JP6251067B2 - Coloring composition, cured film, method for producing color filter, color filter, solid-state imaging device, and image display device - Google Patents

Description

  The present invention relates to a colored composition, a cured film, a method for producing a color filter, a color filter, a solid-state imaging device, and an image display device.

  Conventionally, a color filter is manufactured by forming a colored pattern by a photolithography method, a dry etching method, or the like using a coloring composition containing a dye compound, a curable compound, and other components as necessary. Such a colored composition is used for forming a filter layer from a solid-state imaging device or an image display device.

  Here, the xanthene compound is described in, for example, Patent Document 1 and Patent Document 2. Patent Document 3 discloses a colored curable composition containing a dye multimer containing a dye moiety derived from a xanthene compound as a partial structure.

International Publication WO2013 / 089197 Pamphlet International Publication WO2013 / 146218 Pamphlet JP 2012-32754 A

  Here, the dye multimer can make the dye concentration in the colored composition higher than the low molecular weight compounds described in Patent Document 1 and Patent Document 2, and the dye compound falls off when it is used as a cured film. There is a merit that it is difficult. However, as a result of studies by the inventors of the present application, it has been found that a xanthene dye compound having a specific structure tends to undergo spectral fluctuations during development or have poor light resistance. The present invention aims to solve such problems, and uses a colored composition that does not cause spectral fluctuations during development and that provides a cured film excellent in light resistance, and the colored composition. An object of the present invention is to provide a cured film, a color filter manufacturing method, a color filter, a solid-state imaging device, and an image display device.

一般式（Ａ１−１）中、Ｒ¹〜Ｒ¹⁵のうち１つが下記一般式（Ａ１−１−１）で表される主鎖構造であり、Ｒ¹〜Ｒ¹⁵の他の少なくとも１つがアニオン性基またはアニオン性基を有する置換基であり、Ｒ¹およびＲ³はそれぞれ独立に、脂肪族炭化水素基であり、Ｒ²およびＲ⁴はそれぞれ独立に、芳香族炭化水素基であり、Ｒ⁵〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹¹〜Ｒ¹⁵は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、カルボニル基、ニトロ基、アミノ基、アルキルアミノ基、アリールアミノ基、または、スルホニル基を表す；
一般式（Ａ１−１−１）

一般式（Ａ１−１−１）中、Ｌ¹¹は、単結合または２価の連結基を表し、Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す；
一般式（Ａ１−２）

一般式（Ａ１−２）中、Ｒ¹〜Ｒ¹⁵のうち１つが上記一般式（Ａ１−１−１）で表される主鎖構造を含み、Ｒ¹およびＲ³はそれぞれ独立に、脂肪族炭化水素基であり、Ｒ²およびＲ⁴はそれぞれ独立に、芳香族炭化水素基であり、Ｒ⁵〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹¹〜Ｒ¹⁵は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、カルボニル基、ニトロ基、アミノ基、アルキルアミノ基、アリールアミノ基、または、スルホニル基を表す；Ｘは、キサンテンのカチオンと対塩を形成するアニオンを表す。
＜２＞一般式（Ａ１−１）におけるアニオン性基が、カルボン酸アニオン、スルホン酸アニオン、一般式（Ａ１−１−２）で表されるアニオンまたは一般式（Ａ１−１−３）で表されるアニオンを含むか、一般式（Ａ１−２）中のＸが、カルボン酸アニオン、スルホン酸アニオン、イミドアニオン、メチドアニオン、およびボレートアニオンのうちのいずれかのアニオンである、＜１＞に記載の着色組成物；
一般式（Ａ１−１−２）

一般式（Ａ１−１−２）中、Ｌ¹は、単結合または２価の連結基を表し、Ｌ²は、−ＳＯ₂−または−ＣＯ−を表し、Ｇは、炭素原子または窒素原子を表し、ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表し、Ｒ⁶は、フッ素原子を含むアルキル基またはフッ素原子を含むアリール基を表し、ｎ１が２の場合、２つのＲ⁶はそれぞれ同一でも異なっていても良い；
一般式（Ａ１−１−３）

一般式（Ａ１−１−３）中、Ｌ¹は、単結合または２価の連結基を表し、Ｌ²は、−ＳＯ₂−または−ＣＯ−を表し、Ｌ³は、２価の連結基を表し、Ｇは、炭素原子または窒素原子を表し、ｎ２は、Ｇが炭素原子の場合１を表し、Ｇが窒素原子の場合０を表し、Ｒ^7AおよびＲ^7Bはそれぞれ独立してフッ素原子を含むアルキレン基またはフッ素原子を含むアリーレン基を表し、Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す。
＜３＞色素化合物（Ａ）が、さらに、アルカリ可溶性基を有する、＜１＞または＜２＞に記載の着色組成物。
＜４＞色素化合物（Ａ）が、さらに、重合性基を有する＜１＞〜＜３＞のいずれかに記載の着色組成物。
＜５＞硬化性化合物が、重合性化合物であり、さらに、光重合開始剤を含有する、＜１＞〜＜４＞のいずれかに記載の着色組成物。
＜６＞さらに、フタロシアニン骨格を有する顔料を含有する、＜１＞〜＜５＞のいずれかに記載の着色組成物。
＜７＞一般式（Ａ１−１）のＲ¹¹〜Ｒ¹⁵の１つおよび一般式（Ａ１−２）のＲ¹¹〜Ｒ¹⁵の１つが一般式（Ａ１−１−１）で表される主鎖構造である、＜１＞〜＜６＞のいずれかに記載の着色組成物；
＜８＞
一般式（Ａ１−１）のＲ²およびＲ⁴ならびに一般式（Ａ１−２）のＲ²およびＲ⁴が、フェニル基である、＜１＞〜＜７＞のいずれかに記載の着色組成物。
＜９＞一般式（Ａ１−１）のＲ²およびＲ⁴ならびに一般式（Ａ１−２）のＲ²およびＲ⁴の少なくとも１つが、下記一般式（Ａ１−１−２）で表される、＜１＞〜＜８＞のいずれかに記載の着色組成物；

一般式（Ａ１−１−２）において、Ｒ²³〜Ｒ²⁵は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、アルコキシ基、炭素数１〜１２のアルキル基、カルボニル基、カルボニルアミド基、スルホニル基、スルホニルアミド基、ニトロ基、アミノ基、アミノカルボニル基、アミノスルホニル基、スルホニルイミド基またはカルボニルイミド基を表し、Ｒ²²およびＲ²⁶は、それぞれ独立に炭素数１〜５のアルキル基を表す。
＜１０＞一般式（Ａ１−１）のＲ¹およびＲ³ならびに一般式（Ａ１−２）のＲ¹およびＲ³が、それぞれ独立に、炭素数１〜５のアルキル基である、＜１＞〜＜９＞のいずれかに記載の着色組成物。
＜１１＞カラーフィルタの着色層形成に用いる、＜１＞〜＜１０＞のいずれかに記載の着色組成物。
＜１２＞＜１＞〜＜１１＞のいずれかに記載の着色組成物を硬化して得られた硬化膜。
＜１３＞＜１＞〜＜１１＞のいずれかに記載の着色組成物を用いて支持体に着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、露光された着色組成物層の未露光部を現像する工程と、を含むカラーフィルタの製造方法。
＜１４＞＜１２＞に記載の硬化膜を有するカラーフィルタ、または、＜１３＞に記載のカラーフィルタの製造方法により得られるカラーフィルタ。
＜１５＞＜１４＞に記載のカラーフィルタを有する固体撮像素子。
＜１６＞＜１４＞に記載のカラーフィルタを有する画像表示装置。 Under such circumstances, as a result of intensive studies by the inventor of the present application, the above problem can be solved by adopting a predetermined xanthene dye structure in a dye multimer including a repeating unit having a xanthene dye structure. I found it. Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <16>.
<1> a dye multimer having a repeating unit represented by formula (A1-1) and / or a repeating unit represented by formula (A1-2);
A coloring composition comprising a curable compound;
Formula (A1-1)

In general formula (A1-1), ^one of R ^{1 to} R ¹⁵ is a main chain structure represented by the following general formula (A1-1-1), and at least one of R ^{1 to} R ¹⁵ is an anion. R ¹ and R ³ are each independently an aliphatic hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, R ^{5 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ^{11 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. Represents a group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group;
General formula (A1-1-1)

In general formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group;
Formula (A1-2)

In General Formula (A1-2), ^one of R ^{1 to} R ¹⁵ includes a main chain structure represented by General Formula (A1-1-1), and R ¹ and R ³ are each independently aliphatic. A hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ^{5 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon. R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group. X represents an anion which forms a counter salt with the cation of xanthene.
<2> The anionic group in the general formula (A1-1) is represented by a carboxylic acid anion, a sulfonic acid anion, an anion represented by the general formula (A1-1-2) or a general formula (A1-1-3). <1>, wherein X in the general formula (A1-2) is an anion selected from a carboxylate anion, a sulfonate anion, an imide anion, a metide anion, and a borate anion A coloring composition of
General formula (A1-1-2)

In General Formula (A1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents —SO ₂ — or —CO—, and G represents a carbon atom or a nitrogen atom. N1 represents 2 when G is a carbon atom, 1 when G is a nitrogen atom, R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and n1 is 2 The two R ^{6 s} may be the same or different;
General formula (A1-1-3)

In General Formula (A1-1-3), L ¹ represents a single bond or a divalent linking group, L ² represents —SO ₂ — or —CO—, and L ³ represents a divalent linking group. G represents a carbon atom or a nitrogen atom, n2 represents 1 when G is a carbon atom, represents 0 when G is a nitrogen atom, and R ^7A and R ^7B each independently represents a fluorine atom. Represents an alkylene group or an arylene group containing a fluorine atom, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.
<3> The colored composition according to <1> or <2>, wherein the dye compound (A) further has an alkali-soluble group.
<4> The colored composition according to any one of <1> to <3>, wherein the dye compound (A) further has a polymerizable group.
<5> The colored composition according to any one of <1> to <4>, wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator.
<6> The colored composition according to any one of <1> to <5>, further comprising a pigment having a phthalocyanine skeleton.
<7> The main one of R ¹¹ to R ¹⁵ of one and the general formula of R ¹¹ to R ¹⁵ in formula (A1-1) (A1-2) is represented by the general formula (A1-1-1) The coloring composition according to any one of <1> to <6>, which is a chain structure;
<8>
R ² and R ⁴ R ² and R ⁴ as well as of the general formula (A1-1) (A1-2) is a phenyl group, <1> - coloring composition according to any one of <7> .
<9> At least one of R ² and R ^{4 in} the general formula (A1-1) and R ² and R ^{4 in the} general formula (A1-2) is represented by the following general formula (A1-1-2). <1> to the colored composition according to any one of <8>;

In general formula (A1-1-2), R ^{23 to} R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonylamide group, or a sulfonyl group. Represents a group, a sulfonylamide group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, and R ²² and R ²⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. .
<10> is R ¹ and R ³ of R ¹ and R ³ as well as of the general formula (A1-1) (A1-2), each independently, an alkyl group having 1 to 5 carbon atoms, <1> The coloring composition in any one of <9>.
<11> The colored composition according to any one of <1> to <10>, which is used for forming a colored layer of a color filter.
<12> A cured film obtained by curing the colored composition according to any one of <1> to <11>.
<13> A step of forming a colored composition layer on the support using the colored composition according to any one of <1> to <11>, a step of exposing the colored composition layer in a pattern, and exposure. And a step of developing an unexposed portion of the colored composition layer.
<14> A color filter having the cured film according to <12>, or a color filter obtained by the method for producing a color filter according to <13>.
<15> A solid-state imaging device having the color filter according to <14>.
<16> An image display device having the color filter according to <14>.

  According to the present invention, a colored composition that does not cause spectral fluctuation during development and provides a cured film excellent in light resistance, a cured film using the colored composition, a method for producing a color filter, a color filter, and a solid-state imaging device And an image display device can be provided.

Below, the coloring composition of this invention, a cured film, the pattern formation method, the manufacturing method of a color filter, a color filter, a solid-state image sensor, and an image display apparatus are explained in full detail.
The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
The solid content concentration in this specification refers to the solid content concentration at 25 ° C.

In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
The present invention has been made in view of the above situation, and an object thereof is to provide a coloring composition having excellent color characteristics.

  In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

  In this specification, the methyl group may be represented as Me, the ethyl group as Et, the propyl group as Pr, the butyl group as Bu, and the phenyl group as PH or Ph.

