula (I), R ³ and R ⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and more preferably A substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;

In general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. More specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group , A cyclohexyl group, and a benzyl group, more preferably a branched chain having 1 to 12 carbon atoms, or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, isopropyl group, cyclopropyl Group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group, more preferably 1 to 1 carbon atoms. 2 is a secondary or tertiary substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group, a cyclopropyl group, an i-butyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group. It is done.

In the general formula (I), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, more preferably Is a substituted or unsubstituted phenyl group.
When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 3 -Pyridyl group, substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1 -An imidazolyl group, a substituted or unsubstituted 1-pyrazolyl group, a substituted or unsubstituted benzotriazol-1-yl group, more preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4- Examples include a pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, and a substituted or unsubstituted 1-pyridyl group.

Next, the metal atom or metal compound that forms the dipyrromethene-based metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, in addition to B, such as, AlCl, InCl, FeCl, TiCl 2, SnCl 2, SiCl 2 Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is more preferable. Most preferred. Among these, Zn is particularly preferable.

In the dipyrromethene metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, preferred embodiments are shown below. That is, in general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone An amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, Atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydro Sil group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group , An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, Aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group , Alkoxycarbonylamino group Sulfonamide group, represented by azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group or a phosphinoylamino group,, R ⁷ is a hydrogen atom, a halogen atom, an alkyl Group, aryl group, or heterocyclic group, and a metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO An embodiment is mentioned.

The more preferable aspect of a dipyrromethene type metal complex compound is shown below. That is, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, Amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide Group, alkylsulfonyl group, arylsulfonyl group, or sulfo Represented by Amoiru group, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, Represented by a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, R ⁷ is a hydrogen atom, a halogen atom , An alkyl group, an aryl group, or a heterocyclic group, and the metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.

  Preferred embodiments of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound include the following general formulas (I-1), (I-2), and (I-3) ).

（一般式（Ｉ−１）において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、およびＲ⁶は、各々独立に、水素原子、または置換基を表す。Ｒ⁷は、水素原子、ハロゲン原子、アルキル基、アリール基、またはヘテロ環基を表す。Ｍａは、金属原子または金属化合物を表し、Ｘ¹は、Ｍａに結合可能な基を表し、Ｘ²は、Ｍａの電荷を中和するために必要な基を表す。なお、Ｘ¹とＸ²とは、互いに結合して５員、６員、または７員の環を形成していてもよい。）

(In General Formula (I-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ is a hydrogen atom, Represents a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, and X ² neutralized the charge of Ma. And X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring.)

R < ¹ > -R < ⁶ > in General formula (I-1) is synonymous with R < ¹ > -R < ⁶ > in General formula (I), and its preferable aspect is also the same.
Ma in the general formula (I-1) represents a metal atom or a metal compound, and the metal atom or metal compound in the “complex in which the compound represented by the general formula (I) is coordinated to the metal atom or metal compound” The preferred range is also the same.
Formula (I-1) R ⁷ in has the same meaning as R ⁷ in formula (I), preferable embodiments thereof are also the same.

X ¹ in the general formula (I-1) may be any group as long as it is capable of binding to Ma, such as water, alcohols (for example, methanol, ethanol, propanol) and the like, and “metal chelate” [1 ] Groups derived from the compounds described in Takeichi Sakaguchi and Keihei Ueno (1995 Nanedou), [2] (1996), [3] (1997), and the like. Among these, water, carboxylic acid compounds, alcohols, amine compounds, and amide compounds are preferable from the viewpoint of production, and water, carboxylic acid compounds, and amide compounds are more preferable.

X ^{2 in the} general formula (I-1) represents a group necessary for neutralizing the electric charge of Ma, such as a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxyl group, aliphatic imide. A monovalent group derived from (for example, succinimide, maleimide, glutarimide, diacetamide, etc., preferably succinimide, maleimide), an aromatic imide group or a heterocyclic imide (for example, phthalimide, Naphthalimide, 4-bromophthalimide, 4-methylphthalimide, 4-nitrophthalimide, naphthalenecarboximide, tetrabromophthalimide, etc., preferably phthalimide, 4-bromophthalimide, 4-methylphthalimide) Valent groups, aromatic carboxylic acids (eg benzoic acid, 2-methoxy Benzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-tert-butyl Benzoic acid, etc., preferably monovalent groups derived from benzoic acid, 4-methoxybenzoic acid, salicylic acid, etc., aliphatic carboxylic acids (eg, formic acid, acetic acid, acrylic acid, methacrylic acid, ethanoic acid) , Propanoic acid, lactic acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyloctadecanoic acid, 2 -Hexyldecanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene- 2-carboxylic acid, 1-adamantanecarboxylic acid, etc., preferably monovalent group derived from acetic acid, methacrylic acid, lactic acid, pivalic acid, 2-ethylhexanoic acid, stearyl acid, etc.), dithiocarbamic acid ( For example, a monovalent group derived from dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibenzyldithiocarbamic acid), sulfonamide (for example, benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 4- A monovalent group derived from methylbenzenesulfonamide, 2-methylbenzenesulfonamide, and methanesulfonamide, preferably benzenesulfonamide and methanesulfonamide), hydroxamic acid (for example, acetohydroxamic acid) Monovalent groups derived from octanohydroxamic acid and benzohydroxamic acid, nitrogen-containing ring compounds (hydantoin, 1-benzyl-5-ethoxyhydantoin, 1-allylhydantoin, 5,5-diphenylhydantoin, 5,5 -Dimethyl-2,4-oxazolidinedione, barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzimidazole, diethyl 1H-imidazole-4,5-dicarboxylate, etc. And preferably 1-benzyl-5-ethoxyhydantoin, 5,5-dimethyl-2,4-oxazolidinedione, 4,5-dicyanoimidazole, diethyl 1H-imidazole-4,5-dicarboxylate) Represents a valent group.
Among them, in terms of production, a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, and a nitrogen-containing ring compound are preferable, and a hydroxyl group and an aliphatic carboxylic acid group An aromatic imide group and a nitrogen-containing ring compound are more preferable.

X ¹ and X ² in formula (I-1) 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 are heterocycles having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, which may be composed of only carbon and hydrogen atoms. There may be.

In the general formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are each independently Represents a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound.

R < ¹ > -R < ⁶ > in General formula (I-2) is synonymous with R < ¹ > -R < ⁶ > in General formula (I), and its preferable aspect is also the same.
The substituent represented by R ^{8 to} R ¹³ in the general formula (I-2) is synonymous with the substituent represented by R ^{1 to} R ⁶ of the compound represented by the general formula (I). The preferred embodiment is also the same. When the substituents represented by R ^{8 to} R ¹³ of the compound represented by the general formula (I-2) are further substitutable groups, they may be substituted with any of the substituents R described above. In the case of being substituted with two or more substituents, those substituents may be the same or different.

Formula (I-2) R ⁷ in has the same meaning as R ⁷ in formula (I), preferable embodiments thereof are also the same.
R ¹⁴ in the general formula (I-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a preferable range of R ^{14 is} the same as the preferable range of R ⁷ . When R ¹⁴ is a further substitutable group, it may be substituted with any of the aforementioned substituents R, and when it is substituted with two or more substituents, those substituents are They may be the same or different.

