JP7130055B2 - Coloring composition, film, color filter, method for producing color filter, solid-state imaging device, and image display device - Google Patents

Description

The present invention relates to coloring compositions. The present invention also relates to a film using the coloring composition, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device.

2. Description of the Related Art In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements. A color filter usually comprises three primary color pixels of red, green and blue and serves to separate the transmitted light into the three primary colors.

A color filter is manufactured, for example, by using a coloring composition containing a coloring agent and forming a pattern by a photolithographic method. In forming a pattern by photolithography, the coloring composition further contains, in addition to the coloring agent, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin. things are used.

In recent years, the use of a phthalocyanine compound using Al as a central metal (hereinafter also referred to as an aluminum phthalocyanine compound) as a coloring agent has been studied (Patent Documents 1 to 3).

JP 2015-063593 A JP 2016-170370 A JP 2013-171063 A

The present inventors have extensively studied a coloring composition containing a coloring agent containing an aluminum phthalocyanine compound, and have found that the film obtained using this coloring composition tends to cause color unevenness. In particular, when a compound represented by the formula (1) or a compound represented by the formula (2) described later was used as the aluminum phthalocyanine compound, it was found that color unevenness tends to occur.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a coloring composition capable of forming a film with excellent photolithography properties and with suppressed color unevenness. Another object of the present invention is to provide a film using the coloring composition, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device.

式（１）中、Ｘ^１～Ｘ^４はそれぞれ独立して、置換基を表す；
Ｚ^１はヒドロキシ基、ハロゲン原子、－ＯＰ（＝Ｏ）Ｒ^１Ｒ^２、または－Ｏ－ＳｉＲ^３Ｒ^４Ｒ^５を表し、Ｒ^１～Ｒ^５はそれぞれ独立して、水素原子、ヒドロキシ基、アルキル基、アリール基、アルコキシ基、またはアリールオキシ基を表し、Ｒ^１とＲ^２、Ｒ^３とＲ^４は互いに結合して環を形成しても良い；
ｍ１～ｍ４は、それぞれ独立して０～４の整数を表し、ｍ１～ｍ４が２以上のとき、Ｘ^１～Ｘ^４はそれぞれ同一でも異なっていてもよい；

式（２）中、Ｘ^５～Ｘ^１２はそれぞれ独立して、置換基を表す；
Ｌ^Ａは、－Ｏ－ＳｉＲ^６Ｒ^７－Ｏ－、－Ｏ－ＳｉＲ^６Ｒ^７－Ｏ－ＳｉＲ^８Ｒ^９－Ｏ－、または－Ｏ－Ｐ（＝Ｏ）Ｒ^１０－Ｏ－を表し、Ｒ^６～Ｒ^１０はそれぞれ独立して、水素原子、ヒドロキシ基、アルキル基、アリール基、アルコキシ基、またはアリールオキシ基を表す；
ｍ５～ｍ１２は、それぞれ独立して０～４の整数を表し、ｍ５～ｍ１２が２以上のとき、Ｘ^５～Ｘ^１２はそれぞれ同一でも異なっていてもよい。
＜２＞ 着色剤は、カラーインデックスピグメントグリーン６２および、カラーインデックスピグメントグリーン６３から選ばれる少なくとも１種を含む、＜１＞に記載の着色組成物。
＜３＞ 着色剤は、カラーインデックスピグメントイエロー１３８、カラーインデックスピグメントイエロー１３９、カラーインデックスピグメントイエロー１５０及びカラーインデックスピグメントイエロー２３１から選択される少なくとも１種を含む、＜１＞または＜２＞に記載の着色組成物。
＜４＞ 着色剤は、更に下記式（３）で表される化合物を含む、＜１＞～＜３＞のいずれか１つに記載の着色組成物；