一般式（Ａ１−１）中、Ｒ¹〜Ｒ¹¹のうち１つが下記一般式（Ａ１−１−１）で表される主鎖構造であり、Ｒ¹〜Ｒ¹¹の他の少なくとも１つがアニオン性基またはアニオン性基を有する置換基であり、Ｒ¹およびＲ³はそれぞれ独立に、脂肪族炭化水素基であり、Ｒ²およびＲ⁴はそれぞれ独立に、芳香族炭化水素基であり、Ｒ⁵〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹¹〜Ｒ¹⁵は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、カルボニル基、ニトロ基、アミノ基、アルキルアミノ基、アリールアミノ基、または、スルホニル基を表す；
一般式（Ａ１−１−１）

一般式（Ａ１−１−１）中、Ｌ¹¹は、単結合または２価の連結基を表し、Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す；
一般式（Ａ１−２）

一般式（Ａ１−２）中、Ｒ¹〜Ｒ¹⁵のうち１つが上記一般式（Ａ１−１−１）で表される主鎖構造を含み、Ｒ¹およびＲ³はそれぞれ独立に脂肪族炭化水素基であり、Ｒ²およびＲ⁴はそれぞれ独立に芳香族炭化水素基であり、Ｒ⁵〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹¹〜Ｒ¹⁵は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、カルボニル基、ニトロ基、アミノ基、アルキルアミノ基、アリールアミノ基、または、スルホニル基を表す；Ｘは、キサンテンのカチオンと対塩を形成するアニオンを表す。
このような構成とすることにより、アルカリ現像時に分光変動が起こらず、耐熱性に優れた硬化膜が得られる着色組成物が得られる。 The colored composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is represented by the repeating unit represented by the general formula (A1-1) and / or the general formula (A1-2). A dye multimer having a repeating unit and a curable compound.
Formula (A1-1)

In general formula (A1-1), ^one of R ^{1 to} R ¹¹ is a main chain structure represented by the following general formula (A1-1-1), and at least one of R ^{1 to} R ¹¹ is an anion. R ¹ and R ³ are each independently an aliphatic hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, R ^{5 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ^{11 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. Represents a group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group;
General formula (A1-1-1)

In general formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group;
Formula (A1-2)

In General Formula (A1-2), ^one of R ^{1 to} R ¹⁵ includes the main chain structure represented by General Formula (A1-1-1), and R ¹ and R ³ are each independently aliphatic carbonized. R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ^{5 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. And R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group; X Represents an anion that forms a counter salt with the cation of xanthene.
By setting it as such a structure, the coloring composition which a spectral fluctuation does not occur at the time of alkali image development, and the cured film excellent in heat resistance is obtained is obtained.

This mechanism is presumed, but is thought to be as follows.
There are several known light-fading paths of dyes, but chemical species are always exposed to light under lightfastness test conditions. Under such conditions, electrophilic species typified by singlet oxygen are generated, and there is a path that fades when these and the dyes react. The reactivity with the electrophilic species is governed by the oxidation potential of the dye, and the higher the oxidation potential, the more easily the electrons are deprived and fading. However, the dye has an electronic distribution, and a portion having a relatively high potential such as HOMO easily reacts with an electrophilic species. However, there is a factor that lowers reactivity such as steric bulk. In some cases, it may be difficult to receive a fading color.
In the case of the xanthene structure used in the present invention, it is considered that the nitrogen atom is likely to react with the electrophilic species. Here, when the substituent of the nitrogen atom is an electron-donating group such as an alkyl group, the oxidation potential is further increased, and thus fading easily occurs. It is considered to be. In the present invention, it is presumed that the light resistance could be improved by using an aliphatic hydrocarbon group and an aromatic hydrocarbon group as the group bonded to the nitrogen atom of the xanthene structure.

In addition, the colored composition of the present invention is usually subjected to an alkali development treatment to remove unexposed portions. At that time, since a part of the alkaline developer penetrates into the pattern of the exposed portion, the dye is exposed to basic conditions. When there is a proton having high acidity in the xanthene structure, the spectrum changes under basic conditions, and the original spectral characteristics are impaired. In the case of a xanthene structure, it is considered that protons on nitrogen atoms are easily affected by pH, and if the acidity is high, spectral fluctuation may occur during alkali development.
In the present invention, it is presumed that spectral fluctuations during alkali development can be suppressed by using an aliphatic hydrocarbon group and an aromatic hydrocarbon group as the group bonded to the nitrogen atom of the xanthene structure.
In the present invention, the dye multimer contains one or both of the repeating unit represented by the general formula (A1-1) and the repeating unit represented by the general formula (A1-2). A1-1) is preferably included.

一般式（Ａ１−１）中、Ｒ¹〜Ｒ¹⁵のうち１つが上記一般式（Ａ１−１−１）で表される主鎖構造を含み、Ｒ¹およびＲ³はそれぞれ独立に、脂肪族炭化水素基であり、Ｒ²およびＲ⁴はそれぞれ独立に、芳香族炭化水素基であり、Ｒ⁵〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹¹〜Ｒ¹⁵は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、カルボニル基、ニトロ基、アミノ基、アルキルアミノ基、アリールアミノ基、または、スルホニル基を表す；Ｘは、キサンテンのカチオンと対塩を形成するアニオンを表す。 <Dye multimer>
<< Repeating unit represented by formula (A1-1) >>
The repeating unit represented by formula (A1-1) in the present invention is as follows.
Formula (A1-1)

In General Formula (A1-1), ^one of R ^{1 to} R ¹⁵ includes a main chain structure represented by General Formula (A1-1-1), and R ¹ and R ³ are each independently aliphatic. A hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ^{5 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon. R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group. X represents an anion which forms a counter salt with the cation of xanthene.

一般式（Ａ１−１−２）において、Ｒ²³〜Ｒ²⁵は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、アルコキシ基、炭素数１〜１２のアルキル基、カルボニル基、カルボニルアミド基、スルホニル基、スルホニルアミド基、ニトロ基、アミノ基、アミノカルボニル基、アミノスルホニル基、スルホニルイミド基またはカルボニルイミド基を表し、Ｒ²²およびＲ²⁶は、それぞれ独立に炭素数１〜５のアルキル基を表す。
一般式（Ａ１−１−２）において、Ｒ²³〜Ｒ²⁵は、水素原子またはハロゲン原子が好ましく、水素原子がより好ましい。
一般式（Ａ１−１−２）において、Ｒ²²およびＲ²⁶は、それぞれ独立に炭素数１〜５のアルキル基（より好ましくは炭素数３〜５のアルキル基）であることが好ましい。炭素数１〜５のアルキル基は、メチル基、エチル基、プロピル基、ブチル基がさらに好ましく、メチル基、エチル基、ｎ−プロピル基、iso−プロピル基、ｎ−ブチル基がより好ましく、iso−プロピル基が特に好ましい。 In general formula (A1-1), R ¹ and R ³ are each independently an aliphatic hydrocarbon group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, A methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group are particularly preferable. R ¹ and R ³ may be different but are preferably the same. The alkyl group as R ¹ and R ³ may have a substituent, but preferably has no substituent.
In General Formula (A1-1), R ² and R ⁴ are each independently an aromatic hydrocarbon group, and a phenyl group is more preferable. The aromatic hydrocarbon group as R ² and R ⁴ may have a substituent, is selected from the group of substituents described later, more preferably an alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group , A propyl group and a butyl group are more preferable, and a methyl group, an ethyl group, an n-propyl group and an n-butyl group are particularly preferable.
Formula (A1-1), at least one of R ² and R ⁴ in R ² and R ⁴ as well as the general formula (A1-2), further be represented by the following general formula (A1-1-2) preferable.

In general formula (A1-1-2), R ^{23 to} R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonylamide group, or a sulfonyl group. Represents a group, a sulfonylamide group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, and R ²² and R ²⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. .
In general formula (A1-1-2), R ^{23 to} R ²⁵ are preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom.
In General Formula (A1-1-2), R ²² and R ²⁶ are each independently preferably an alkyl group having 1 to 5 carbon atoms (more preferably an alkyl group having 3 to 5 carbon atoms). The alkyl group having 1 to 5 carbon atoms is more preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group or an n-butyl group. A -propyl group is particularly preferred.

In General Formula (A1-1), R ^{5 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and a hydrogen atom is preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom or a chlorine atom is preferable. As an aliphatic hydrocarbon group, a C1-C10 aliphatic hydrocarbon group is preferable. In addition, examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkenyl group, and an alkyl group is preferable. As the aromatic hydrocarbon group, an aryl group is preferable, and a phenyl group is more preferable.

In General Formula (A1-1), R ^{11 to} R ¹⁴ are each independently preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom.
In general formula (A1-1), R ¹⁵ is preferably a carbonyl group or a sulfonyl group.

Substituent group A:
Examples of the substituent that the dye may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, and a carboxyl group. , Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryl Oxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or Arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, etc. Is mentioned. Details are described below.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms substituted or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3 Yl) or group of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

  Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Oct-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Le group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydride Hexyl group, a nitro group, a carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 2 carbon atoms) 30 substituted or unsubstituted heterocyclic oxy groups Heterocyclic portion is preferably described in the heterocyclic portion described above heterocyclic group, e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonyla Bruno, butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbocycle having 7 to 30 carbon atoms) D Groups such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl groups (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) A carbonyl group, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenyl Zo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably 2 carbon atoms). -30 substituted or unsubstituted phosphinyl groups such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl)

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups. Examples of functional groups that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specifically, methylsulfonylaminocarbonyl, Examples include p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

<< Main chain structure represented by formula (A1-1-1) >>
In the general formula (A1-1), the dye multimer used in the present invention includes a main chain structure in which one of R ^{1 to} R ¹⁵ is represented by the general formula (A1-1-1), and the general formula (A1 -1) one of R ^{11 to} R ¹⁵ is a main chain structure represented by the general formula (A1-1-1), or R ¹ , R ² , R ³ and R of the general formula (A1-1) It is preferable that at least one of ⁴ includes a main chain structure represented by the general formula (A1-1-1), and one of R ^{11 to} R ^{15 in} the general formula (A1-1) is represented by the general formula (A1-1-1-). The main chain structure represented by 1) is more preferable, and R ¹⁵ is more preferably the main chain structure represented by the general formula (A1-1-1).
When ^one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (A1-1) includes a main chain structure, the main chain in which R ² or R ⁴ is represented by the general formula (A1-1-1) preferably includes a structure, more preferably one of R ²² to R ²⁶ is a main chain structure represented by the general formula (A1-1-1) of the general formula (A1-1-2), R ²² Is more preferably a main chain structure represented by the general formula (A1-1-1).

一般式（Ａ１−１−１）中、Ｌ¹¹は、単結合または２価の連結基を表し、Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す。 General formula (A1-1-1)

In General Formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group, or an alkoxymethyl group.

L ¹¹ represents a single bond or a divalent linking group and is preferably a divalent linking group. Examples of the divalent linking group include substituted or unsubstituted alkylene groups having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted groups having 6 to 30 carbon atoms. A substituted arylene group (for example, a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linking group formed by linking two or more thereof are represented. A configuration in which L ¹¹ contains an anion is also preferable.
L ¹¹ is preferably —CO ₂ — or a phenylene group, more preferably —CO ₂ —.
R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group, preferably a hydrogen atom or a methyl group.

One type of main chain structure represented by the general formula (A1-1-1) may be included in one molecule of the dye multimer, or two or more types may be included.
The main chain structure preferably used in the present invention is exemplified below, but it goes without saying that the present invention is not limited thereto.
Particularly preferred are linking groups represented by the following (XX-1) to (XX-24), (meth) acrylic linking chains represented by (XX-1) and (XX-2), (XX-10) More preferably selected from a styrene-based linking chain represented by (XX-17), (XX-18) and (XX-19), and a vinyl-based linking chain represented by (XX-24). (XX-1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains, (XX-24) More preferably, it is selected from the represented vinyl-based linkage chains, (meth) acrylic linkage chains represented by (XX-1) and (XX-2), and styrene-series represented by (XX-11) A linking chain is more preferred.
In (XX-1) to (X-24), it represents that L ₁ is linked at the site indicated by *. Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

<< Anionic group >>
General formula (A1-1) contains an anionic group. An anionic group is contained according to the valence of the cation contained in the dye multimer.
In formula (A1-1), the anionic group can be any one of R ¹ to R ^15, a group included as one of the substituents R ¹ to R ^15, of R ¹¹ and R ¹⁵ It is preferable that it is either or a group included as a substituent of any of R ¹¹ and R ¹⁵ .
Further, when the general formula (A1-1) includes a structure represented by the general formula (A1-1-2), it is also preferable that R ²² or R ²⁶ is an anionic group or an anionic group.
The anionic group contained in the dye multimer of the present invention may be one type or two or more types.
The anionic group in general formula (A1-1) is a carboxylate anion, a sulfonate anion, an anion represented by general formula (A1-1-2) or an anion represented by general formula (A1-1-3). It is preferable to contain.