  Ma in the general formula (I-2) represents a metal or a metal compound, and a metal atom or a metal compound in the “complex in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound” It is synonymous and the preferable range is also the same.

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ in formula (I-2) are each independently bonded to each other to form a 5-membered, 6-membered, or 7-membered compound. A membered saturated ring or an unsaturated ring may be formed. The saturated or unsaturated ring formed is synonymous with the saturated or unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ^6. The preferred examples are also the same.

In the general formula (I-3), R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, Represents 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 alkylamino group, an arylamino group, or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or Represents a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, Represents a sulfur atom or a carbon atom. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed.

R ² to R ⁵ in formula (I-3), and R ⁷ of the general formula (I) R ² ~R ⁵ in, and R ⁷ in the above formula, preferable embodiments thereof are also the same.
Ma in the general formula (I-3) represents a metal or a metal compound, and has the same meaning as the metal atom or the metal compound in the complex in which the compound represented by the general formula (I) is coordinated to the metal atom or the metal compound. The preferred range is also the same.

In general formula (I-3), R ⁸ and R ⁹ are each independently an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms). For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl Group), an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably a carbon number). An aryl group having 6 to 36, more preferably 6 to 18, for example, a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably Is a 1-12 heterocyclic group, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl Group, benzotriazol-1-yl group), alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy Group, 2-ethylhexyloxy group, dodecyloxy group, cyclohexyloxy group), aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as a phenoxy group or a naphthyloxy group). An alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, , Methylamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, tert-butylamino group, tert-octylamino group, cyclohexylamino group, N, N -Diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl-N-ethylamino group), arylamino group (preferably having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms) An arylamino group such as a phenylamino group, a naphthylamino group, an N, N-diphenylamino group, an N-ethyl-N-phenylamino group, or a heterocyclic amino group (preferably having 1 to 24 carbon atoms, Preferably it is a 1-12 heterocyclic amino group, for example, 2-aminopyrrole group, 3-aminopyrazo Le represents group, 2-aminopyridine group, a 3-aminopyridine group).

In general formula (I-3), an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R ⁸ and R ⁹ Is a further substitutable group, it may be substituted with any of the substituents R, and when it is substituted with two or more substituents, these substituents are the same. It may or may not be.

In general formula (I-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom, or a sulfur atom. Ra is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 24 carbon atoms, more Preferably it is a 2-12 alkenyl group, for example, a vinyl group, an allyl group, 3-buten-1-yl group), an aryl group (preferably a C6-C36, more preferably a 6-18 aryl group, For example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), acyl A group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, for example, acetyl group, pivaloyl group, 2-ethylhexyl group, benzoyl group, cyclohexanoyl group), alkylsulfonyl group (preferably carbon An alkylsulfonyl group having 1 to 24, more preferably 1 to 18, for example, a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, a cyclohexylsulfonyl group, an arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably Is an arylsulfonyl group of 6 to 18, for example, phenylsulfonyl Group, a naphthylsulfonyl group). Further, when Ra can be substituted, it may be further substituted with a substituent, and when it is substituted with a plurality of substituents, these substituents may be the same or different.
X ³ and X ⁴ are preferably each independently an oxygen atom or a sulfur atom, and X ³ and X ⁴ are particularly preferably both oxygen atoms.

In General Formula (I-3), Y ¹ and Y ² each independently represent NRb, a sulfur atom, or a carbon atom, and Rb has the same meaning as Ra in X ³ .
Y ¹ and Y ² are preferably each independently NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ² are particularly preferably both NH.

In general formula (I-3), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ , and the carbon atom, a 5-membered ring (eg, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole) , Furan, thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline) Or a 7-membered ring (eg, cycloheptane, hexamethyleneimine).

In General Formula (I-3), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. Examples of the 5-membered, 6-membered, and 7-membered rings include rings in which one bond in the ring formed by R ⁸ , Y ^1, and a carbon atom is changed to a double bond.

In the general formula (I-3), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are further substitutable rings May be substituted with the group described in any of the substituents R, and when it is substituted with two or more substituents, these substituents may be the same or different. Good.

In General Formula (I-3), X ⁵ represents a group capable of binding to Ma, and examples thereof include the same groups as X ² in General Formula (I-1). a represents 0, 1, or 2.

Preferred embodiments of the compound represented by formula (I-3) are shown below. That is, R ^{2 to} R ⁵ , R ⁷ , and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are Each independently NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group) or an oxygen atom, and Y ¹ and Y ² are each independently NRb (Rb is a hydrogen atom or an alkyl group), a nitrogen atom, or A carbon atom, X ⁵ is a group bonded through an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group. R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring, a is 0 Or it is an aspect represented by 1.

The more preferable aspect of a compound represented by general formula (I-3) is shown below. That is, R ^{2 to} R ⁵ , R ⁷ and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are oxygen atoms. Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is an oxygen atom or a group bonded through a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, Represents an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, and R ⁹ and Y ² are bonded to each other A forms a 5-membered or 6-membered ring, and a is an embodiment represented by 0 or 1.

  The general formulas (I-1), (I-2) and (I-) are preferred embodiments of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound. Among the complex compounds represented by 3), the complex compound represented by the general formula (I-3) is a particularly preferred embodiment.

  Hereinafter, specific examples of the dipyrromethene metal complex compound in which the compound represented by the general formula (I) used in the present invention is coordinated to a metal atom or a metal compound are shown. However, the present invention is not limited to these.

  Among the exemplary compounds of the dipyrromethene metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, the exemplary compounds (40) to (44) are represented by the general formula (I-1). It is also an exemplary compound, exemplary compound (45) is also an exemplary compound of general formula (I-2), and exemplary compounds (1)-(39) are also exemplary compounds of general formula (I-3).

  In addition to the above exemplary compounds, exemplary compounds (Ia-3) to (Ia-83), (Ia-1) to (IIa-20), (I-1) described in JP-A-2008-292970 To (I-36) (II-1) to (II-11) and (III-1) to (III-103), exemplified compounds (I-1) to (I-35) described in Japanese Patent No. 3324279 Exemplified compounds (I-1) to (I-13) described in Japanese Patent No. 3279035, Exemplified compounds (2-1) to (2-32) and (3-1) described in JP-A No. 11-256057 To (3-32), (4-1) to (4-26), and (5-1) to (5-26), exemplified compound (I-1) described in JP-A-2005-77953, (I-6) and (VII-1) to (VII-8), JP-A-11-352686 Listed in Exemplified Compounds (1-1) to (1-45), Exemplified Compounds (1-1) to (1-50) described in JP-A No. 2000-19729, and JP-A No. 11-352585. Exemplified compounds (1-1) to (1-45) are also examples of dipyrromethene-based metal complex compounds in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.

(Triarylmethane)

(Xanthene)

(Phthalocyanine series)

In the following compound abbreviations, Pc represents a phthalocyanine nucleus, Zn represents a central metal, represents a substituent substituted at the α-position immediately after Pc, and substituted at the β-position after the substituent substituted at the α-position. Represents a substituent and represents a substituent independent of the substitution position. x and y are positive numbers whose number of substituents is 0 or more.