式（３）中、Ｒｙ^１～Ｒｙ^１３は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アリール基、スルホ基、スルホ基の塩、カルボキシル基、カルボキシル基の塩、フタルイミドメチル基、またはスルファモイル基を表す；
Ｒｙ^１～Ｒｙ^４のうち隣接した２つの基同士は結合して環を形成していてもよく、Ｒｙ^１０～Ｒｙ^１３のうち隣接した２つの基同士は結合して環を形成していてもよい。
＜５＞ 着色剤中における、式（１）で表される化合物と式（２）で表される化合物との合計の含有量が３０質量％以上である、＜１＞～＜４＞のいずれか１つに記載の着色組成物。
＜６＞ 樹脂は、エチレン性不飽和結合基を有する樹脂を含む、＜１＞～＜５＞のいずれか１つに記載の着色組成物。
＜７＞ 樹脂は、下記式（Ｉ）で表される化合物由来の繰り返し単位を含む樹脂を含有する、＜１＞～＜６＞のいずれか１つに記載の着色組成物；

式中、Ｘｉ^１は、ＯまたはＮＨを表し、
Ｒｉ^１は水素原子またはメチル基を表し、
Ｌｉ^１は２価の連結基を表し、
Ｒｉ^１０は置換基を表し、
ｍは０～２の整数を表し、
ｐは０以上の整数を表す。
＜８＞ 式（Ｉ）で表される化合物由来の繰り返し単位を含む樹脂は、更に、アルキル（メタ）アクリレート由来の繰り返し単位を含む、＜７＞に記載の着色組成物。
＜９＞ 着色組成物に含まれる重合性モノマーの質量Ｍ^１と、着色組成物に含まれる樹脂の質量Ｂ^１との比であるＭ^１／Ｂ^１が０．０３～０.１５である、＜１＞～＜８＞のいずれか１つに記載の着色組成物。
＜１０＞ 重合性モノマーは、コハク酸変性ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートおよびジペンタエリスリトールペンタ（メタ）アクリレートから選ばれる少なくとも１種を含む、＜１＞～＜９＞のいずれか１つに記載の着色組成物。
＜１１＞ ＜１＞～＜１０＞のいずれか１つに記載の着色組成物から得られる膜。
＜１２＞ ＜１１＞に記載の膜を有するカラーフィルタ。
＜１３＞ ＜１＞～＜１０＞のいずれか１つに記載の着色組成物を用いて支持体上に着色組成物層を形成する工程と、フォトリソグラフィ法により着色組成物層に対してパターンを形成する工程と、を有するカラーフィルタの製造方法。
＜１４＞ ＜１１＞に記載の膜を有する固体撮像素子。
＜１５＞ ＜１１＞に記載の膜を有する画像表示装置。The present inventor has extensively studied a coloring composition containing a coloring agent containing an aluminum phthalocyanine compound, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin, and found that such coloring It was considered that the reason why the film obtained using the composition tends to cause color unevenness is that the compatibility between the aluminum phthalocyanine compound and the polymerizable monomer having an ethylenically unsaturated bond group is insufficient. Therefore, as the aluminum phthalocyanine compound, while using the compound represented by the formula (1) or the compound represented by the formula (2) described later, the content of the polymerizable monomer having an ethylenically unsaturated bond group is adjusted to a predetermined range. The present inventors have found that a film having excellent photolithography properties and suppressed color unevenness can be formed by adjusting the ratio to , and have completed the present invention. Accordingly, the present invention provides the following.
<1> A coloring composition comprising a coloring agent, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin,
The coloring agent contains at least one selected from compounds represented by the following formula (1) and compounds represented by the following formula (2),
A coloring composition containing 0.1 to 6.0% by mass of a polymerizable monomer in the total solid content of the coloring composition;

In formula (1), X ¹ to X ⁴ each independently represent a substituent;
Z ¹ represents a hydroxy group, a halogen atom, —OP(=O)R ¹ R ² , or —O—SiR ³ R ⁴ R ⁵ , and R ¹ to R ⁵ each independently represent a hydrogen atom, a hydroxy group, represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ¹ and R ² , R ³ and R ⁴ may combine with each other to form a ring;
m1 to m4 each independently represent an integer of 0 to 4, and when m1 to m4 are 2 or more, X ¹ to X ⁴ may be the same or different;