一般式（Ａ１−１−２）中、Ｌ¹は、単結合または２価の連結基を表し、Ｌ²は、−ＳＯ₂−または−ＣＯ−を表し、Ｇは、炭素原子または窒素原子を表し、ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表し、Ｒ⁶は、フッ素原子を含むアルキル基またはフッ素原子を含むアリール基を表し、ｎ１が２の場合、２つのＲ⁶はそれぞれ同一でも異なっていても良い General formula (A1-1-2)

In General Formula (A1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents —SO ₂ — or —CO—, and G represents a carbon atom or a nitrogen atom. N1 represents 2 when G is a carbon atom, 1 when G is a nitrogen atom, R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and n1 is 2 The two R ^{6 s} may be the same or different

In General Formula (A1-1-2), R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom.
1-6 are preferable, as for carbon number of the alkyl group containing a fluorine atom, 1-4 are more preferable, and 1-3 are more preferable. The alkyl group containing a fluorine atom may be linear, branched or cyclic, but is more preferably linear.
6-18 are preferable, as for carbon number of the aryl group containing a fluorine atom, 6-12 are more preferable, and 6 is more preferable.
The alkyl group containing a fluorine atom or the aryl group containing a fluorine atom preferably has a fluorine atom content of 50% or more, and more preferably a perfluoro group. The fluorine atom content is expressed as follows.
Fluorine atom content = [(Atom weight of fluorine atom) × (Number of fluorine atoms) / (Molecular weight of alkyl group containing fluorine atom or aryl group containing fluorine atom)] × 100
In general formula (A1-1-2), * represents R ^{1 to} R ¹⁵ or a bonding site with a substituent of these groups.

Although the example of general formula (A1-1-2) is shown below, it cannot be overemphasized that this invention is not limited to these.

一般式（Ａ１−１−３）中、Ｌ¹は、単結合または２価の連結基を表し、Ｌ²は、−ＳＯ₂−または−ＣＯ−を表し、Ｌ³は、２価の連結基を表し、Ｇは、炭素原子または窒素原子を表し、ｎ２は、Ｇが炭素原子の場合１を表し、Ｇが窒素原子の場合０を表し、Ｒ^7AおよびＲ^7Bはそれぞれ独立してフッ素原子を含むアルキレン基またはフッ素原子を含むアリーレン基を表し、Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す。 General formula (A1-1-3)

In General Formula (A1-1-3), L ¹ represents a single bond or a divalent linking group, L ² represents —SO ₂ — or —CO—, and L ³ represents a divalent linking group. G represents a carbon atom or a nitrogen atom, n2 represents 1 when G is a carbon atom, represents 0 when G is a nitrogen atom, and R ^7A and R ^7B each independently represents a fluorine atom. Represents an alkylene group or an arylene group containing a fluorine atom, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.

In General Formula (A1-1-3), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. As a bivalent coupling group, the group etc. which consist of a C1-C6 alkylene group, a C6-C12 arylene group, -O-, -S-, or these combination are mentioned.
In General Formula (A1-1-3), L ³ represents a divalent linking group. The divalent linking group includes, as a divalent linking group, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 18 carbon atoms, —O—, —CO—, —S—, —SO ₂ —, ^A group consisting of —NR ^A R ^B — or a combination thereof; The alkylene group having 1 to 6 carbon atoms may be linear, branched or cyclic. The arylene group having 6 to 18 carbon atoms may be monocyclic or polycyclic. In —NR ^A R ^B —, R ^A and R ^B each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^A and R ^B are bonded to each other to form a ring. Also good.
In general formula (A1-1-3), R ^7A and R ^7B each independently represent an alkylene group containing a fluorine atom or an arylene group containing a fluorine atom, and the alkyl group containing a fluorine atom has 1 to 1 carbon atoms. 6 is preferable, 1-4 is more preferable, and 1-3 are more preferable. The alkyl group containing a fluorine atom may be linear, branched or cyclic, but is more preferably linear.
6-18 are preferable, as for carbon number of the aryl group containing a fluorine atom, 6-12 are more preferable, and 6 is more preferable.
The alkyl group containing a fluorine atom or the aryl group containing a fluorine atom preferably has a fluorine atom content of 50% or more, and more preferably a perfluoro group.
In general formula (A1-1-3), R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group, and preferably a hydrogen atom or a methyl group. When R ^X represents an alkoxymethyl group, the alkoxymethyl group preferably has 1 to 3 carbon atoms.

Although the example of general formula (A1-1-3) is shown below, it cannot be overemphasized that this invention is not limited to these. Rx represents a hydrogen atom or a methyl group.

一般式（Ａ１−２）中、Ｒ¹〜Ｒ¹⁵のうち１つが上記一般式（Ａ１−１−１）で表される主鎖構造を含み、Ｒ¹およびＲ³はそれぞれ独立に、脂肪族炭化水素基であり、Ｒ²およびＲ⁴はそれぞれ独立に、芳香族炭化水素基であり、Ｒ⁵〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹¹〜Ｒ¹⁵は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、カルボニル基、ニトロ基、アミノ基、アルキルアミノ基、アリールアミノ基、または、スルホニル基を表す；Ｘは、キサンテンのカチオンと対塩を形成するアニオンを表す。 << Repeating unit represented by formula (A1-2) >>
The repeating unit represented by formula (A1-2) in the present invention is as follows.
Formula (A1-2)

In General Formula (A1-2), ^one of R ^{1 to} R ¹⁵ includes a main chain structure represented by General Formula (A1-1-1), and R ¹ and R ³ are each independently aliphatic. A hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ^{5 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon. R ^{11 to} R ¹⁵ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group. X represents an anion which forms a counter salt with the cation of xanthene.

In the general formula (A1-2), when R ¹ and R ³ are each independently an aliphatic hydrocarbon group, R ² and R ⁴ are each independently an aromatic hydrocarbon group, and R ^{5 to} R ¹⁰ In the case where each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, the preferred range is the same as R ^{1 to} R ^{15 in} formula (A1-2). Is the same.

The dye multimer used in the present invention includes a main chain structure in which one of R ^{1 to} R ¹⁵ is represented by the general formula (A1-1-1) in the general formula (A1-2), and the general formula (A1 -2) one of R ^{11 to} R ¹⁵ is the main chain structure represented by the general formula (A1-1-1), or R ¹ , R ² , R ³ and R of the general formula (A1-2) It is preferable that at least one of ⁴ includes a main chain structure represented by the general formula (A1-1-1), and one of R ^{11 to} R ^{15 in} the general formula (A1-2) is represented by the general formula (A1-1-1-). The main chain structure represented by 1) is more preferable, and R ¹⁵ is more preferably the main chain structure represented by the general formula (A1-1-1).
When ^one of R ¹ , R ² , R ³ and R ^{4 in} the general formula (A1-2) includes a main chain structure, R ² or R ⁴ is the main chain represented by the general formula (A1-1-1) preferably includes a structure, more preferably one of R ²² to R ²⁶ is a main chain structure represented by the general formula (A1-1-1) of the general formula (A1-1-2), R ²² Is more preferably a main chain structure represented by the general formula (A1-1-1).

<< Anion X in General Formula (A1-2) >>
In the general formula (A1-2), X represents an anion that forms a counter salt with a cation of xanthene. An anion is contained according to the valence of the cation contained in the dye multimer.
The dye multimer used in the present invention may contain only one kind of anion X, or may contain two or more kinds.
X is preferably an anion selected from a carboxylate anion, a sulfonate anion, an imide anion, a methide anion, and a borate anion, and is a bis (sulfonyl) imide anion, a tris (sulfonyl) methyl anion, a tetraarylborate anion. Is more preferable.

（式（ＡＮ−１）中、Ｘ¹およびＸ²は、それぞれ独立に、フッ素原子またはフッ素原子を有する炭素数１〜１０のアルキル基を表す。Ｘ¹およびＸ²は互いに結合して環を形成しても良い。） As a bis (sulfonyl) imide anion, the structure represented by the following general formula (AN-1) is preferable.

(In Formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² are bonded to each other to form a ring. It may be formed.)

X ¹ and X ² each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom. 10 to 10 perfluoroalkyl groups, more preferably 1 to 4 carbon perfluoroalkyl groups, and particularly preferably a trifluoromethyl group.

（式（ＡＮ−２）中、Ｘ³、Ｘ⁴およびＸ⁵はそれぞれ独立に、フッ素原子または炭素数１〜１０のフッ素原子を有するアルキル基を表す。） As the tris (sulfonyl) methyl anion, a structure represented by the following general formula (AN-2) is preferable.

(In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represents a fluorine atom or an alkyl group having 1 to 10 carbon atoms.)

X ³ , X ⁴ and X ⁵ are each independently the same as X ¹ and X ² , and the preferred range is also the same.

（式（ＡＮ−５）中、Ａｒ¹、Ａｒ²、Ａｒ³およびＡｒ⁴は、それぞれ独立に、アリール基を表す。） The tetraarylborate anion is preferably a compound represented by the following general formula ((AN-5)).

(In Formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents an aryl group.)

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently more preferably a phenyl group having a halogen atom and / or an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having fluorine. Is more preferable.

Specific examples of the non-nucleophilic counter anion used in the present invention are shown below, but the present invention is not limited thereto.

  Examples of the repeating unit represented by the general formula (A1-1) or the repeating unit represented by the general formula (A1-2) used in the present invention are shown below. Needless to say, the present invention is not limited to these examples.

  The dye multimer used in the present invention is a total of 1 to 100 mol of the repeating unit represented by the general formula (A1-1) and the repeating unit represented by the general formula (A1-2) in all repeating units. %, 5 to 40 mol% is preferable, and 10 to 30 mol% is more preferable. The repeating unit represented by the general formula (A1-1) and the repeating unit represented by the general formula (A1-2) may each include only one type or two or more types.

<< Other functional groups and repeating units >>
The dye multimer of the present invention may have another functional group in the repeating unit containing the dye multimer described above. Examples of other functional groups include polymerizable groups and alkali-soluble groups.
In addition, the dye multimer of the present invention may contain other repeating units in addition to the repeating unit containing the dye structure described above. Other repeating units may have a functional group.
Moreover, as another repeating unit, the repeating unit containing at least 1 sort (s) of a polymeric group and an alkali-soluble group (preferably acid group) is illustrated.

<<< Polymerizable group of dye multimer >>>
The dye multimer of the present invention preferably contains a polymerizable group. One type of polymerizable group may be included, or two or more types may be included.
As for the polymerizable group, the dye structure may contain a polymerizable group, or may contain other parts. In the present invention, the dye structure preferably includes a polymerizable group. By adopting such a configuration, the heat resistance tends to be improved.
Moreover, in this invention, the aspect in which other parts other than a pigment | dye structure contain a polymeric group is also preferable.
As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), or a methylol group. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate-derived (meth) More preferred is an acryloyl group.
The polymerizable group is preferably contained as a repeating unit having a polymerizable group in the dye multimer, and more preferably as a repeating unit having an ethylenically unsaturated bond. That is, an example of a preferred embodiment of the dye multimer of the present invention is an embodiment in which the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having a polymerizable group, and the repeating contains a dye monomer. More preferably, the unit contains a repeating unit having an ethylenically unsaturated bond.

  As a method for introducing a polymerizable group, (1) a method in which a dye multimer is modified and introduced with a polymerizable group-containing compound, and (2) a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced. Etc. Details will be described below.

(1) A method of introducing a dye multimer after modifying it with a polymerizable group-containing compound:
As a method for introducing the dye multimer by modifying with a polymerizable group-containing compound, a known method can be used without any particular limitation. For example, (a) a method of reacting a carboxylic acid of a dye multimer with an unsaturated bond-containing epoxy compound, and (b) a method of reacting a hydroxyl group or amino group of the dye multimer with an unsaturated bond-containing isocyanate compound. (C) A method of reacting an epoxy compound contained in the dye multimer with an unsaturated bond-containing carboxylic acid compound is preferable from the viewpoint of production.

  Examples of the unsaturated bond-containing epoxy compound in the method of reacting the carboxylic acid of the dye multimer with the unsaturated bond-containing epoxy compound include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and 3,4-epoxy. Examples thereof include cyclohexylmethyl acrylate and 3,4-epoxy-cyclohexylmethyl methacrylate. In particular, glycidyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate are preferable because of excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.

  As the unsaturated bond-containing isocyanate compound in the method of reacting the hydroxyl group or amino group of the (b) dye multimer with the unsaturated bond-containing isocyanate compound, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl atacrylate 1,1-bis (acryloyloxymethyl) ethyl isocyanate and the like, and 2-isocyanatoethyl methacrylate is preferable because of its excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.

  If it is a carboxylic acid compound having a known (meth) acryloyloxy group as the unsaturated bond-containing carboxylic acid compound in the method of reacting the epoxy compound of the (c) dye multimer and the unsaturated bond-containing carboxylic acid compound, Although it can be used without particular limitation, methacrylic acid and acrylic acid are preferred, and methacrylic acid is particularly preferred because of excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.

(2) A method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced:
(2) As a method for copolymerizing and introducing a dye monomer and a polymerizable group-containing compound, known methods can be used without any particular limitation. A method of copolymerizing a polymerizable group-containing compound that can be polymerized, and a method (e) a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition are preferred.

  (D) As a radically polymerizable polymerizable group-containing compound in a method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable polymerizable group-containing compound, an allyl group-containing compound (for example, (meth)) Allyl acrylate, etc.), epoxy group-containing compounds (eg, glycidyl (meth) acrylate, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, etc.), oxetane group-containing compounds (eg, 3-methyl-3-oxetanylmethyl (meth) ) Acrylate etc.) and methylol group-containing compounds (for example, N- (hydroxymethyl) acrylamide etc.), and epoxy compounds and oxetane compounds are particularly preferred. Known conditions can be used as the reaction conditions.