(Anthraquinone)

(Organic solvent)
The photosensitive resin composition of the present invention can contain an organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the applicability when a photosensitive resin composition is used. In view of safety, it is preferably selected.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propylpyruvate, a DOO methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

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

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

  The content of the organic solvent in the photosensitive resin composition is preferably such that the total solid concentration in the photosensitive resin composition is 10% by mass to 80% by mass, and 15% by mass to 60% by mass. Is more preferable.

(Surfactant)
The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph No. 0058 of JP-A-2009-098616, and among these, fluorine-based surfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (made by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.
Further, the surfactant includes a structural unit A and a structural unit B represented by the following formula (W), and has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography using tetrahydrofuran as a solvent. A preferred example is a copolymer having a molecular weight of 000 to 10,000.

（式（Ｗ）中、Ｒ¹およびＲ³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ²は炭素数１〜４の直鎖アルキレン基を表し、Ｒ⁴は水素原子または炭素数１〜４のアルキル基を表し、Ｌは炭素数３〜６のアルキレン基を表し、ｐおよびｑは重合比を表す重量百分率であり、ｐは１０重量％〜８０重量％の数値を表し、ｑは２０重量％〜９０重量％の数値を表し、ｒは１〜１８の整数を表し、ｎは１〜１０の整数を表す。）

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

L is preferably a branched alkylene group represented by the following formula (W-2). R ⁵ in Formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. More preferred is an alkyl group of 3.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 to 5,000.

These surfactants can be used alone or in combination of two or more.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 0.01 to 2.0% by mass, particularly 0.02 to 1.0% by mass in the total solid content of the photosensitive resin composition. preferable. Within this range, the coatability and the uniformity of the cured film are good.

(Adhesion improver)
The photosensitive resin composition of the present invention may contain an adhesion improving agent.
The adhesion improver improves the adhesion between the inorganic material serving as the support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the photosensitive resin composition layer. A compound. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
0.1-20 mass% is preferable with respect to the total solid content of the photosensitive resin composition, and, as for content of the adhesion improving agent in the photosensitive resin composition of this invention, 0.2-5 mass% is more preferable. .

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

(Development accelerator)
A development accelerator can also be added in order to promote the alkali solubility of the non-exposed area when the photosensitive resin composition layer is exposed and to further improve the developability of the photosensitive resin composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
If necessary, the photosensitive resin composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
In the photosensitive resin composition of the present invention, the light stabilizer described in paragraph No. [0078] of JP-A No. 2004-295116 and the thermal polymerization inhibitor (polymerization inhibitor) described in paragraph No. [0081] of the same publication are disclosed. ) Can be contained.

(Method for preparing photosensitive resin composition)
The photosensitive resin composition of the present invention is prepared by mixing the above-described components and optional components as necessary. The colorant may be a pigment, a dye, or a mixed system of a pigment and a dye.
In preparing the photosensitive resin composition, the components constituting the photosensitive resin composition may be blended together, or may be blended sequentially after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a photosensitive resin composition.
The photosensitive resin composition prepared as described above can preferably be used after being filtered using a filter having a pore diameter of about 0.01 μm to 3.0 μm.

  Since the photosensitive resin composition of the present invention can form a colored cured film having excellent hue and contrast, it can be used for forming colored pixels such as color filters used in liquid crystal display devices, printing inks, and inkjet inks. And can be suitably used as a production application for paints and the like.

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

The method for producing a color filter of the present invention includes a colored layer forming step (A) in which the above-described photosensitive resin composition is applied onto a support to form a colored layer (photosensitive resin composition layer), and a step ( An exposure step (B) for forming a latent image by performing pattern-like exposure on the colored layer formed in A), and a developing step for developing the colored layer on which the latent image is formed to form a pattern (C).
Moreover, in the manufacturing method of the color filter of this invention, the aspect which further provided the process (D) which heat-processes with respect to the coloring pattern obtained at the process (C) is preferable.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described photosensitive resin composition of the present invention is applied onto a support by spin coating, slit coating, cast coating, roll coating, bar coating, inkjet coating, or the like. Is applied to form a colored layer, and then the colored layer is dried by heating (pre-baking) or vacuum drying.

  Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, silicon substrate, and resin substrate used in liquid crystal display devices. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
Moreover, the thickness of the colored layer formed with the photosensitive resin composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, and the range of 1.0 μm to 4.0 μm is more preferable. In addition, the thickness of a colored layer is a film thickness after drying.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, pattern-like exposure is performed on the colored layer formed on the support. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .

  In addition, as other exposure light sources, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.

~ Exposure process using laser light source ~
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of productivity, preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm ² is more preferable.

  There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. In addition, devices other than those described above are also preferably used.

-Step (C)-
Subsequently, the colored layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

  In the method for producing a color filter of the present invention, it is also preferable to perform post-exposure by ultraviolet irradiation on a colored pattern (pixel) formed using a photosensitive resin composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having a plurality of hue pixels, the above-described step (A), step (B), step (C), and step (D) may be repeated according to the desired number of colors.
In addition, whenever formation, exposure, and development of a single color layer are completed (for each color), the step (D) may be performed, or formation, exposure, and formation of all colored layers having a desired number of colors. After the development is completed, the step (D) may be performed collectively.

  The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast because the photosensitive resin composition of the present invention is used. When used in a liquid crystal display device or the like, an image having excellent spectral characteristics and contrast can be displayed while achieving a good hue.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the above-described color filter of the present invention. For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

  The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can. The color filter of the present invention can also be used for a COA (Color-filter On Array) system.

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

≪Photospacer and its formation method≫
The photospacer of the present invention is formed using the above-described photosensitive resin composition of the present invention. Details and preferred embodiments of the photosensitive resin composition are as described above.
Since the photospacer of the present invention is constituted by using the photosensitive resin composition of the present invention, the cross-sectional shape uniformity and the height uniformity are excellent (that is, the cross-sectional shape variation and the height variation).
Furthermore, when the photosensitive resin composition of the present invention is contained, a photospacer having a high compression elastic modulus and deformation recovery required as a photospacer can be obtained.

In the present invention, the pattern structure such as a photo spacer is “excellent in the uniformity of the cross-sectional shape”. The shape of the cross-sectional shape of the pattern structure is almost rectangular at a plurality of positions (preferably three or more) in the substrate. The state which becomes is preferable.
As the shape close to the rectangle, in the cross section of the pattern structure, an angle formed by a line corresponding to the side surface of the pattern structure and a line corresponding to the bottom surface of the pattern structure (hereinafter also referred to as “taper angle”) is 40 ° to A shape that is 100 ° is more preferable.
Here, the lower surface of the pattern structure means a contact surface of the surface of the pattern structure with the base on which the pattern structure is formed. Further, the side surface of the pattern structure is a pattern structure upper surface (a surface parallel to the lower surface of the pattern structure and not in contact with the base) among the surfaces of the pattern structure. Also refers to a surface that does not fall under.

The photospacer of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention, but a method including the following steps (i) to (c) is used. Therefore, it can be most suitably formed.
The method for forming a photospacer of the present invention comprises (a) a step of forming a film of the above-described photosensitive resin composition of the present invention on a substrate (hereinafter also referred to as “film formation step”), and (b). A step of exposing at least a part of the coating (hereinafter also referred to as “exposure step”) and (c) a step of developing the coating after exposure (hereinafter also referred to as “development step”) are provided. If necessary, (d) a step of heating the film after development (hereinafter also referred to as “film heating step”) and other steps may be provided.