In formula (2), X ⁵ to X ¹² each independently represent a substituent;
L ^A represents -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁶ R ⁷ -O-SiR ⁸ R ⁹ -O-, or -OP(=O)R ¹⁰ -O-; R ⁶ to R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
m5 to m12 each independently represent an integer of 0 to 4, and when m5 to m12 are 2 or more, X ⁵ to X ¹² may be the same or different.
<2> The coloring composition according to <1>, wherein the coloring agent contains at least one selected from Color Index Pigment Green 62 and Color Index Pigment Green 63.
<3> The colorant according to <1> or <2>, wherein the coloring agent contains at least one selected from Color Index Pigment Yellow 138, Color Index Pigment Yellow 139, Color Index Pigment Yellow 150 and Color Index Pigment Yellow 231. coloring composition.
<4> The coloring composition according to any one of <1> to <3>, wherein the coloring agent further contains a compound represented by the following formula (3);

In formula (3), Ry ¹ to Ry ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group, a salt of a sulfo group, a carboxyl group, a salt of a carboxyl group, phthalimidomethyl group, or represents a sulfamoyl group;
Two adjacent groups among Ry ¹ to Ry ⁴ may be bonded together to form a ring, and two adjacent groups among Ry ¹⁰ to Ry ¹³ may be bonded together to form a ring. good.
<5> Any of <1> to <4>, wherein the total content of the compound represented by formula (1) and the compound represented by formula (2) in the colorant is 30% by mass or more. or the coloring composition according to one.
<6> The colored composition according to any one of <1> to <5>, wherein the resin comprises a resin having an ethylenically unsaturated bond group.
<7> The colored composition according to any one of <1> to <6>, wherein the resin contains a resin containing a repeating unit derived from a compound represented by the following formula (I);

wherein Xi ¹ represents O or NH,
Ri ¹ represents a hydrogen atom or a methyl group;
Li ¹ represents a divalent linking group,
Ri ¹⁰ represents a substituent,
m represents an integer from 0 to 2,
p represents an integer of 0 or more.
<8> The colored composition according to <7>, wherein the resin containing a repeating unit derived from the compound represented by formula (I) further contains a repeating unit derived from an alkyl (meth)acrylate.
<9> M ¹ /B ¹ , which is the ratio of the mass M ¹ of the polymerizable monomer contained in the coloring composition and the mass B ¹ of the resin contained in the coloring composition, is 0.03 to 0.15, The colored composition according to any one of <1> to <8>.
<10> The polymerizable monomer contains at least one selected from succinic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate, <1>- The coloring composition according to any one of <9>.
<11> A film obtained from the colored composition according to any one of <1> to <10>.
<12> A color filter having the film according to <11>.
<13> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <10>, and patterning the colored composition layer by a photolithographic method A method for manufacturing a color filter comprising:
<14> A solid-state imaging device having the film according to <11>.
<15> An image display device comprising the film according to <11>.

ADVANTAGE OF THE INVENTION According to this invention, the coloring composition which is excellent in photolithography property and can form the film|membrane by which color nonuniformity was suppressed can be provided. Also, a film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the coloring composition can be provided.

The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "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).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, a pigment means a compound that is difficult to dissolve in a solvent.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .

<Coloring composition>
The coloring composition of the present invention is a coloring composition containing a coloring agent, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin, wherein the coloring agent is a coloring composition of the formula ( 1) containing at least one selected from the compound represented by the formula and the compound represented by formula (2), and containing 0.1 to 6.0% by mass of polymerizable monomers in the total solid content of the coloring composition It is characterized by

In the coloring composition of the present invention, since the content of the polymerizable monomer in the total solid content of the coloring composition is 0.1 to 6.0% by mass, the compound represented by (1) as a coloring agent or the formula Although the compound represented by (2) is used, it is possible to effectively suppress the occurrence of color unevenness in the resulting film while maintaining excellent photolithography properties.