  (E) As a polymerizable group-containing compound capable of polyaddition in a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition, an unsaturated bond-containing diol compound (for example, 2, 3-dihydroxypropyl (meth) acrylate). Known conditions can be used as the reaction conditions.

  As a method for introducing a polymerizable group, a method of reacting a carboxylic acid possessed by a dye multimer, a carboxylic acid possessed by a dye multimer, and an unsaturated bond-containing epoxy compound is particularly preferred.

The amount of the polymerizable group possessed by the dye multimer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, relative to 1 g of the dye multimer, and 0.3 to 1. Particularly preferred is 0 mmol.
Moreover, when a pigment | dye multimer contains the repeating unit which has a polymeric group, the ratio of the said repeating unit is 1-60 mol% of all the repeating units, 10-50 mol is more preferable, 15-40 More preferred is mol%.

  As a method for introducing the polymerizable group, a method in which the carboxylic acid contained in the dye multimer, the carboxylic acid contained in the dye multimer, and the unsaturated bond-containing epoxy compound are particularly preferred.

  Specific examples of the repeating unit having a polymerizable group include the following. However, the present invention is not limited to these.

  Among the specific examples described above, from the viewpoint of substrate adhesion and surface roughness, a dye monomer having an ethylenically unsaturated bond is preferable, among which a methacryloyl group, an acryloyl group, a styryl group, or a vinyloxy group is preferable, and a methacryloyl group. An acryloyl group is more preferable, and a methacryloyl group is more preferable.

<<< Alkali-soluble group of dye multimer >>>
An example of the alkali-soluble group that the dye multimer in the present invention may have is an acid group, and examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. The alkali-soluble group may contain only 1 type, and may contain 2 or more types.
In the present invention, the alkali-soluble group (preferably an acid group) is preferably contained in the dye multimer as a repeating unit having an alkali-soluble group (acid group).
In the present invention, the acid value of the dye multimer can be calculated from the average content of acid groups in the dye multimer, for example. Moreover, the resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises a pigment | dye multimer.

  As a method for introducing an alkali-soluble group into a dye multimer, a method in which an alkali-soluble group is introduced into a dye monomer in advance, and a monomer other than a dye monomer having an alkali-soluble group ((meth) acrylic acid, acrylic Modified product of caprolactone of acid, modified product of succinic anhydride of 2-hydroxyethyl (meth) acrylate, modified product of phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-hydroxyethyl (meth) acrylate 2-cyclohexanedicarboxylic acid anhydride modified product, carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomer such as acid phosphooxyethyl methacrylate, vinyl phosphonic acid, vinyl sulfonic acid, Such as 2-acrylamido-2-methylsulfonic acid A method of copolymerizing a phosphate-containing monomer) may be mentioned, more preferably to use both methods.

The amount of the alkali-soluble group that the dye multimer has is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and more preferably 0.5 mmol to 1. Particularly preferred is 0 mmol.
Further, when the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is the total repeating unit in the dye monomer. On the other hand, 5-70 mol% is preferable, 10-60 mol% is more preferable, and 10-50 mol% is more preferable.

Other functional groups possessed by the dye multimer include lactone, acid anhydride, amide, —COCH ₂ CO—, cyano group and other development promoting groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups And an affinity adjusting group such as a hydroxyl group, a maleimide group, and an amino group, and the like, which can be appropriately introduced.
Examples of the introduction method include a method of introducing the dye monomer in advance and a method of copolymerizing the monomer having the functional group.

（一般式（Ｐ）中、Ｘ¹は重合によって形成される連結基を表し、Ｌ¹は単結合または２価の連結基を表す。Ｐはアルキレンオキシ鎖の繰り返しからなる基を含む基を表す。）
一般式（Ｐ）におけるＸ¹およびＬ¹はそれぞれ、一般式（Ａ）におけるＸ１およびＬ１と同義であり、好ましい範囲も同様である。
Ｐは、アルキレンオキシ鎖の繰り返しからなる基を含む基を表し、−アルキレンオキシ鎖の繰り返しからなる基−末端原子または末端基からなることがより好ましい。
末端原子または末端基としては、水素原子、アルキル基、アリール基、水酸基が好ましく、水素原子、炭素数１〜５のアルキル基、フェニル基、水酸基がより好ましく、水素原子、メチル基、フェニル基および水酸基がさらに好ましく、水素原子が特に好ましい。
（ｂ）２〜２０個の無置換のアルキレンオキシ鎖の繰り返しからなる基を側鎖に有する繰り返し単位の割合が、前記色素多量体を構成する全繰り返し単位の２〜２０モル％であることが好ましく、５〜１５モル％がより好ましい。
以下、本発明で用いることができる（ｂ）繰り返し単位の例を示すが、本発明はこれらに限定されるものではないことは言うまでもない。

The dye multimer used in the present invention has, as a repeating unit containing an alkali-soluble group, a repeating unit having a group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains in the side chain (hereinafter referred to as “(b) repeating unit”. May be included). By including such an alkali-soluble group, a colored composition having more excellent anti-color loss properties can be obtained.
The number of repeating alkyleneoxy chains in the repeating single (b) position is preferably 2 to 10, more preferably 2 to 15, and still more preferably 2 to 10.
One alkyleneoxy chain is represented by — (CH ₂ ) _n O—, and n is an integer, but n is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 or 3.
In the present invention, the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains may contain only one kind of alkyleneoxy chain, or may contain two or more kinds.
In the present invention, the repeating unit (b) is preferably represented by the following general formula (P).
General formula (P)

(In general formula (P), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group. P represents a group containing a group consisting of repeating alkyleneoxy chains. .)
X ¹ and L ¹ in the general formula (P) have the same meanings as X1 and L1 in the general formula (A), respectively, and preferred ranges thereof are also the same.
P represents a group containing a group consisting of repeating alkyleneoxy chains, more preferably a group consisting of repeating alkyleneoxy chains-terminal atom or terminal group.
The terminal atom or terminal group is preferably a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a hydroxyl group, a hydrogen atom, a methyl group, a phenyl group and A hydroxyl group is more preferred, and a hydrogen atom is particularly preferred.
(B) The ratio of the repeating unit having a group composed of repeating 2 to 20 unsubstituted alkyleneoxy chains in the side chain is 2 to 20 mol% of all repeating units constituting the dye multimer. Preferably, 5 to 15 mol% is more preferable.
Examples of the repeating unit (b) that can be used in the present invention are shown below, but it goes without saying that the present invention is not limited thereto.

Other functional groups possessed by the dye multimer include lactone, acid anhydride, amide, —COCH ₂ CO—, cyano group and other development promoting groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups And an affinity adjusting group such as a hydroxyl group, a maleimide group, and an amino group, and the like, which can be appropriately introduced.
Examples of the introduction method include a method of introducing the dye monomer in advance and a method of copolymerizing the monomer having the functional group.

Specific examples of the repeating unit having an alkali-soluble group or other functional group that the dye multimer may have are shown below, but the present invention is not limited thereto.

<<< Structural unit having at least one of structures represented by formulas (1) to (5) >>>
The dye multimer used in the present invention may have at least one of the structures represented by the formulas (1) to (5) in the same molecule. By setting it as such a structure, when a cured film is produced, exposure sensitivity and light resistance can be made favorable. Here, the structures represented by the formulas (1) to (5) contribute to improvement in exposure sensitivity and light resistance by functioning as a light stabilizer. Moreover, adhesiveness can be improved. Furthermore, the generation of development residues can be suppressed. Although this mechanism is presumed, by using a dye multimer having at least one of the dye structure and the structures represented by the formulas (1) to (5) in the same molecule, the dye structure and the formula (1) The distance to the structure represented by (5) becomes closer. As a result, it is considered that exposure sensitivity and light resistance can be improved more effectively.
The structure represented by the formula (1) is generically called a hindered amine system. The structure represented by the formula (2) is generically called a hindered phenol type. The structure represented by the formula (3) is generically called a benzotriazole type. The structure represented by the formula (4) is generically referred to as a hydroxybenzophenone series. The structure represented by the formula (5) is generically called a triazine type.

式（１）中、Ｒ¹は水素原子、炭素数１〜１８のアルキル基、アリール基、オキシラジカルを表す。Ｒ²およびＲ³はそれぞれ独立に炭素数１〜１８のアルキル基を表す。Ｒ²およびＲ³は互いに結合して炭素数４〜１２の脂肪族環を表してもよい。「＊」は式（１）で表される構造とポリマー骨格との結合手を表す。

In formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or an oxy radical. R ² and R ³ each independently represents an alkyl group having 1 to 18 carbon atoms. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms. “*” Represents a bond between the structure represented by the formula (1) and the polymer skeleton.

In Formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group, or an oxy radical, and an alkyl group having 1 to 18 carbon atoms is preferable.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear. 1-12 are preferable, as for carbon number of a C1-C18 alkyl group, 1-8 are more preferable, 1-3 are more preferable, and 1 or 2 is especially preferable. In particular, the alkyl group having 1 to 18 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group.
6-18 may be sufficient as carbon number of an aryl group, 6-12 may be sufficient, and 6-6 may be sufficient. Specific examples include a phenyl group.
When R ¹ in Formula (1) represents an alkyl group or aryl group having 1 to 18 carbon atoms, the alkyl group or aryl group having 1 to 18 carbon atoms may have a substituent or is unsubstituted. It may be. Examples of the substituent which may have include a substituent selected from the substituent group A described above.
In formula (1), R ² and R ³ each independently represent a methyl group or an ethyl group, and a methyl group is preferred. R ² and R ³ may be bonded to each other to represent an aliphatic ring having 4 to 12 carbon atoms.
In formula (1), “*” represents a bond between the structure represented by formula (1) and the polymer skeleton. The bond may be bonded to the polymer backbone directly or via a linking group, or may be bonded to the above-described dye structure directly or via a linking group. In particular, “*” in formula (1) is preferably bonded to the polymer backbone directly or via a linking group.
Hereinafter, although the specific example of the structure represented by Formula (1) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (2) and the polymer skeleton.

In formula (2), R ⁴ represents the following formula (2A), an alkyl group having 1 to 18 carbon atoms or an aryl group. R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. “*” Represents a bond between the structure represented by the formula (2) and the polymer skeleton.
In formula (2), R ⁴ represents the above formula (2A), an alkyl group having 1 to 18 carbon atoms or an aryl group, and is preferably represented by formula (2A). Alkyl and aryl groups having 1 to 18 carbon atoms has the same meaning as the alkyl and aryl groups having 1 to 18 carbon atoms described in R ¹ in the formula (1). “*” Is synonymous with the bond described in the formula (1).

In formula (2A), R < ⁶ > represents a C1-C18 alkyl group each independently. “*” Represents a bond between the structure represented by the formula (2A) and the structure represented by the formula (2).
In the formula (2A), R ⁶ has the same meaning as the alkyl group having 1 to 18 carbon atoms described for R ¹ in the formula (1). “*” Is synonymous with the bond described in the formula (1).
Hereinafter, although the specific example of the structure represented by Formula (2) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (2) and the polymer skeleton.

Wherein (3), R ⁷ represents an alkyl group having 1 to 18 carbon atoms; n1 represents an integer of 0 to 3. When n1 is 2 or 3, each R ⁷ may be the same or different. “*” Represents a bond between the structure represented by the formula (3) and the polymer skeleton.
In the formula (3), R ⁷ has the same meaning as alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1).
In Formula (3), n1 represents an integer of 0 to 3, an integer of 0 to 2 is preferable, and 0 or 1 is preferable.
In formula (3), “*” is synonymous with the bond described in formula (1).
Hereinafter, although the specific example of the structure represented by Formula (3) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (3) and the polymer skeleton.

In formula (4), R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 18 carbon atoms. n2 represents an integer of 0 to 3. n3 represents an integer of 0 to 4. When n2 is 2 or 3, each R ⁸ may be the same or different. When n3 represents an integer of 2 to 4, each R ⁹ may be the same or different. “*” Represents a bond between the structure represented by the formula (4) and the polymer skeleton.
In formula (4), R ⁸ and R ⁹ has the same meaning as alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1).
In formula (4), n2 represents the integer of 0-3, the integer of 0-2 is preferable and 0 or 1 is preferable.
In Formula (4), n3 represents an integer of 0 to 4, an integer of 0 to 2 is preferable, and 0 or 1 is preferable.
In formula (4), “*” is synonymous with the bond described in formula (1).
Hereinafter, although the specific example of the structure represented by Formula (4) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (4) and the polymer skeleton.

In formula (5), R ^{10 to} R ¹² each independently represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. n4 to n6 each independently represents an integer of 0 to 5. n7 to n9 each independently represents 0 or 1, and at least one of n7 to n9 represents 1. “*” Represents a bond between the structure represented by the formula (5) and the polymer skeleton.