(A) Film formation process A film formation process forms the film of the photosensitive resin composition of this invention as stated above on a board | substrate. A photosensitive resin layer can be formed as a film, and this photosensitive resin layer constitutes a photospacer that can maintain a uniform cell thickness by passing through other steps such as an exposure step and a development step described later. By using the photospacer of the present invention, display unevenness in an image in a display device (particularly a liquid crystal display device) that tends to cause display unevenness due to a change in cell thickness is effectively eliminated.

  As a method for forming a photosensitive resin layer on a substrate, (a) a coating method in which a photosensitive resin composition containing at least the above-described resin, a polymerizable compound, and a photopolymerization initiator is applied; and (b) the above-described method A transfer method in which a photosensitive transfer material having a photosensitive resin layer is used, and the photosensitive resin layer is laminated and transferred by heating and / or pressurization is preferable.

(A) Application method The photosensitive resin composition is applied by a known application method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, or wire bar coating. , Gravure coating, or extrusion coating using a popper described in US Pat. No. 2,681,294. Among them, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A, A method using a slit nozzle or a slit coater described in JP 2001-310147 A is suitable.

(B) Transfer method Transfer is performed by using a photosensitive transfer material, for example, a roller or a flat plate in which a photosensitive resin layer formed in a film shape on a temporary support is heated and / or pressurized on a desired substrate surface. Then, the photosensitive resin layer is transferred onto the substrate by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

When the photosensitive resin layer is formed, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) can be further provided between the photosensitive resin layer and the temporary support. Thereby, exposure sensitivity can be improved. In order to improve transferability, a thermoplastic resin layer having cushioning properties may be provided.
Paragraph numbers [0024] to [0024] of Japanese Patent Application Laid-Open No. 2006-23696 describe the temporary support, the oxygen-blocking layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer material and the method for producing the photosensitive transfer material. The structure and manufacturing method described in [0030] can be applied.

  When the photosensitive resin layer is formed by both the coating method (a) and the transfer method (b), the layer thickness is preferably 0.5 to 10.0 μm, more preferably 1 to 6 μm. When the layer thickness is within the above range, the generation of pinholes during the formation of coating during production can be prevented, and development and removal of unexposed portions can be performed without requiring a long time.

  Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), a substrate with a color filter (also referred to as a color filter substrate), and the like. Examples thereof include a drive substrate with a drive element (for example, a thin film transistor [TFT]). The thickness of the substrate is generally preferably 700 to 1200 μm.

(B) Exposure step / (c) Development step In the exposure step, at least a part of the coating formed in the coating formation step is exposed to form a latent image. In the subsequent development step, the coating film exposed in the exposure step can be developed to form a spacer pattern having a desired shape.

  Specific examples of these processes include the formation examples described in paragraphs [0071] to [0077] of JP-A-2006-64921, and paragraph numbers [0040] to [0051] of JP-A-2006-23696. The process described in 1 can be given as a suitable example in the present invention.

The method for forming a photospacer of the present invention may be provided with a film heating step described later (d), but without providing a film heating step by increasing the exposure amount in the exposure (hereinafter referred to as “heating step”). It is also possible to form a photo spacer having excellent cross-sectional shape uniformity and excellent height uniformity.
By setting “no heating process”, it is possible to more effectively suppress the deterioration of the photo spacer to be formed and the deterioration of the already formed pattern structure (colored pattern, etc.) and protective film.
The exposure amount at which a "no heating step" is preferably 1 to 500 mJ / cm ^2, preferably 10 to 300 mJ / cm ^2.

(D) Film heating step The photospacer forming method of the present invention may include a film heating step of heating the film after development in the development step. By heating, curing of the film is further promoted, and a photospacer having high strength is obtained. Moreover, when the photosensitive resin composition contains the resin A, a photospacer having a good compressive modulus and elastic recoverability can be obtained.

  As described above, a display device substrate including a photospacer on a substrate can be manufactured. The photo spacer is preferably formed on a black light shielding portion such as a black matrix formed on the substrate or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or an alignment film such as polyimide may be present between a black light shielding portion such as a black matrix, a driving element such as a TFT, and a photo spacer.

For example, when the photo spacer is provided on the black light shielding portion or the driving element, the black light shielding portion (black matrix or the like) or the driving element previously disposed on the substrate is covered with, for example, a photosensitive transfer material. A photosensitive resin layer is laminated on the support surface, peeled and transferred to form a photosensitive resin layer, which is then subjected to exposure, development, heat treatment, etc. to form a photo spacer, thereby producing a display device substrate. can do.
The display device substrate may further be provided with colored pixels of three colors such as red (R), blue (B), and green (G) as necessary.

The photospacer of the present invention can be formed after forming a color filter including a black shielding part such as a black matrix and a colored part such as a colored pixel.
The black shielding portion and the colored portion and the photo spacer are arbitrarily combined with a coating method for applying a photosensitive resin composition and a transfer method using a transfer material having a photosensitive resin layer made of the photosensitive resin composition. It is possible to form.
The black shielding part, the colored part, and the photospacer can each be formed from a photosensitive resin composition. Specifically, for example, the photosensitive resin layer is formed by directly applying the liquid photosensitive resin composition to a substrate. After the formation, exposure / development is performed to form the black shielding part and the colored part in a pattern, and then the photosensitive resin composition of another liquid is different from the substrate (temporary support). A transfer material prepared by forming a photosensitive resin layer on the surface was used, and the transfer material was brought into close contact with the substrate on which the black shielding portion and the colored portion were formed to transfer the photosensitive resin layer. Later, by performing exposure and development, the photospacer can be formed in a pattern.
In this manner, a color filter provided with a photospacer can be manufactured.

≪Protective film≫
The protective film of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention, but is formed by a method similar to the method for forming the photospacer of the present invention described above. it can. Here, when the protective film is not patterned, that is, when the protective film is formed as a so-called solid film, a method of exposing the entire surface of the film in the (b) exposure step is preferable.

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

<Synthesis Example of Polymer P-1—Compound Via General Formula II>
2-methoxypropanol (500 g) as a reaction solvent was placed in a 3 liter four-necked flask equipped with a stir bar and stirring blade, a reflux condenser, a dropping funnel and a thermometer, and heated to 70 ° C. while purging with nitrogen. To the dropping funnel, allyl methacrylate (82.3 g), methacrylic acid (17.7 g) and 2,2′-azobis (2,4-dimethylvaleronitrile) (0.74 g) as a polymerization initiator were added to 500 g of 2-methoxy. The mixture was dissolved in propanol and added dropwise to the flask with stirring over 2 hours. After completion of the reaction, the mixture was further stirred at a reaction temperature of 70 ° C. for 2 hours, and cooled after completion of heating. The reaction solution was dropped into 5 liters of distilled water, and the precipitated solid was collected by filtration. This solid was dried at 50 ° C. to obtain a white powder polymer (88 g) (compound of general formula II). From the acid value measurement, it was methacrylic acid / allyl methacrylate = 24/76 (unit: mol%).
The 1 liter three-necked flask was charged with the polymer (50 g) obtained above and 2-methoxypropanol (82 g), and heated to 110 ° C. with stirring. Methoxyphenol (0.6 g) was added as a polymerization inhibitor and dissolved. While this solution was being stirred in an oxygen atmosphere, glycidyl methacrylate (2.44 g) was added dropwise and allowed to react for 6 hours. After completion of the reaction, the reaction solution was added dropwise to the place where distilled water (820 g) was being stirred to cause reprecipitation. The polymer was collected by filtration and dried at 50 ° C. to obtain white powder A (46 g). As a result of measuring the acid value again, it was methacrylic acid / allyl methacrylate / glycidyl adduct = 20/76/4 (unit: mol%). The weight average molecular weight in GPC was 30,000.