Further, according to the coloring composition of the present invention, since the content of the polymerizable monomer is 0.1 to 6.0% by mass, the carbon-carbon bond is broken over time, but the polymerizable monomer that scatters from the film component is small, and film shrinkage over time of the obtained film can be suppressed. In particular, film shrinkage can be effectively suppressed even when the film is exposed to an environment with high humidity for a long period of time. Therefore, it is also possible to suppress the generation of voids between the film formed using the coloring composition of the present invention and the member adjacent to this film. For example, the colored composition of the present invention is used between pixels of other colors to form pixels, or the composition of the present invention is used to form pixels of other colors to form a structure such as a color filter. , the formation of voids between adjacent pixels can be suppressed even when such a structure is exposed to a high-humidity environment for a long period of time. In addition, when a structure such as a color filter is produced by forming pixels in regions partitioned by partition walls using the coloring composition of the present invention, such a structure may be kept in a humid environment for a long period of time. Even when exposed, it is possible to suppress the generation of voids between the pixels and the partition walls.

The coloring composition of the present invention can be preferably used as a coloring composition for color filters. Specifically, it can be preferably used as a coloring composition for forming pixels of a color filter. In addition, the coloring composition of the present invention can be preferably used as a coloring composition for solid-state imaging devices, and more preferably used as a coloring composition for pixel formation of color filters used in solid-state imaging devices. In addition, the coloring composition of the present invention can be preferably used as a coloring composition for display devices, and more preferably used as a coloring composition for pixel formation of color filters used in display devices. The colored composition of the present invention can also be used as a composition for forming colored microlenses. Examples of a method for manufacturing a color microlens include the method described in Japanese Patent Application Laid-Open No. 2018-010162.

The coloring composition of the present invention will be described in detail below.

<<coloring agent>>
The coloring composition of the present invention contains a coloring agent. In the present invention, a colorant containing at least one selected from compounds represented by formula (1) and compounds represented by formula (2) is used. Hereinafter, the compound represented by formula (1) is also referred to as compound (1). Moreover, the compound represented by Formula (2) is also called compound (2).

In formula (1), X ¹ to X ⁴ each independently represent a substituent. Substituents represented by X ¹ to X ⁴ include substituents T described later. Substituents represented by X ¹ to X ⁴ are preferably halogen atoms, nitro groups, alkyl groups, aryl groups, heterocyclic groups, —ORt ¹ , —SRt ¹ , —SO ₂ NRt ¹ Rt ² , halogen atoms or alkyl groups is more preferred, and a halogen atom is even more preferred. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

In formula (1), Z ¹ represents a hydroxy group, a halogen atom, —OP(=O)R ¹ R ² , or —O—SiR ³ R ⁴ R ⁵ , and R ¹ to R ⁵ each independently represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ¹ and R ² and R ³ and R ⁴ may combine with each other to form a ring.

Z ¹ is preferably a hydroxy group, -OP(=O)R ¹ R ² or -O-SiR ³ R ⁴ R ⁵ , more preferably -OP(=O)R ¹ R ² , and R ¹ and R ² are More preferred are -OP(=O)R ¹ R ² each independently being an aryl group. The halogen atom represented by Z ¹ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The number of carbon atoms in the alkyl group and alkoxy group represented by R ¹ to R ⁵ is preferably 1-30, more preferably 1-15, even more preferably 1-8. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The aryl group and aryloxy group represented by R ¹ to R ⁵ preferably have 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The alkyl group, aryl group, alkoxy group and aryloxy group represented by R ¹ to R ⁵ may further have a substituent. Examples of the substituent include the substituent T described later.

R ¹ and R ² and R ³ and R ⁴ may combine with each other to form a ring. That is, when Z ¹ is —OP(=O)R ¹ R ² , R ¹ and R ² may combine with each other to form a ring. Also, when Z ¹ is —O—SiR ³ R ⁴ R ⁵ , R ³ and R ⁴ may combine with each other to form a ring. The ring formed by combining these groups may be an aliphatic ring, an aromatic ring, or a heterocyclic ring.

In formula (1), m1 to m4 each independently represent an integer of 0 to 4, preferably 0 or 1, more preferably 0. When m1 to m4 are 2 or more, X ¹ to X ⁴ may be the same or different.