If R ¹⁰ in the formula (5) represents an alkyl group having 1 to 18 carbon atoms, it has the same meaning as alkyl group having 1 to 18 carbon atoms described in R ¹ in the formula (1), 1 to 3 carbon atoms The alkyl group is preferably a methyl group. If R ¹⁰ represents an alkoxy group having 1 to 8 carbon atoms, carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 5, 1 to 4 is more preferred.
R ¹⁰ in Formula (5) may further have a substituent. Examples of the substituent which may have include a substituent selected from the substituent group A described above.
N4 in Formula (5) represents an integer of 0 to 5, an integer of 1 to 4 is preferable, and 2 or 3 is preferable. When n4 represents an integer of 2 to 5, each R ¹⁰ may be the same or different.
R ¹¹ in formula (5) has the same meaning as R ¹⁰ in formula (5), and the preferred range is also the same.
N5 in Formula (5) represents an integer of 0 to 5, an integer of 1 to 3 is preferable, and 1 or 2 is preferable. When n5 represents an integer of 2 to 5, each R ¹¹ may be the same or different.
R ¹² in formula (5) has the same meaning as R ¹⁰ in formula (5), and the preferred range is also the same.
N6 in Formula (5) represents an integer of 0 to 5, an integer of 0 to 3 is preferable, and 0 or 1 is preferable. When n6 represents an integer of 2 to 5, each R ¹² may be the same or different.
N7 to n9 in the formula (5) each independently represents 0 or 1, and at least one of n7 to n9 represents 1. In particular, it is preferable that only n7 represents 1, only n8 and n9 represent 1, or only one of n7, n8 and n9 represents 1.
In formula (5), “*” is synonymous with the bond described in formula (1).
Hereinafter, although the specific example of the structure represented by Formula (5) is shown, it is not limited to these. In the following structure, “*” represents a bond between the structure represented by the formula (5) and the polymer skeleton.

The structural unit having at least one of the structures represented by the formulas (1) to (5) of the dye multimer used in the present invention is preferably represented by the following formula (E).
Formula (E)

In the general formula (E), X ³ is as defined R ^x in the general formula (A-1-1). L ⁴ has the same meaning as L ^{11 in} formula (A-1-1). Z ¹ represents a structure represented by the above-described formulas (1) to (5).
Hereinafter, although the specific example of the structural unit which has at least 1 of the structure represented by Formula (1)-(5) is shown, this invention is not limited to these.

  The dye multimer may not have a structural unit having at least one of the structures represented by the formulas (1) to (5), but if it has, 100 masses of all the structural units in the dye multimer. %, The content of the structural unit having at least one of the structures represented by formulas (1) to (5) is preferably 0.5 to 20% by mass, and preferably 1 to 10% by mass. Is more preferable, and it is especially preferable that it is 1-5 mass%.

<<< specific end group >>>
The dye multimer used in the present invention preferably has a group represented by the general formula (I) or a group represented by the general formula (II) (hereinafter sometimes referred to as “specific end group”). By setting it as such a structure, solvent resistance and light resistance can be provided. For example, since it is synthesized by living radical polymerization, the dispersity (Mw / Mn) of the dye multimer can be reduced. That is, it is a dye multimer, and the light resistance can be further improved by reducing the proportion of the high molecular weight component, and the solvent resistance can be improved by reducing the proportion of the low molecular weight component. Can do. Furthermore, heat resistance, applicability, and developability can be further improved.

一般式（Ｉ）中、Ｚは水素原子または１価の置換基を表す。＊は、主鎖末端との結合位置を示す； Formula (I)

In general formula (I), Z represents a hydrogen atom or a monovalent substituent. * Indicates the position of binding to the end of the main chain;

In general formula (I), Z represents a monovalent substituent. Z is a hydrogen atom, a halogen atom, a carboxyl group, a cyano group, an alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or the total number of atoms of carbon atoms and hetero atoms. 3 to 30 monovalent heterocyclic groups, —OR ¹ , —SR ¹ , —OC (═O) R ¹ , —N (R ¹ ) (R ² ), —C (═O) OR ¹ , —C (═O) N (R ¹ ) (R ² ), —P (═O) (OR ¹ ) ₂ , —P (═O) (R ¹ ) ² or a monovalent group having a polymer chain is preferred, It is preferably selected from —SR ¹ , an aryl group, a heteroaryl group, an amino group substituted with an alkyl group and / or an aryl group, an alkoxy group, and an aryloxy group, and —SR ¹ (preferably an alkylthio group) , Arylthio group) or aryl group, more preferably an alkylthio group. More preferably an aryl group is particularly preferably an alkylthio group.
The aryl group as Z is preferably a phenyl group or a naphthyl group. The heteroaryl group as Z is preferably a nitrogen-containing 5-membered ring or 6-membered ring compound. The amino group substituted with an alkyl group and / or an aryl group as Z is preferably an amino group substituted with an alkyl group having 1 to 5 carbon atoms or a phenyl group. The alkoxy group as Z is preferably an alkoxy group having 2 to 5 carbon atoms. The aryloxy group as Z is preferably a phenoxy group.

R ¹ and R ² are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a carbon atom and a hetero atom. And a monovalent heterocyclic group having 3 to 30 atoms in total, the alkyl group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a carbon atom and a hetero atom. These monovalent heterocyclic groups having a total of 3 to 30 atoms, R ¹ and R ² may be either substituted or unsubstituted. Examples of the substituent when substituted include an alkyl group and an aryl group.
R ¹ and R ² are each independently preferably an alkyl group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms or a phenyl group. preferable.

一般式（ＩＩ）中、ＡおよびＢは、それぞれ独立に、１価の置換基を表す。ＡとＢは互いに連結して環を形成しても良い。＊は、主鎖末端との結合位置を示す。 Formula (II)

In general formula (II), A and B each independently represent a monovalent substituent. A and B may be connected to each other to form a ring. * Indicates the binding position to the end of the main chain.

The monovalent substituents represented by A and B are each independently preferably an alkyl group having 1 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms. The alkyl group having 1 to 30 carbon atoms is more preferably 3 to 10 carbon atoms.
In particular, one of A and B is a secondary or tertiary alkyl group having 1 to 30 carbon atoms, and the other is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferably, one of A and B is tertiary alkyl having 1 to 30 carbon atoms, the other of A and B is more preferably an alkyl group having 1 to 30 carbon atoms, and one of A and B is It is particularly preferred that it is a tertiary alkyl group having 1 to 30 carbon atoms and the other is a secondary or tertiary alkyl group having 1 to 30 carbon atoms (more preferably a secondary alkyl group having 1 to 30 carbon atoms).
As a substituent which the C1-C30 alkyl group may have, an aryl group is preferable and a phenyl group is more preferable. As the substituent that the aryl group may have, an aryl group is preferable. Furthermore, these groups may be substituted with other substituents. A and B may be bonded to each other to form a ring.

Particularly in the present invention, Z in the general formula (I) is —SR ¹ or an aryl group, and A and B in the general formula (II) are each a secondary or tertiary alkyl group having 1 to 30 carbon atoms. (However, A and B may be bonded to each other to form a ring).

  Although the specific example of a terminal group is shown, this invention is not limited to this.

  As a method for introducing the terminal group represented by the general formula (I) or (II) into the polymer main chain, a compound represented by the general formula (Ia), a compound represented by the general formula (IIa), and A method in which a polymerizable compound having a dye structure is radically polymerized in the presence of at least one radical represented by formula (IIb) is preferred.

一般式（Ｉａ）中、Ｚは一般式（Ｉ）と同義である。Ｃは一価の有機基を表す。 Formula (Ia)

In general formula (Ia), Z has the same meaning as in general formula (I). C represents a monovalent organic group.

一般式（ＩＩａ）中、Ｚは一般式（ＩＩ）と同義である。Ｄは一価の有機基を表す。 Formula (IIa)

In general formula (IIa), Z is synonymous with general formula (II). D represents a monovalent organic group.

一般式（ＩＩｂ）中、ＡおよびＢは一般式（ＩＩ）と同義である。 Formula (IIb)

In general formula (IIb), A and B are synonymous with general formula (II).

  By blending such an additive, the terminal inactivation at the time of radical polymerization is in an equilibrium state, and the radical is not apparently deactivated. By polymerizing by such living radical polymerization, a multimer having a low degree of dispersion can be obtained.

The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000, more preferably 3,000 to 30,000, and preferably 6,000 to 20,000. Particularly preferred.
Moreover, the ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dye multimer is preferably 1.0 to 2.0, and preferably 1.1 to 2.0. It is more preferable that it is 1.8, and it is especially preferable that it is 1.1-1.5.

  The glass transition temperature (Tg) of the dye multimer according to the present invention is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. By being in this region, when applying the colored composition of the present invention to the production of a color filter or the like, it becomes possible to reduce the concentration change caused by the heating process.

  When the dye multimer used in the present invention contains a repeating unit having a dye structure and another repeating unit, it is preferably a random polymer of a polymerizable compound containing a dye and another polymerizable compound. By using a random polymer, the dye structure is present randomly in the dye multimer, and the effects of the present invention are more effectively exhibited.

  Further, the extinction coefficient per unit weight of the dye multimer according to the present invention (hereinafter referred to as ε ′; ε ′ = ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, and 60 More preferably, it is more preferably 100 or more. By being in this range, when a color filter is produced by applying the colored composition of the present invention, a color filter with good color reproducibility can be produced.

The molar extinction coefficient of the dye multimer used in the colored composition of the present invention is preferably as high as possible from the viewpoint of coloring power.
From the viewpoint of color transfer, the reduced viscosity of the dye multimer used in the colored composition of the present invention is preferably 4.0 to 10.0, more preferably 5.0 to 9.0, and 6 More preferably, it is 0.0 to 7.0. The reduced viscosity can be measured using, for example, an Ubbelohde viscometer.

The dye multimer according to the present invention is preferably a compound that dissolves in the following organic solvent.
Examples of the organic solvent include esters (eg, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate). , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), ketones (methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), aromatic hydrocarbons (for example, toluene, xylene, etc.), and these solvents 1% by mass or more and 50% by mass or less is preferable, more preferably 5% by mass or more and 40% by mass or less, and further preferably 10% by mass or more and 30% by mass or less. By being in this region, when the colored composition of the present invention is applied to the production of a color filter or the like, it becomes possible to reduce a decrease in density due to a suitable coated surface shape or elution after application of other colors. .

  In the colored composition of the present invention, the dye multimer may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount corresponds to content mentioned later.

The content of the dye multimer in the colored composition of the present invention is set in consideration of the content ratio with the pigment described later.
The mass ratio of the dye multimer to the pigment (dye multimer / pigment) is preferably 0.1 to 5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.
The colorant component in the coloring composition of the present invention (pigment multimer, the sum of pigments and other dyes described later) is preferably 10 to 80% by mass of the total solid content of the coloring composition, and is preferably 15 to 60%. More preferably, it is mass%.

The coloring composition of the present invention contains a curable compound in addition to the dye multimer. Furthermore, the coloring composition of the present invention may contain other components. For example, for the purpose of adjusting the color value, it is preferable to include other colorant (preferably pigment) and pigment dispersant in addition to the dye multimer.
Moreover, the coloring composition of this invention is used for formation of the colored layer of a color filter. In the case of forming a color filter, it usually contains a curable compound in addition to the dye multimer, the pigment, and the pigment dispersion. Examples of the curable compound include a polymerizable compound and an alkali-soluble resin (including an alkali-soluble resin containing a polymerizable group), and are appropriately selected depending on the application and production method. The curable compound is preferably a polymerizable compound. Furthermore, the coloring composition of the present invention preferably contains a photopolymerization initiator.
For example, when the colored layer is formed by a photoresist, the colored composition of the present invention comprises the dye multimer of the present invention, an alkali-soluble resin as a curable compound, a pigment, a pigment dispersion, and a photopolymerization initiator. Things are preferred. Furthermore, components such as a surfactant and a solvent may be included.
Moreover, when forming a colored layer by dry etching, the composition containing the pigment | dye multimer in this invention, the polymeric compound as a sclerosing | hardenable compound, a pigment, a pigment dispersion, and a photoinitiator is preferable. Furthermore, components such as a surfactant and a solvent may be included.
Details of these will be described below.

<Polymerizable compound>
The coloring composition of the present invention preferably contains a polymerizable compound.
Known polymerizable compounds that can be cross-linked by radicals, acids, and heat can be used, and examples thereof include polymerizable compounds containing an ethylenically unsaturated bond, cyclic ether (epoxy, oxetane), methylol and the like. The polymerizable compound is suitably selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, from the viewpoint of sensitivity. Among them, a polyfunctional polymerizable compound having 4 or more functional groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.

  Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylates obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as nurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A Urethane (meth) acrylates as described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Other preferable polymerizable compounds include a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated group. It is also possible to use a compound having two or more functions, a cardo resin.

  Moreover, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, paragraph numbers [0254] to [0257] of JP-A-2008-292970 are disclosed. Also suitable are the compounds described in.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (═O) CH═CH ₂ or —OC. A group represented by (═O) C (CH ₃ ) ═CH ₂ is represented.
Specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) include the compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.