<Synthesis Example of Polymers P-2 to P-4—Compound Via General Formula II>
In the synthesis example of the polymer P-1, poly (methacrylic acid / allyl methacrylate / glycidyl methacrylate) was replaced as follows to synthesize polymers P-2 to P-4, respectively.
Polymer P-2: Poly (methacrylic acid / allyl methacrylate / glycidyl methacrylate) (copolymerization molar ratio 24/70/6, weight average molecular weight: 32,000)
Polymer P-3: Poly (methacrylic acid / allyl methacrylate / glycidyl methacrylate) (copolymerization molar ratio 24/60/16, weight average molecular weight: 35,000)
Polymer P-4: Poly (methacrylic acid / allyl methacrylate / glycidyl methacrylate) (copolymerization molar ratio 24/50/26, weight average molecular weight: 33,000)

<Synthesis Example of Polymers P-5 to P-8—Compound Via General Formula II>
In the synthesis example of the polymer P-1, glycidyl methacrylate was synthesized by the same method as the synthesis example of the polymer P-1, except that glycidyl methacrylate was changed to a cyclomer (CYCLOMERA-200: manufactured by Daicel Chemical Industries, Ltd.) Alkali-soluble resin polymers P-5 to P-8 were synthesized.

<Synthesis Example of Polymers P-9 to P-12—Compound Via General Formula III>
Polymers P-9 to P-12 were synthesized via the general formula III. Specifically, general formula III in which R ^{6 in} general formula III is an ethyl group is prepared in the same manner as in general compound synthesis II except that 2-ethylhexyl methacrylate monomer is further copolymerized during the synthesis of general II compound. This compound was synthesized.
To the obtained polymer, 2-methoxypropanol (82 g) was added and heated to 50 ° C. with stirring. Methoxyphenol (0.6 g) was added as a polymerization inhibitor and dissolved. This solution was synthesized by reacting 2-methacryloylethyl isocyanate (produced by Showa Denko, Karenz MOI) with stirring in an oxygen atmosphere.

<Synthesis Example of Polymers P-13 to P-16>
In the synthesis example of the polymer P-1, in synthesizing the white powder polymer, in addition to methacrylic acid and allyl methacrylate, in addition to hexyl methacrylate or dicyclopentenyl methacrylate, the polymer P- 1 was synthesized by the same method as in Synthesis Example 1, and alkali-soluble resin polymers P-13 to P-16 were synthesized.

<Synthesis Example of Polymers P-17 to P-18—Compound Via General Formula III>
In the synthesis example of the polymer P-9, the compound of the general formula III was synthesized by the same method as the synthesis example of the polymer P-9, except that dicyclopentenyl methacrylate was further copolymerized. Polymers P-17 and P-18 were synthesized.

<Synthesis Example of Polymers P-19 to P-20—Compound Via General Formula III>
Polymers P-19 to P-20 were synthesized via the general formula III. Further, glycidyl methacrylate was dropped into general formula III in the same manner as in the synthesis example of polymer P-1, to synthesize polymers P-19 to P-20.

<Synthesis Example 1> Phthalonitrile compound [α-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _a , β-{(4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _{1 -a} Cl ₃ phthalonitrile] (0 ≦ a <1) (Intermediate 1) In a 150 ml flask, 7.98 g (0.030 mol) of tetrachlorophthalonitrile (hereinafter abbreviated as TCPN) and p-hydroxybenzoic acid were added. 5.95 g (0.030 mol) of acid methyl cellosolve and 31.91 g of acetonitrile were added, and the mixture was stirred for about 30 minutes using a magnetic stirrer until the internal temperature was stabilized at 40 ° C. Then, 4.56 g of potassium carbonate (0.033 mol) was added and allowed to react for about 3 hours. After cooling, the solvent was distilled off from the solution obtained by suction filtration by evaporation under conditions of about 110 ° C. × 1 hour. Furthermore, it vacuum-dried at about 110 degreeC overnight, and about 13.1g (yield of 102.4 mol% with respect to TCPN) was obtained.

Synthesis Example 2 Phthalocyanine Compound (hereinafter abbreviated as Pc-1) [ZnPc- {α- (4-COOC ₂ H ₄ OCH ₃ ) C ₆ H ₄ O} _x , {β- (4-COOC ₂ H ₄ Synthesis of OCH ₃ ) C ₆ H ₄ O} _3.8-x H _0.8 Cl _11.4 ] (0 ≦ x <3.8) In a 150 ml flask, intermediate 1, 10.21 g (0.024 g) obtained in Synthesis Example 1 was added. Mol), 0.16 g (0.001 mol) of phthalonitrile, and 3.46 g of benzonitrile (BN) are added, and the temperature is stabilized at 160 ° C. using a magnetic stirrer under nitrogen flow (10 ml / min). After stirring for about 1 hour, 2.22 g (0.007 mol) of zinc iodide was added and allowed to react for about 12 hours. After cooling, the reaction solution was evaporated under conditions of 140 ° C. × 1 hr and the solvent was distilled off. Then, the resulting solid was added to the sum of the weight of intermediate 1 and phthalonitrile used in the phthalocyanination reaction (10 Methyl Cellosolve (6.9 g) corresponding to the weight obtained by subtracting the weight of BN (3.46 g) from .37 g) was added, and the mixture was stirred and dissolved to prepare a crystallization solution. Next, the prepared crystallization solution was dropped into methanol (103.8 g) corresponding to 10 times the sum of the weight of intermediate 1 and phthalonitrile used in the phthalocyanination reaction, and stirred for 30 minutes. Thereafter, distilled water (72.6 g) corresponding to 7 times the sum of the weight of the intermediate was added dropwise over 30 minutes. After completion of the addition, the mixture was further stirred for 30 minutes to precipitate crystals. The obtained crystals were suction filtered, and then 1/2 times the amount of methanol (51.9 g) at the time of crystallization was added again and stirred for 30 minutes, and then 1/2 times the amount of distilled water at the time of crystallization (36 .3 g) was added dropwise over 30 minutes, and after completion of the addition, the mixture was further stirred for 30 minutes for washing and purification. After suction filtration, the taken-out crystal was vacuum-dried at about 60 ° C. overnight to obtain about 10.7 g (yield of 99.2 mol% based on intermediate 1 and phthalonitrile).

[Example 1]
-Preparation of colored photosensitive resin composition-
The following components were mixed and dissolved to prepare a colored photosensitive resin composition.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 33.1 g
Organic solvent 2 (ethyl 3-ethoxypropionate) 25.2g
Alkali-soluble binder P-2 Poly (methacrylic acid / allyl methacrylate / glycidyl methacrylate) (copolymerization molar ratio 24/70/6, weight average molecular weight: 32,000)
6.9g
Polymerizable compound 1 KAYARAD DPHA 2.8 g, manufactured by Nippon Kayaku Co., Ltd.
・ Polymerizable compound 2 manufactured by Toa Gosei Co., Ltd., Aronix TO-2349 2.8 g
・ Polymerization inhibitor (p-methoxyphenol) 0.003g
Photopolymerization initiator 1 CGI-242: 0.39 g manufactured by Ciba Specialty Chemicals
-Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2g
・ Fluorine-based surfactant (Megafac F554, manufactured by DIC) 0.01 g
-Blue pigment dispersion (Pigment Blue 15: 6 dispersion (solid content concentration 16.8%, pigment concentration 9.9%))
28.5g

The blue pigment dispersion was prepared as follows.
C. I. 12.8 parts of Pigment Blue 15: 6 and 7.2 parts of a dispersant (Solsperse 5500 manufactured by Nippon Lubrizol Co., Ltd.) are mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently mixed using a bead mill. The blue pigment dispersion was prepared by dispersing.

-Formation of colored photosensitive resin composition layer (colored layer)-
After applying the colored photosensitive resin composition prepared above on a glass (# 1737; manufactured by Corning) by spin coating, the volatile components are volatilized by drying at room temperature for 30 minutes, and the colored layer A Formed. The colored layer A was irradiated with i rays (wavelength 365 nm) to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm ² . Next, the colored layer A on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. Thereafter, it was dried by spraying to obtain a fine line pattern image. The obtained fine line pattern image was post-baked at 230 ° C. for 20 minutes to obtain a colored layer B having a thickness of 2 μm.

-Evaluation-
The sensitivity of the colored layer obtained above, the specific resistance of the liquid crystal, the spectral characteristics, the contrast, and the adhesion were evaluated by the following methods. The evaluation results are shown in Table 2 below.

(1) Sensitivity The colored layer A after coating and drying obtained above was irradiated with an irradiation light amount of 40 mJ / cm ² through a mask having a wavelength of 365 nm and a line width of 20 μm using an i-line reduction projection exposure apparatus. After the irradiation, development was performed at 26 ° C. for 45 seconds using a developer (an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%)). Subsequently, after rinsing with running water for 20 seconds, the film was dried by spraying to obtain a fine line pattern image. An image of a fine line pattern was taken from the obtained image with an optical microscope at a magnification of 200 times.
At this time, the width of the fine line was measured from the obtained image. Since the width of the fine line becomes thicker as the sensitivity is higher, the width of the fine line width from the mask width is defined as the line width sensitivity. Larger numbers are preferred because of higher sensitivity.

(2) Specific resistance of liquid crystal The colored layer B obtained above was scraped off from the substrate, and 9.0 mg of the scraped material was added to 2.00 g of liquid crystal material ZLI-4792 (Merck) and heated at 120 ° C. for 5 hours. did. Then, it filtered and the specific resistance of liquid crystal material was measured with the liquid crystal specific resistance measuring apparatus (model number ADVANTEST R8340 ULTRA HIGH RESISTANCE ME Co., Ltd. product made by Advantest). Since the specific resistance of the liquid crystal material is reduced by elution of metal ions, elution of metal ions can be evaluated based on the degree of the specific resistance.
<Evaluation criteria>
○: Specific resistance ≧ 1.0 × 10 ¹¹ MΩ, and no seizure failure was observed when the panel was assembled in a liquid crystal display device.
×: Specific resistance <1.0 × 10 ¹¹ MΩ, and a seizure failure occurred when a panel was assembled in a liquid crystal display device.

(3) Spectral characteristics The transmission spectrum of the colored layer B obtained above was measured using a microspectrophotometer OSP-SP200 (trade name) manufactured by Olympus Corporation. From the obtained transmission spectrum, the color coordinate x value, y value, and Y value in the CIE 1931 color system were determined.
The spectral characteristics can be said to have excellent spectral characteristics when the Y value at (x, y) = (0.138, 0.085) is high. It can be said that the larger the Y value, the better the spectral characteristics.

(4) Contrast The obtained substrate having each colored layer B is sandwiched between two polarizing films, and the luminance value is measured when the polarization axes of the two polarizing films are parallel and perpendicular. (Topcon Co., Ltd., model number: BM-5A), and the value obtained by dividing the luminance when the polarization axes of the two polarizing films are parallel by the luminance when perpendicular is obtained. Obtained as contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.

(5) Adhesiveness About the colored layer A obtained above, a mask having a mask width of 5, 10, 15, 20, and 25 μm on the colored layer A at a wavelength of 365 nm using an i-line reduction projection exposure apparatus. And irradiated with an exposure amount of 40 mJ / cm ² . After irradiation, the developer was used and developed at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, the film was dried by spraying to obtain a fine line pattern image. Image formation was observed by an ordinary method using an optical microscope and SEM photograph observation. The pattern dimension of the thinnest fine line pattern remaining on the substrate was used as the evaluation of adhesion.
It can be said that the thinner the fine wire remains, the better the adhesion.

[Example 2]
-Preparation of colored photosensitive resin composition-
The following components were mixed and dissolved to prepare a colored photosensitive resin composition.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 33.1 g
Organic solvent 2 (ethyl 3-ethoxypropionate) 25.2g
Alkali-soluble binder P-2 poly (methacrylic acid / allyl methacrylate / glycidyl methacrylate) (copolymerization molar ratio 24/70/6, weight average molecular weight 32,000)
6.9g
Polymerizable compound 1 Dipentaerythritol hexaacrylate
Nippon Kayaku Co., Ltd., KAYARAD DPHA 2.8 g
Polymerizable compound 2
Toa Gosei Co., Ltd., Aronix TO-2349 2.8g
・ Polymerization inhibitor (p-methoxyphenol) 0.003g
Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] ethanone): 0.39 g
・ Polyfunctional thiol compound 1 0.2g
-Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2g
・ Fluorine-based surfactant (Megafac F554, manufactured by DIC) 0.01 g
-Blue pigment dispersion (Pigment Blue 15: 6 dispersion (solid content concentration 16.8%, pigment concentration 9.9%))
27.0g
・ Dye (A-1) 1.1g
・ Dye (B-1) 0.4g

The polyfunctional thiol compound used above is 1,4-bis (3-mercaptobutyryloxy) butane.
In the above, the dye (A-1) is a dye that is a dipyrromethene metal complex compound, and the dye (B-1) is an anthraquinone compound (a compound having an anthracene-9,10-dione skeleton).
The colored photosensitive resin composition was prepared and evaluated in the same manner as in Example 1.

[Examples 3 to 8]
In Example 2, the alkali-soluble binder was changed as described in the following table, and other than that, a colored photosensitive resin composition was prepared in the same manner as in Example 2 to form a colored layer, Evaluation was performed.

Example 9
A colored photosensitive resin composition was prepared in the same manner as in Example 2, except that the dye (A-1 / B-1) was changed to the dye (A-3) (0.6 g) in Example 2. A colored layer was formed and evaluated.
The dye (A-3) is a xanthene dye.

Example 10
In Example 1, a blue pigment dispersion (Pigment Blue 15: 6 dispersion (solids concentration 16.8%, pigment concentration 9.9%)) was converted into a yellow pigment dispersion (Pigment Yellow 150 dispersion) (9.0 g). A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to a green pigment dispersion (Pigment Green 58 dispersion) (21.0 g), and a colored layer was formed and evaluated. It was.