  In addition, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof, and (meth) acrylated, It can be used as a polymerizable compound.

  Among these, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.) ), Ethyleneoxy-modified dipentaerythritol hexaacrylate (commercially available product is A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and propylene glycol residues. Is preferred. These oligomer types can also be used.

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone modified polyfunctionality obtained by esterifying polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone ( Mention may be made of (meth) acrylates. Especially, the polyfunctional monomer which has a caprolactone structure represented with the following general formula (Z-1) is preferable.

  In the general formula (Z-1), all six Rs are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs are represented by the following general formula (Z -2), and the remainder is a group represented by the following general formula (Z-3).

In General Formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (1) to (3)) , Number of groups represented by formula (2) = 2, compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, number of groups represented by formula (2) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, compounds in which R ¹ are all hydrogen atoms), DPCA- 120 (a compound in which m = 2 in the same formula, the number of groups represented by formula (2) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

  The specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

In the general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —. Y represents each independently an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (Z-4), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. is there. However, when the total of each m is 0, any one of X is a carboxyl group.
In said general formula (ii), the sum total of acryloyl group and methacryloyl group is 5 or 6, n represents the integer of 0-10 each independently, and the sum total of each n is an integer of 0-60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the oxygen atom side A form in which the terminal of X is bonded to X is preferred.

  The compounds represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) is a conventionally known process, in which ethylene oxide or propylene oxide is opened to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by an addition reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable compounds. By using the compounds, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  Examples of the cyclic ether (epoxy, oxetane) include those having an epoxy group such as JER-827, JER-828, JER-834, JER-1001, JER-1002, and JER-1003 as bisphenol A type epoxy resins. , JER-1055, JER-1007, JER-1009, JER-1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation), etc., and bisphenol F As a type epoxy resin, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON830 EPICLON 835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and phenol novolac type epoxy resins such as JER-152, JER-154, JER- 157S70, JER-157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. As cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) , EO CN-1020 (manufactured by Nippon Kayaku Co., Ltd.), as an aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation) Celoxide 2021P, Celoxide 2081 Celoxide 2083, Celoxide 2085, EHPE-3150 (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol), EPOLEEAD PB 3600, PB 4700 (Above, manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-401 S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER -1031S (made by Japan Epoxy Resin Co., Ltd.) and the like. Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

About these polymeric compounds, the details of usage methods, such as the structure, single use or combined use, and addition amount, can be arbitrarily set according to the final performance design of a coloring composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, from the viewpoint of increasing the strength of the cured film formed from the colored composition, those having three or more functional groups are preferable, and further, different numbers of functional groups / different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, A method of adjusting both sensitivity and strength by using a combination of vinyl ether compounds) is also effective. Furthermore, it is preferable to use a trifunctional or higher functional polymerizable compound having a different ethylene oxide chain length in that the developability of the colored composition can be adjusted and an excellent pattern forming ability can be obtained.
In addition, the compatibility and dispersibility with other components (for example, photopolymerization initiators, dispersions, alkali-soluble resins, etc.) contained in the colored composition are also selected and used as a polymerizable compound. This is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

When blended, the content of the polymerizable compound in the colored composition of the present invention is preferably 0.1% by mass to 90% by mass, and 1.0% by mass to 60% by mass with respect to the total solid content in the colored composition. % By mass is more preferable, and 2.0% by mass to 40% by mass is particularly preferable.
The composition of the present invention may contain only one type of polymerizable compound or two or more types. When two or more types are included, the total amount is preferably within the above range.

（式中、ｎは２〜４の整数を表し、Ｌは２〜４価の連結基を表す。） <Multifunctional thiol compound>
The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (I).
Formula (I)

(In the formula, n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

  In the general formula (I), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (II) to (IV), and a compound represented by (II) is particularly preferable. These polyfunctional thiols can be used alone or in combination.

  About the compounding quantity of the polyfunctional thiol in the composition of this invention, it is 0.3-8.9 weight% with respect to the total solid except a solvent, More preferably, it is the range of 0.8-6.4 weight%. It is desirable to add at. Polyfunctional thiols may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.

<Photopolymerization initiator>
The colored composition of the present invention preferably contains a photopolymerization initiator from the viewpoint of further improving sensitivity.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like, with oxime compounds being preferred.

  From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

トリアリールイミダゾール化合物、ベンゾイミダゾール化合物としては、以下の化合物が例示される。

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, triarylimidazole compounds, benzimidazole compounds, onium compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzimidazole compound is particularly preferable. The triarylimidazole compound may be a mixture with benzimidazole.
Specifically, examples of the trihalomethyltriazine compound include the following compounds. Note that Ph is a phenyl group.

Examples of the triarylimidazole compound and the benzimidazole compound include the following compounds.

A commercially available product can be used as the trihalomethyltriazine compound, for example, TAZ-107 (manufactured by Midori Chemical Co., Ltd.) can also be used.
In particular, when the colored composition of the present invention is used for the production of a color filter included in a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it is developed without any problems. From such a viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in paragraph No. 0075 of JP2013-077009A, and the like.

  Moreover, an acridine derivative is illustrated as photoinitiators other than the above. Specific examples include the compounds described in paragraph No. 0076 of JP2013-077009A, and the contents thereof are incorporated in the present specification.

  Examples of the ketone compound include compounds described in paragraph No. 0077 of JP2013-077009A, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are suitably used as photopolymerization initiators in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) are also suitably used as commercial products.

  Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, and ketoxime compounds described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

Particularly preferred are oxime compounds having a specific substituent as disclosed in JP-A-2007-2699779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061.
Specifically, the oxime compound that is a photopolymerization initiator is preferably a compound represented by the following general formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In General Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

Although the specific example of general formula (OX-1) is shown below, it cannot be overemphasized that this invention is not limited to these.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

When the photopolymerization initiator is contained in the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.1% by mass or more and 50% by mass or less based on the total solid content of the color composition, More preferably, they are 0.5 mass% or more and 30 mass% or less, More preferably, they are 1 mass% or more and 20 mass% or less. Within this range, better sensitivity and pattern formability can be obtained.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Pigment>
The colored composition of the present invention may further contain a colorant other than the above-mentioned dye multimer. Specifically, it is preferable to contain a pigment.
As the pigment used in the present invention, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferably used. The pigment preferably has a high transmittance.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Etc.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment Black 1,7

  These organic pigments can be used alone or in various combinations in order to adjust the spectrum and increase the color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm. When the ratio is 100: 51 or more, the main wavelength tends to be closer to the short wavelength, and the color resolution may not be improved. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the required spectrum.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

  The coloring composition of the present invention preferably contains a pigment other than black, and is suitable for a blue pigment.

When used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle size of the pigment can be measured by a known method such as an electron microscope.
Among these, the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments. In particular, C.I. I. Pigment red 177 (anthraquinone pigment), C.I. I. Pigment red 254 (diketopyrrolopyrrole pigment), C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment Blue 15: 6 (phthalocyanine pigment), C.I. I. Pigment yellow 138 (quinophthalone pigment), C.I. I. Pigment yellow 139,185 (isoindoline pigment), C.I. I. Pigment yellow 150 (azomethine pigment), C.I. I. Pigment violet 23 (dioxazine pigment) is particularly preferred.

The content of the pigment is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and still more preferably 25% with respect to all components excluding the solvent contained in the coloring composition. It is mass%-50 mass%.
The composition of the present invention may contain only one type of pigment or two or more types of pigment. When two or more types are included, the total amount is preferably within the above range.

  Moreover, in this invention, you may contain dyes other than the said pigment | dye multimer, and pigments other than the above-mentioned. For example, JP-A 64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Toho 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No., U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. The chemical structure uses dyes such as pyrazole azo, anilino azo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. it can.

<Pigment dispersant>
When the coloring composition of the present invention has a pigment, a pigment dispersant can be used in combination as desired.
Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives, etc. Can do.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  Examples of the terminal-modified polymer having an anchor site to the pigment surface include polymers having a phosphate group at the terminal described in JP-A-3-112992, JP-T2003-533455, and the like. Examples thereof include a polymer having a sulfonic acid group at the terminal end described in JP-A-273191, and a polymer having a partial skeleton of an organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, a polymer in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocycle, etc.) to the surface of the pigment described in JP-A-2007-277514 are introduced. It is preferable because of excellent dispersion stability.

  Examples of the graft polymer having an anchor site to the pigment surface include a polyester-based dispersant, specifically, JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, and JP-A-10-339949 Copolymers of macromonomer and nitrogen atom monomer described in JP-A-2004-37986, International Publication Pamphlet WO2010 / 110491, etc., JP-A-2003-238837, JP-A-2008-9426, JP-A Grafts having partial skeletons and heterocyclic rings of organic dyes described in JP-A-2008-81732 Polymer, and a copolymer of a macromonomer and acid group-containing monomers described in JP 2010-106268 Publication. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 has the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion. From the viewpoint of

  As the macromonomer used when the graft polymer having an anchor site to the pigment surface is produced by radical polymerization, a known macromonomer can be used. Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate whose group is a methacryloyl group), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), PLACEL FM5 manufactured by Daicel Chemical Industries Ltd. ε-caprolactone 10 molar equivalent addition product), and JP-A-2-272 And polyester-based macromonomers described in Japanese Patent No. 009. Among these, a polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion, Furthermore, a polyester macromonomer represented by a polyester macromonomer described in JP-A-2-272009 is particularly preferable.

  As the block polymer having an anchor site to the pigment surface, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.

  The pigment dispersant that can be used in the present invention is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate) manufactured by BYK Chemie. ), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), “EFKA 4047, 4050 to 4010 to 4165 (polyurethane system), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), manufactured by EFKA, 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid) ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) manufactured by Kyoeisha Chemical Co., Ltd. ) ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid) ”, # 7004 (poly) Ether ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin polycondensate) ", MS, C, SN-B (aromatic sulfonic acid formalin) manufactured by Kao Corporation Polycondensate) ”,“ homogenol L-18 (polymeric polycarbohydrate) Acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," Acetamine 86 (stearylamine acetate) "," Solsperse 5000 (phthalocyanine derivative) "manufactured by Nippon Lubrizol Co., Ltd., 22000 ( Azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 manufactured by Nikko Chemicals ” (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawano Fine Chemical Co., Ltd. Hinoact T-8000E, etc., Shin-Etsu Chemical Co., Ltd., organosiloxane polymer P341, Yusho Co., Ltd. “W001: Cationic surfactant”, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, Nonionic surfactants such as polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47 manufactured by Morishita Sangyo Co., Ltd.” , EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by San Nopco" Disperse Aid 6, Disperse Aid " , Disperse Aid 15, Disperse Aid 9100, etc., manufactured by ADEKA Corporation “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant may be used in combination with an alkali-soluble resin together with a terminal-modified polymer, a graft polymer, or a block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples thereof include acidic cellulose derivatives, and (meth) acrylic acid copolymers are particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred. Specifically, an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.

In the coloring composition, when the pigment dispersant is contained, the total content of the pigment dispersant is preferably 1 part by mass to 80 parts by mass with respect to 100 parts by mass of the pigment, and 5 parts by mass to 70 parts by mass. Part is more preferable, and it is further more preferable that it is 10 mass parts-60 mass parts. The specific dispersion resin is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, among the dispersant components contained in the coloring composition.
The composition of the present invention may contain only one type of pigment dispersant, or two or more types of pigment dispersants. When two or more types are included, the total amount is preferably within the above range.

Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts by mass in terms of mass with respect to 100 parts by mass of the pigment, and 10 to 80 parts by mass. More preferred is the range of parts.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1 mass part-30 mass parts in conversion of mass as a usage-amount of a pigment derivative with respect to 100 mass parts of pigments, 3 mass parts-20 mass parts. More preferably, it is in the range, and particularly preferably in the range of 5 to 15 parts by mass.

  In the coloring composition, from the viewpoint of curing sensitivity and color density, the total content of the coloring agent and the dispersing agent component is 50% by mass or more and 90% by mass or less with respect to the total solid content constituting the coloring composition. Is more preferable, 55 mass% or more and 85 mass% or less is more preferable, and 60 mass% or more and 80 mass% or less is further more preferable.

<(F) Alkali-soluble resin>
The coloring composition of the present invention preferably further contains an alkali-soluble resin.
The molecular weight of the alkali-soluble resin is not particularly defined, but it is preferable that Mw is 5000 to 100,000. Moreover, it is preferable that Mn is 1000-20,000.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.

  Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable. These acid groups may be used alone or in combination of two or more.

Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  As the alkali-soluble resin, a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”) are essential. It is also preferable to include a polymer (a) obtained by polymerizing the monomer component.

一般式（ＥＤ２）中、Ｒは、水素原子または炭素数１〜３０の有機基を表す。一般式（ＥＤ２）の具体例としては、特開２０１０−１６８５３９号公報の記載を参酌できる。 In General Formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
General formula (ED2)

In General Formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP 2010-168539 A can be referred to.