Example 11
Example 11 is the same as Example 10 except that the pigment was changed to only the yellow pigment dispersion (Pigment Yellow 150 dispersion) and the dye (TA-1) (0.6 g) was used. In the same manner as in Example 10, a colored photosensitive resin composition was prepared, and a colored layer was formed and evaluated.
TA-1 is a triarylmethane dye.

TA-1

Example 12
-Phthalocyanine compound Pc-1 10 parts-Yellow coloring material YG-1 30 parts-Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw: 30,000) in propylene glycol monomethyl ether acetate solution (Solid content 50%)
12 parts DPHA (manufactured by Nippon Kayaku Co., Ltd.) 12 parts 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (photopolymerization initiator)
3 parts 2-mercaptobenzothiazole (hydrogen-donating compound) 2 parts Polymerization inhibitor: p-methoxyphenol 0.001 part Fluorosurfactant (trade name: Megafac F475, manufactured by Dainippon Ink) 0.5 Parts ・ Propylene glycol monomethyl ether acetate 129 parts

<Preparation of pigment dispersion composition YG-1>
Ingredients having the following composition were mixed, and the number of revolutions was 3,000 rpm using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
〔composition〕
Pigment Yellow 138 130 parts Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw: 5,000) propylene glycol monomethyl ether acetate solution (solid content 50%) 15 parts (Disperbyk-161, manufactured by Big Chemie Japan Co., Ltd.) 60 parts Propylene glycol monomethyl ether acetate 795 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 12 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition YG-1.

[Example 13] to [Example 17]
Adjustment was made in the same manner as in Example 12 except that the yellow colorant YG-1 used in Example 12 was changed to components D-1 to D-5.

(D-1): Propylene glycol monomethyl ether acetate solution of the dye compound (B-1) represented by the following structural formula (solid content: 13%)

(D-2): Propylene glycol monomethyl ether acetate solution of the dye compound (B-10) represented by the following structural formula (solid content: 13%)

(D-3): Propylene glycol monomethyl ether acetate solution of the dye compound (B-9) represented by the following structural formula (solid content: 13%)

(D-4): Propylene glycol monomethyl ether acetate solution of a dye compound represented by the following structural formula (solid content: 13%)

(D-5): Propylene glycol monomethyl ether acetate solution of azo dye described in Examples [Synthesis example of azo dye (3)] of JP 2011-197669 A (solid content 13%)

[Comparative Example 1]
In Example 1, a colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the alkali-soluble resin polymer Q-1 having the following structure was used instead of P-2, and a colored layer was formed. Evaluation was performed. The evaluation results are shown in Table 2 below.

Alkali-soluble polymer: Q-1

[Comparative Example 2]
In Example 2, a colored photosensitive resin composition was used in the same manner as in Example 2 except that instead of P-2, the copolymer resin (1 ′) described in the example of JP-A-2002-293737 was used. The product was prepared to form a colored layer and evaluated.

[Comparative Example 3]
In Example 2, it changed into P-2, used alkali-soluble resin polymer Q-1, and also changed dye into dye (A-3) (0.6g), and carried out similarly to Example 2. A colored photosensitive resin composition was prepared to form a colored layer and evaluated.

[Comparative Example 4]
In Example 10, a colored photosensitive resin composition was prepared in the same manner as in Example 10 except that the alkali-soluble resin polymer Q-1 having the following structure was used instead of P-2, and a colored layer was formed. Evaluation was performed.

[Comparative Example 5]
In Example 11, a colored photosensitive resin composition was prepared in the same manner as in Example 11 except that the alkali-soluble resin polymer Q-1 having the following structure was used instead of P-2, and a colored layer was formed. Evaluation was performed.

[Comparative Example 6]
In Example 13, a colored photosensitive resin composition was prepared in the same manner as in Example 13 except that the alkali-soluble resin polymer Q-1 having the following structure was used instead of P-2, and a colored layer was formed. Evaluation was performed.

Table 2 shows the following.
The colored photosensitive resin compositions using the alkali-soluble resins of Examples 1 to 17 are excellent in sensitivity and spectral characteristics (Y value), have high contrast, excellent adhesion, and have a large specific resistance value of liquid crystal. The liquid crystal display devices obtained using the colored photosensitive resin compositions of Examples 1 to 17 did not cause burn-in. On the other hand, in Comparative Examples 1 to 6 that do not use the alkali-soluble resin of the present invention, the sensitivity and adhesion were low, and the specific resistance values of the liquid crystals in Comparative Examples 2, 3, 5, and 6 were also low.

[Examples 18 to 20, Comparative Examples 7 and 8]
<Preparation of color filter substrate>
A color filter having a black matrix, an R (red) pixel, a G (green) pixel, and a B (blue) pixel was produced by the method described in paragraph numbers [0084] to [0095] of JP-A-2005-3861. (Hereinafter, this is referred to as a color filter substrate). Here, the substrate size of the color filter substrate was set to 550 mm × 650 mm.
Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the obtained color filter substrate by sputtering.

<Formation of photo spacer>
On the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced above was formed by sputtering, a photosensitive resin layer coating solution having the formulation shown in Table 3 below was slit-coated with a spinner. Subsequently, part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Co., Ltd.) to eliminate the fluidity of the coating film. A photosensitive resin layer having a thickness of 2 μm was formed (film formation step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, a mask (quartz exposure mask having a circular pattern with a diameter of 15 μm), the mask and the photosensitive resin layer In a state where the color filter substrate placed so as to face each other is set up substantially in parallel and vertically, the distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm, and an intensity of 250 W at 365 nm is passed through the mask. / M ² was exposed to ultraviolet light transmitted through an ultraviolet transmission filter (UV-35, manufactured by Toshiba Glass Co., Ltd.) (exposure process, exposure amount 200 mJ / cm ² ).

  Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Containing agent: Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, and shower-developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. An image was formed (development process). Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) diluted 10 times with pure water ) For 20 seconds at 33 ° C. with a cone-type nozzle pressure of 0.02 MPa, and the residue around the formed pattern image is removed to form a cylindrical spacer pattern with one spacer of 300 μm × 300 μm. It formed so that it might become a space | interval.

Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 130 ° C. for 60 minutes (heating step) to produce a photo spacer on the color filter substrate.
Here, about 1000 photo spacers obtained, using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022), the upper surface of the ITO transparent electrode (of the two surfaces parallel to the substrate, from the substrate) The distance from the far side) to the highest position of the photo spacer (hereinafter, this distance is also referred to as “the height of the photo spacer”), and the average value of 1000 photo spacers is defined as the average height of the photo spacer. did.
Moreover, the measurement of the bottom area of the obtained photospacer was performed using the SEM photograph. As a result, it was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm.

<Production of liquid crystal display device>
Separately, a glass substrate was prepared as a counter substrate, and the PVA mode was patterned on the transparent electrode and the counter substrate of the color filter substrate obtained above, and an alignment film made of polyimide was further provided thereon.

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided so as to surround the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained.

  Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, and DB1112H (as a blue (B) LED. A side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd. and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

<Evaluation>
The following evaluation was performed on the obtained photospacer and liquid crystal display device. The results of measurement evaluation are shown in Table 4 below.

(Photo spacer cross-sectional shape)
The cross-sectional shape of the photospacer after the heat treatment obtained in <Formation of photospacer> was observed using a scanning electron microscope. The observation was performed at a total of five locations including four locations (four corners) at the periphery of the substrate and one location at the center of the substrate.
Furthermore, the cross-sectional shape of the photo spacer was evaluated according to the following criteria.

~Evaluation criteria~
A: Photospacers having a cross-sectional shape with a taper angle of 45 ° or more and 90 ° or less were formed at all five locations.
B: Photo spacers having a cross-sectional shape with a taper angle of 45 ° or more and 95 ° or less were formed at all five locations, but did not fall under A above.
C: Photospacers having a cross-sectional shape with a taper angle of 40 ° or more and 100 ° or less were formed at all five locations, but none of the above A and B was applicable.
D: Photo spacers outside the range of the taper angle of 40 ° or more and 100 ° or less were formed at 1 to 4 out of 5 locations.
E: Photo spacers outside the range of the taper angle of 40 ° or more and 100 ° or less were formed at all five locations.

(Photo spacer height uniformity)
The difference between the maximum value and the minimum value was calculated from the result of the height of 1000 photospacers measured in <Formation of Photospacer> and evaluated according to the following criteria.
The smaller the difference, the better the uniformity.

~Evaluation criteria~
A: The difference between the maximum value and the minimum value of the height of the photospacer was less than 0.2 μm.
B: The difference between the maximum value and the minimum value of the height of the photospacer was 0.2 μm or more and less than 0.3 μm.
C: The difference between the maximum value and the minimum value of the height of the photospacer was 0.3 μm or more and less than 0.4 μm.
D: The difference between the maximum value and the minimum value of the height of the photo spacer was 0.4 μm or more and less than 0.5 μm.
E: The difference between the maximum value and the minimum value of the height of the photo spacer was 0.5 μm or more.

(Deformation recovery rate)
The obtained photo spacer was measured and evaluated by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following evaluation criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
Deformation recovery rate (%)
= (Recovery amount after release of load [μm] / Deformation amount under load [μm]) × 100

~Evaluation criteria~
A: The deformation recovery rate was 90% or more.
B: The deformation recovery rate was 87% or more and less than 90%.
C: The deformation recovery rate was 85% or more and less than 87%.
D: Deformation recovery rate was 80% or more and less than 85%.
E: Deformation recovery rate was 75% or more and less than 80%.
F: Deformation recovery rate was less than 75%.

(Display unevenness of liquid crystal display device)
About the liquid crystal display device produced above, the gray display when a gray test signal was input was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.

~Evaluation criteria~
A: There was no display unevenness and a very good display image was obtained.
B: Although the edge portion of the glass substrate was slightly uneven, the display image was good without affecting the display portion.
C: Slight unevenness was observed in the display portion, but it was within a practically acceptable range.
D: Unevenness was observed in the display section.

  The evaluation results are shown in Table 4 below.

  As shown in Table 4, the photo spacers of the examples had a uniform cross-sectional shape and suppressed height variation. Further, the display unevenness is suppressed in the liquid crystal display device provided with the photo spacer.

Example 24
<Formation of protective film>
In the production of the color filter substrate, after the black matrix, R pixel, G pixel, and B pixel are formed, the photosensitive resin composition of Example 21 is further applied on the black matrix and each pixel, without using a mask. Were exposed (entire exposure) and heat-treated to form a protective film. Here, the conditions for coating, exposure, and heat treatment are the same as the conditions for coating, exposure, and heat treatment in the formation of the photospacer in Example 21, except that exposure is performed without using a mask.
Next, a transparent electrode made of ITO (Indium Tin Oxide) was further formed on the obtained protective layer by sputtering.

<Formation of photo spacer>
On the ITO transparent electrode formed as described above, a photospacer was formed in the same manner as in Example 21 except that the photosensitive resin composition used in Example 21 was used as the photosensitive resin composition.

<Production and Evaluation of Liquid Crystal Display Device>
Next, a liquid crystal display device was produced in the same manner as in Example 12 using the color filter substrate on which the photospacer was formed.
The obtained protective film and liquid crystal display device were evaluated by the same method as in Example 21. The evaluation results are shown in Table 5.

  As shown in Table 5, when the protective film was formed using the photosensitive resin composition of the present invention, good results were obtained as in the case where the photo spacer was formed.

Claims (13)

Photosensitivity containing an alkali-soluble resin (A) having a group having an acidic group and two or more different polymerizable unsaturated groups in the side chain, a polymerizable compound (B), and a photopolymerization initiator (C) Resin composition. Furthermore, the photosensitive resin composition of Claim 1 containing a coloring agent. The photosensitive resin composition of Claim 1 or 2 in which the said alkali-soluble resin has a repeating unit represented by the following general formula (A).
Formula (A)

(In General Formula (A), R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group. is there.) The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin has a repeating unit represented by the following general formula (A) and a repeating unit represented by the following general formula (B).
Formula (A)

(In the general formula (A), R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, respectively. Represents.)
General formula (B)

(In general formula (B), R represents a hydrogen atom or a methyl group.) The alkali-soluble resin has a repeating unit represented by the following general formula (A), a repeating unit represented by the following general formula (B), and a repeating unit represented by the following general formula (C). Or the photosensitive resin composition of 2.
Formula (A)

(In the general formula (A), R represents a hydrogen atom or a methyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, respectively. Represents.)
General formula (B)

(In general formula (B), R represents a hydrogen atom or a methyl group.)
General formula (C)

(In general formula (C), R represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Ac represents a (meth) acryloyloxy group.) In any one of the repeating unit represented by the general formula (A), the repeating unit represented by the general formula (B), and the repeating unit represented by the general formula (C), R is a methyl group. The photosensitive resin composition of any one of Claims 3-5. The photosensitive resin according to any one of claims 3 to 6, wherein in the repeating unit represented by the general formula (A), R is a methyl group, and R ^{1 to} R ⁵ are all hydrogen atoms. Composition. A color filter, a protective film, a photo spacer, or a substrate for a liquid crystal display device, comprising the photosensitive resin composition according to claim 1. Applying the photosensitive resin composition according to any one of claims 2 to 7 to a support to form a colored layer, a pattern-like exposure to the colored layer, A method for producing a color filter, comprising: an exposure step for forming a latent image; and a development step for developing a colored layer on which the latent image is formed to form a pattern. A liquid crystal display device or a solid-state imaging device comprising the color filter according to claim 8, the color filter manufactured by the method for manufacturing a color filter according to claim 9, a protective film, or a photospacer. A resin having a repeating unit represented by the following general formula (1-1), a repeating unit represented by the following general formula (2-1), and a repeating unit represented by the following general formula (3-1).
General formula (1-1)

General formula (2-1)

Formula (3-1)

(In General Formula (3-1), X represents a divalent linking group, and Ac represents a (meth) acryloyloxy group.) 90 mol% or more of the repeating units constituting the resin are the repeating unit represented by the general formula (1-1), the repeating unit represented by the general formula (2-1), and the general formula (3- The resin according to claim 11, which is any one of the repeating units represented by 1). The resin contains 40 to 80 mol% of the repeating unit represented by the general formula (1-1) and 15 to 30 mol% of the repeating unit represented by the general formula (2-1). The resin according to claim 11 or 12, comprising 1 to 30 mol% of the repeating unit represented by 3-1).