Thereby, the coloring composition of this invention can form the cured coating film which was very excellent also in transparency with heat resistance. In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2 ′-[oxybis (methylene)] bis-2-prope , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) Cyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

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

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

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

  Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, it is preferable to use an alkali-soluble resin having a polymerizable group. When such an alkali-soluble resin is used, the effect of the present invention tends to improve the solvent resistance. Furthermore, light resistance and heat resistance tend to be further improved. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting compound having polymerizable group, JP 2002-229207 A Resin obtained by basic treatment of a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-2003-335814 Etc. are preferable.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers is suitable. . In addition, benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2 described in JP-A-7-140654 -Hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Are particularly preferred examples include a copolymer of benzyl methacrylate / methacrylic acid.

As the alkali-soluble resin, paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to and the contents thereof can be referred to. Is incorporated herein.
Furthermore, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, No. 024934, paragraph numbers 0132 to 0143 described in paragraphs 0132 to 0143 and the binder resins used in the examples, JP 2011-242752A paragraphs 0092 to 0098 and the binder resins used in the examples, Paragraph No. of Kokai 2012-032770 It preferred to use a binder resin according to 030-0072. These contents are incorporated herein. More specifically, the following resins are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

When the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1% by mass to 15% by mass, more preferably 2% by mass with respect to the total solid content of the coloring composition. It is -12 mass%, Most preferably, it is 3 mass%-10 mass%.
The composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
In addition to the above-mentioned components, the coloring composition of the present invention is within the range that does not impair the effects of the present invention, and further includes an organic solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, and an organic carboxylic acid anhydride. It may contain other components such as products.

<< Organic solvent >>
The coloring composition of the present invention may contain an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but in particular, the solubility, coating property, and safety of ultraviolet absorbers, alkali-soluble resins and dispersants, etc. It is preferable to select in consideration of the properties. Moreover, when preparing the coloring composition in this invention, it is preferable that at least 2 type of organic solvent is included.

  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. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And ethers For example, 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, and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons such as toluene And xylene are preferred.

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

The content of the organic solvent in the colored composition is preferably such that the total solid concentration of the composition is 5% by mass to 80% by mass from the viewpoint of applicability, and 5% by mass to 60% by mass. More preferably, 10% by mass to 50% by mass is particularly preferable.
The composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.

<< Crosslinking agent >>
It is also possible to further increase the hardness of the cured film obtained by curing the colored composition by using a crosslinking agent in the colored composition of the present invention.
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.
The details of paragraphs 0134 to 0147 of JP-A No. 2004-295116 can be referred to for details such as specific examples of the crosslinking agent.
When the coloring composition of the present invention contains a crosslinking agent, the blending amount of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass, and 3 to 20% by mass of the total solid content of the composition. More preferred.
The composition of the present invention may contain only one type of cross-linking agent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
In the colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When the coloring composition of the present invention contains a polymerization inhibitor, the addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition.
The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Surfactant >>
Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the coloring composition of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved. Liquidity can be further improved.
That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, wetting the coated surface by reducing the interfacial tension between the coated surface and the coating liquid. The coating property is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Rusupasu 20000 (Lubrizol Japan Co., Ltd.), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
When the coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass with respect to the total mass of the coloring composition, more preferably It is 0.005 mass%-1.0 mass%.
The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<< Organic carboxylic acid, organic carboxylic anhydride >>
The coloring composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

When the colored composition of the present invention contains an organic carboxylic acid or an organic carboxylic acid anhydride, the amount of the organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% by weight in the total solid content. , Preferably 0.03 to 5% by weight, more preferably 0.05 to 3% by weight.
The composition of the present invention may contain only one type of organic carboxylic acid and / or organic carboxylic acid anhydride, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the residual undissolved coloring composition while maintaining high pattern adhesion. .

In addition to the above, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the coloring composition as necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116, the contents of which are incorporated herein.
The coloring composition of the present invention can contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the publication.
The composition of the present invention may contain only one type of the above components, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Method for preparing colored composition>
The coloring composition of the present invention is prepared by mixing the aforementioned components.
In preparing the colored composition, the components constituting the colored composition may be mixed together, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored composition prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm, more preferably about 0.05 μm to 0.5 μm. Can be provided.

  The colored composition of the present invention is preferably used for forming a colored layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film having excellent heat resistance and color characteristics, it is suitably used for forming a colored pattern (colored layer) of a color filter. . The colored composition of the present invention is used for forming a colored pattern such as a solid-state imaging device (for example, CCD, CMOS, etc.), a color filter used in an image display device such as a liquid crystal display device (LCD) or an organic EL display device. Can be suitably used. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. In particular, a color filter for a solid-state imaging device such as a CCD and a CMOS can be suitably used as a production application.

<Curing film, pattern forming method, color filter, and color filter manufacturing method>
Next, the cured film, the pattern forming method, and the color filter in the present invention will be described in detail through the manufacturing method.
The cured film of the present invention is formed by curing the colored composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method of the present invention, the colored composition of the present invention is applied onto a support to form a colored composition layer, and unnecessary portions are removed to form a colored pattern.
The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.
The composition of the present invention may produce a color filter by pattern formation by a so-called photolithography method, or may form a pattern by dry etching.
That is, as a first production method of the color filter of the present invention, a step of forming a colored composition layer on a support using the colored composition of the present invention, and a step of exposing the colored composition layer in a pattern form And a step of developing an unexposed portion of the exposed colored composition layer.
In addition, as a second production method of the color filter of the present invention, a step of applying a colored composition on a support to form a colored composition layer and curing to form a colored layer; A process for producing a color filter, comprising: a step of forming a resist layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and a step of dry etching the colored layer using the resist pattern as an etching mask A method is illustrated.
In the present invention, it is more preferable to manufacture by photolithography.
These details are described below.

  Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.

<< Step of Forming Colored Composition Layer >>
In the step of forming the colored composition layer, the colored composition layer forming step is formed on the support by applying the colored composition of the present invention.

As a support that can be used in this step, for example, a solid-state imaging in which an imaging element (light receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate). An element substrate can be used.
The colored pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light shielding film may be provided between the colored patterns in the solid-state image sensor or on the back surface of the substrate for the solid-state image sensor.
Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface. In the undercoat layer, a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like can be blended, and each of these components is derived from the components blended in the above-described composition of the present invention. It is preferable to select appropriately.

  As a method for applying the colored composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  The coloring composition layer coated on the support can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

<Process for pattern formation by photolithography>
<< Exposure Step >>
In the exposure step, the colored composition layer formed in the colored composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern, for example, using an exposure apparatus such as a stepper. Thereby, a cured film is obtained.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is more preferably 30mJ / cm ² ~1500mJ / cm ² is preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 is particularly preferred.

The film thickness of the cured film (colored film) is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2 μm to 0.8 μm.
It is preferable to set the film thickness to 1.0 μm or less because high resolution and high adhesion can be obtained.
In addition, in this step, a cured film having a thin film thickness of 0.7 μm or less can also be suitably formed, and the obtained cured film is developed in a pattern forming process described later, thereby forming a thin film. Although it exists, the coloring pattern excellent in developability, surface roughness suppression, and pattern shape can be obtained.

<< Development process >>
Next, by performing an alkali development treatment, the colored composition layer of the light non-irradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the photocured portion remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is conventionally 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. And organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001% by mass to 10% by mass, An alkaline aqueous solution diluted with pure water so as to be preferably 0.01% by mass to 1% by mass is preferably used as the developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate and the like are preferable.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Next, it is preferable to perform heat treatment (post-bake) after drying. If a multicolor coloring pattern is formed, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

<When patterning by dry etching>
When forming a pattern by dry etching, the description of JP2013-64993A can be referred to, and the contents thereof are incorporated in the present specification.

  In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes other than the above as needed. For example, after performing the coloring composition layer forming step, the exposure step, and the pattern forming step described above, a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary.

Further, when the colored composition according to the present invention is used, for example, clogging of the nozzle of the coating device discharge section or the piping section, contamination due to adhesion, sedimentation, or drying of the colored composition or pigment in the coating machine may occur. is there. Therefore, in order to efficiently clean the contamination caused by the colored composition of the present invention, it is preferable to use the solvent relating to the present composition described above as a cleaning liquid. JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can also be suitably used for cleaning and removing the colored composition according to the present invention.
Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid with respect to contaminants, a surfactant related to the present composition described above may be added to the cleaning liquid.

Since the color filter of the present invention uses the colored composition of the present invention, the color filter of the present invention can be exposed with an excellent exposure margin, and the formed colored pattern (colored pixel) is excellent in pattern shape, and the surface of the pattern is not rough. Since the residue in the developing part is suppressed, the color characteristics are excellent.
The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

In addition, as a film thickness of the coloring pattern (color pixel) in the color filter of this invention, 2.0 micrometers or less are preferable, 1.0 micrometer or less is more preferable, and 0.7 micrometer or less is further more preferable.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

A transfer electrode comprising a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like that is open only in the light-receiving portion of the photodiode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.

<Image display device>
The color filter of the present invention can be used not only for the solid-state imaging device but also for an image display device such as a liquid crystal display device or an organic EL display device, and is particularly suitable for use in a liquid crystal display device. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). 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 may be used in 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.
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. In the color filter of the present invention, since a dye multimer excellent in hue is used, the color purity, light transmittance, etc. are good and the color pattern (pixel) is excellent in color, so the resolution is high and the long-term durability is excellent. A COA type liquid crystal display device can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

In addition to the color filter of the present invention, the liquid crystal display device provided with the color filter of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Have been described.

  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.

  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. Unless otherwise specified, “%” and “parts” are based on mass.

<Synthesis Example of Dye Compound A-1>

(Synthesis of Intermediate 1)
Compound No. of International Publication WO2013 / 082409 pamphlet. In Synthesis Example 2, Intermediate 1 was obtained by changing iodomethane to iodoethane.

(Synthesis of Intermediate 2)
In acid chloride conversion of Acid Red 289 of Exemplified Compound 1 in the pamphlet of International Publication No. WO2013 / 031838, Intermediate 2 was obtained using Intermediate 1.

(Synthesis of Intermediate 3)
Intermediate 2 (7.98 g) was dissolved in 40 ml of methylene chloride and stirred in an ice bath. N-ethylethanolamine (1.88 g) was added dropwise to the solution, and the mixture was stirred at room temperature for 3 hours, washed with 100 ml of 1N aqueous hydrochloric acid, and then washed with saturated brine. The organic layer was dried over sodium sulfate, and the residue obtained by concentration under reduced pressure was dissolved in 50 ml of chloroform and purified by column chromatography (chloroform: ethyl acetate = 7: 3) to obtain 6.65 g of Intermediate 3.
Maximum absorption wavelength: 543 nm (methanol)

(Synthesis of Intermediate 4)
Intermediate 3 (5 g), 2-isocyanatoethyl methacrylate (0.96 g), Neostan U-600 (manufactured by Nitto Kasei) 10 mg, 2,6-ditertiary butyl-4-methylphenol (5 mg) in dimethylacetamide 30 ml And stirred at 60 ° C. for 4 hours. The reaction solution was added to 100 ml of water and extracted with 100 ml of ethyl acetate. Then, it dried with sodium sulfate and concentrated under reduced pressure. To the residue, 100 ml of acetonitrile was added, stirred for 1 hour, and filtered to obtain 4.5 g of Intermediate 4.
Maximum absorption wavelength: 543 nm (methanol)

(Synthesis of Dye Compound A-1)
Intermediate 4 (4 g) was dissolved in 20 ml of methanol, lithium N, N-bis (trifluoromethanesulfonyl) imide (1.16 g) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, extraction was performed with 100 ml of water and 100 ml of ethyl acetate, and the organic layer was dried over sodium sulfate and concentrated under reduced pressure. To the obtained residue, 50 ml of acetonitrile was added, dispersed and washed, and filtered to obtain dye compound A-1 (4 g).
Maximum absorption wavelength: 543 nm (methanol)

<Synthesis Example of Dye Compound A-2>
In the synthesis example of the dye compound A-1, lithium N, N-bis (trifluoromethanesulfonyl) imide is changed to potassium N, N-bis (nonafluorobutanesulfonyl) imide, and the others are performed in the same manner. 2 was obtained.
Maximum absorption wavelength: 543 nm (methanol)

<Synthesis Example of Dye Compound A-3>
In the synthesis example of the dye compound A-1, lithium N, N-bis (trifluoromethanesulfonyl) imide is changed to potassium N, N-hexafluoropropane-1,3-disulfonylimide, and the others are performed in the same manner. Compound A-2 was obtained.
Maximum absorption wavelength: 543 nm (methanol)

<Synthesis Example of Dye Compound A-4>
In the synthesis example of the dye compound A-1, lithium N, N-bis (trifluoromethanesulfonyl) imide was changed to a lithium tetrakis (pentafluorophenyl) borate-ethyl ether complex, and the others were carried out in the same manner. Got.
Maximum absorption wavelength: 543 nm (methanol)

<Dye compounds A-5 to A-15>
Following the above synthesis example, monomers as raw materials for repeating units A-5 to A-15 described later were synthesized.

<Synthesis Example of Dye Multimer P-1>
24 g of cyclohexanone was added to the three-necked flask and heated to 90 ° C. under a nitrogen atmosphere. Dye compound A-1 (31.3 g, 25 mmol), methacrylic acid (6.45 g, 75 mmol), dodecyl mercaptan (1.89 g, 9.35 mmol), 2,2′-azobis (isobutyric acid) dimethyl) [Product name: V601, Wako Pure Chemical Industries, Ltd.] (4.31 g, 18.7 mmol) and a mixed solution of cyclohexanone (65.9 g) were added dropwise over 1 hour. Thereafter, the mixture was stirred at 90 ° C. for 3 hours, then cooled to room temperature, and reprecipitated by adding dropwise to a mixed solvent of ethyl acetate / acetonitrile = 1156 mL / 144 mL. After air blowing and drying at 40 ° C. for 1 day, 20.1 g of intermediate P-1 was obtained. Intermediate P-1 had an acid value of 2.02 mmol / g, and the composition ratio (molar ratio) was confirmed by ¹ H-NMR. As a result, the pigment part: methacrylic acid part = 25: 75.
In a three-necked flask, intermediate P-1 (12.5 g) obtained above, glycidyl methacrylate (2.68 g), tetraethylammonium bromide (0.5 g), p-methoxyphenol (0.015 g), cyclohexanone (83 3 g) was added and stirred at 105 ° C. under air for 4 hours. Thereafter, the mixture was allowed to cool to room temperature, and re-precipitated by adding dropwise to a mixed solvent of ethyl acetate / acetonitrile = 748 mL / 39 mL. After air-drying at 40 ° C. for 1 day, 5.52 g of dye multimer P-1 was obtained. The dye multimer P-1 has an acid value of 0.94 mmol / g, and the composition ratio (molar ratio) was confirmed by ¹ H-NMR. As a result, the dye part: methacrylic acid part: polymerizable group-containing part = 25: 40: 35.

<Synthesis Example of Dye Multimer P-2 to P-15>
The dye compound A-1 and other compounds in the dye multimer P-1 were synthesized by performing the same operation except that the monomers were changed so as to be the repeating units shown in Table 1 below.

上記色素多量体を構成する各繰り返し単位を下記に示す。

Each repeating unit constituting the dye multimer is shown below.

[Examples and Comparative Examples]
1. Preparation of resist solution Components of the following composition were mixed and dissolved to prepare an undercoat layer resist solution.
<Composition of resist solution for undercoat layer>
Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22 / 18, 40% propylene glycol monomethyl ether acetate (PGMEA) solution having a weight average molecular weight of 15,000 and a number average molecular weight of 9,000 (30.51 parts) -ethylenically unsaturated double bond-containing compound: dipentaerythritol hexaacrylate
12.20 parts-Polymerization inhibitor: p-methoxyphenol 0.0061 parts-Fluorine surfactant: F-475, manufactured by DIC Corporation 0.83 parts-Photopolymerization initiator: trihalomethyltriazine-based photopolymerization Initiator 0.586 parts (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

2. Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A substrate was obtained.

3. Preparation of coloring composition 3-1. Preparation of blue pigment dispersion Blue pigment dispersion 1 was prepared as follows.
C. I. Pigment Blue 15: 6 (13.0 parts (blue pigment, average particle size 55 nm)), Dispersbyk 111 (pigment dispersant) 5.0 parts, and PGMEA 82.0 parts were mixed with a beads mill (zirconia beads). 0.3 mm diameter) was mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion 1 (CI Pigment Blue 15: 6 dispersion, pigment concentration 13%) used in the coloring compositions of Examples and Comparative Examples.
With respect to the obtained blue pigment dispersion, the particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.

3-2. Preparation of colored composition The following components were mixed, dispersed, and dissolved to obtain colored compositions of Examples and Comparative Examples.
-Dye compound (compound described in the following table) 0.04 part as solid content-Solvent (PGMEA) 1.133 part-Alkali-soluble resin (compound of J12 below) 0.03 part-Dispersant (Solsperse 20000: (1 % Cyclohexane solution, manufactured by Nippon Lubrizol Co., Ltd.) 0.125 part. Photopolymerization initiator (compound of C-9 below) 0.012 part. Pigment dispersion (13% pigment concentration) 0.615 part. Curing 0.07 part of active compound and surfactant (glycerol propoxide: (1% cyclohexane solution)) 0.048 part

Ａ−ＤＰＨ−１２Ｅ（新中村化学製、エチレンオキシ変性ジペンタエリスリトールヘキサアクリレート） Curable compound KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate)

A-DPH-12E (manufactured by Shin-Nakamura Chemical, ethyleneoxy-modified dipentaerythritol hexaacrylate)

4). Fabrication of color filter by coloring composition <Pattern formation>
Each of the coloring compositions of Examples and Comparative Examples prepared as described above was added to the above 2. The colored composition layer (coating film) was formed by coating on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.6 μm.

Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm. .
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying.
As described above, a monochromatic color filter having a colored pattern formed by the colored composition of the example or the comparative example was produced.
Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern size was 1.0 μm was determined as the optimum exposure amount.

5). Performance evaluation 5-1. Heat resistance A glass substrate coated with the obtained colored composition was placed on a hot plate at 200 ° C. so as to be in contact with the substrate surface and heated for 1 hour, and then the chromaticity meter MCPD-1000 (Otsuka Electronics Co., Ltd.). )), The color difference (ΔE * ab value) before and after heating was measured as an index for evaluating heat fastness, and evaluated according to the following criteria. A smaller ΔE * ab value indicates better heat resistance. The ΔE * ab value is a value obtained from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (New Color Science Handbook edited by the Japan Color Society (1985) p. 60). 266).
ΔE * ab = {(ΔL *) ² + (Δa *) ² + (Δb *) ² } ^1/2
Evaluation was made according to the following criteria.
A: The value of ΔE * ab is 0 or more and less than 1.0 B: The value of ΔE * ab is 1.0 or more and less than 3.0 C: The value of ΔE * ab is 3.0 or more

5-2. Cyclohexane solubility The solubility of the resulting colored composition in PGMEA at 25 ° C. was evaluated according to the following criteria.
A: When the solubility is 12.5 mass% or more B: When 10 mass% or more and less than 12.5 mass% C: When 5 mass% or more and less than 10 mass% D: When less than 5 mass%

5-3. Color Transfer Evaluation The absorbance of the colored pattern in each color filter was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance A).
A CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; transparent base material) was applied to the color pattern forming surface of the color filter so that the dry film thickness was 1 μm, and dried to form a transparent film. Thereafter, heat treatment was performed at 280 ° C. for 5 minutes.
After the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance B).
With respect to the value of absorbance B of the obtained transparent film, the ratio [%] to the value of absorbance A of the colored pattern measured before heating was calculated [the following (formula A)]. This was used as an index for evaluating the color transfer to adjacent pixels.
(Formula A) Color transfer (%) = absorbance B / absorbance A × 100
A: The value of Formula A is 0 or more and less than 2 B: The value of Formula A is 2 or more and less than 5 C: The value of Formula A is 5 or more

5-4. Spectral evaluation before and after development On a glass wafer, a CT-4000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; transparent base material) is applied so that the dry film thickness is 0.1 μm, and dried to obtain a transparent film. After forming, heat treatment was performed at 220 ° C. for 5 minutes.
The colored composition was applied using a spin coater so as to have a film thickness of 0.6 μm, and heat-treated (pre-baked) for 120 seconds using a hot plate at 100 ° C.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at a wavelength of 365 nm and an exposure amount of 500 mJ / cm ² .
The transmittance of the color filter thus obtained was measured in a wavelength region of 300 nm to 800 nm with a spectrophotometer (reference: glass substrate) of an ultraviolet-visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation).
It is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and is used at 23 ° C. for 60 seconds using CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). Paddle development is performed, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying. After drying, the spectroscopic measurement is performed again, and the transmittance variation before and after development (when the transmittance before development is T0 and the transmittance after development is T1 is expressed by the expression | T0−T1 |). Values were evaluated as follows: B and above are practical levels.

AA: Less than 2% change in transmittance before and after development in the entire region of 300 nm to 800 nm A: In all region of 300 nm to 800 nm, the change in transmittance before and after development is 2% or more and less than 5% B: All change of 300 nm to 800 nm In the region, the transmittance variation before and after development is 5% or more and less than 10%. C: The transmittance variation before and after development is 10% or more in the entire region of 300 nm to 800 nm.

As is clear from the above table, it was found that the composition of the present invention has high light resistance and can effectively suppress the spectral change during development. Furthermore, it has been found that it is also effective in suppressing changes in heat resistance, solvent solubility, and color transfer.
On the other hand, when the xanthene dye structure is not a multimer (Comparative Examples 1 to 3), the light resistance and / or the spectrum at the time of development was easily changed. Furthermore, each evaluation of changes in heat resistance, solvent solubility, and color transfer also tended to be inferior.

Claims (12)

A dye multimer having a repeating unit represented by the general formula (A1-1) and / or a repeating unit represented by the general formula (A1-2) (however, the repeating unit represented by the following formula (A′-17)) A dye multimer having a unit and a dye multimer having a repeating unit represented by the following formula (A′-39));

A coloring composition comprising: a curable compound;
Formula (A1-1)

In General Formula (A1-1), ^one of R ^{1 to} R ¹⁵ is a main chain structure represented by the following General Formula (A1-1-1), and at least one of R ^{1 to} R ¹⁵ is A group having a sulfonate anion or a group represented by the general formula (a1-1-2), or a group in which one of R ^{1 to} R ¹⁵ is represented by the general formula (a1-1-3) And
R ¹ and R ³ are each independently an alkyl group having 1 to 5 carbon atoms,
R ² and R ⁴ are each independently a group represented by the following general formula (A1-1-2),
R ^{5 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group;
R ^{11 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group;
General formula (A1-1-1)

In general formula (A1-1-1), L ¹¹ represents a single bond or a divalent linking group, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group;
General formula (A1-1-2)

In general formula (A1-1-2), R ^{23 to} R ²⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonylamide group, or a sulfonyl group. Represents a group, a sulfonylamide group, a nitro group, an amino group, an aminocarbonyl group, an aminosulfonyl group, a sulfonylimide group or a carbonylimide group, and R ²² and R ²⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. ;
Formula (a1-1-2)

In General Formula (a1-1-2), L ¹ represents a single bond or a divalent linking group, L ² represents —SO ₂ — or —CO—, G represents a nitrogen atom, and n 1 represents 1, R ⁶ may be the table to an aryl group containing an alkyl group or a fluorine atom containing fluorine atoms;
General formula (a1-1-3)

In general formula (a1-1-3), L ¹ represents a single bond or a divalent linking group, L ² represents —SO ₂ — or —CO—, and L ³ represents a divalent linking group. G represents a nitrogen atom, n2 represents 0, R ^7A and R ^7B each independently represents an alkylene group containing a fluorine atom or an arylene group containing a fluorine atom, and R ^X represents a hydrogen atom Represents a methyl group, a hydroxymethyl group or an alkoxymethyl group;
Formula (A1-2)

In General Formula (A1-2), ^one of R ^{1 to} R ¹⁵ includes a main chain structure represented by General Formula (A1-1-1),
R ¹ and R ³ are each independently an alkyl group having 1 to 5 carbon atoms,
R ² and R ⁴ are each independently a group represented by the general formula (A1-1-2),
R ^{5 to} R ¹⁰ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group;
R ^{11 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group;
X is an anion that forms a counter salt with a cation of xanthene, and is represented by an anion represented by the formula (AN-1), an anion represented by the formula (AN-2), or the formula (AN-5). An anion

In formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² may combine with each other to form a ring;

In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms;

In formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group.   The coloring composition according to claim 1, wherein the dye multimer further has an alkali-soluble group.   The coloring composition according to claim 1 or 2, wherein the dye multimer further has a polymerizable group.   The coloring composition according to any one of claims 1 to 3, wherein the curable compound is a polymerizable compound and further contains a photopolymerization initiator.   Furthermore, the coloring composition of any one of Claims 1-4 containing the pigment which has a phthalocyanine skeleton. In the main chain structure one of R ¹¹ to R ¹⁵ of one and the general formula of R ¹¹ ~R ¹⁵ (A1-2) is represented by the general formula (A1-1-1) of the general formula (A1-1) A colored composition according to any one of claims 1 to 5;   The colored composition according to any one of claims 1 to 6, which is used for forming a colored layer of a color filter.   The cured film obtained by hardening | curing the coloring composition in any one of Claims 1-7.   A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 7, a step of exposing the colored composition layer in a pattern, and an exposed colored composition Developing a non-exposed portion of the layer.   A color filter having the cured film according to claim 8.   A solid-state imaging device having the color filter according to claim 10.   An image display device comprising the color filter according to claim 10.