In formula (2), X ⁵ to X ¹² each independently represent a substituent. Substituents represented by X ⁵ to X ¹² include substituents T described later. Substituents represented by X ⁵ to X ¹² are preferably halogen atoms, nitro groups, alkyl groups, aryl groups, heterocyclic groups, —ORt ¹ , —SRt ¹ , —SO ₂ NRt ¹ Rt ² , and halogen atoms or alkyl groups. is more preferred, and a halogen atom is even more preferred. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

L ^A represents -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁶ R ⁷ -O-SiR ⁸ R ⁹ -O-, or -OP(=O)R ¹⁰ -O-; Each of R ⁶ to R ¹⁰ independently represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group.

L ^A is preferably -O-SiR ⁶ R ⁷ -O- or -OP(=O)R ¹⁰ -O-, more preferably -OP(=O)R ¹⁰ -O-, R ¹⁰ is an aryl group -OP(=O)R ¹⁰ -O- is more preferred.

The number of carbon atoms in the alkyl group and alkoxy group represented by R ⁶ to R ¹⁰ is preferably 1-30, more preferably 1-15, even more preferably 1-8. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The aryl group and aryloxy group represented by R ⁶ to R ¹⁰ preferably have 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The alkyl group, aryl group, alkoxy group and aryloxy group represented by R ¹ to R ⁵ may further have a substituent. Examples of the substituent include the substituent T described later.

In formula (2), m5 to m12 each independently represent an integer of 0 to 4, preferably 0 or 1, more preferably 0. When m5 to m12 are 2 or more, X ⁵ to X ¹² may be the same or different.

(substituent T)
Substituent T includes halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , —NHCORt ¹ , —CONRt ¹ Rt ² , —NHCONRt ¹ Rt ² , —NHCOORt ¹ , —SRt ¹ , —SO ₂ Rt ¹ , —SO ₂ ORt ¹ , —NHSO ₂ Rt ¹ or —SO ₂ NRt ^{1 Rt2} can be mentioned. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rt ¹ and Rt ² may combine to form a ring.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-15, even more preferably 1-8. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12.
The heterocyclic group may be monocyclic or condensed. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3. A heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12.
Alkyl groups, alkenyl groups, alkynyl groups, aryl groups and heterocyclic groups may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the substituent T described above.

Specific examples of compound (1) and compound (2) include compounds having the following structures, compounds described in paragraph numbers 0046 to 0053 of JP-A-2015-063593, and paragraph numbers 0151 to 0151 of JP-A-2013-171063. 0169, and compounds described in paragraphs 0251 to 0258 of JP-A-2016-170370. Among the compounds having the following structures, PG62 is Color Index Pigment Green 62, and PG63 is Color Index Pigment Green 63.

The total content of compound (1) and compound (2) in the colorant is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more. is more preferred. The upper limit can be 100% by mass, 90% by mass or less, or 80% by mass or less.

The colorant used in the present invention preferably contains a yellow colorant in addition to the compounds (1) and (2) described above. According to this aspect, it is easy to form a film having spectral characteristics suitable for green pixels. Also, the content of the yellow colorant in the coloring composition is preferably 5 to 60 parts by mass with respect to the total of 100 parts by mass of compound (1) and compound (2) described above. The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more.

Examples of yellow colorants include azo compounds, quinophthalone compounds, isoindolinone compounds, isoindoline compounds, and anthraquinone compounds. A yellow colorant may be a pigment or a dye.

As a yellow pigment, Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31 , 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81 , 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126 , 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172 , 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 231, 232 and the like.

Further, as the yellow pigment, the pigment described in JP-A-2017-201003 and the pigment described in JP-A-2017-197719 can be used.

Further, as the yellow colorant, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraph numbers 0013-0058 of JP-A-2014-026228, etc. can also be used. .

The colorant used in the present invention is selected from Color Index Pigment Yellow 138, Color Index Pigment Yellow 139, Color Index Pigment Yellow 150 and Color Index Pigment Yellow 231 in addition to Compound (1) and Compound (2) described above. It is preferable to include at least one of Further, when these colorants are contained, the content thereof is preferably 5 to 60 parts by mass with respect to 100 parts by mass in total of compound (1) and compound (2) described above. The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more.

The colorant used in the present invention preferably contains a compound represented by the following formula (3) (hereinafter also referred to as compound (3)) in addition to the compounds (1) and (2) described above. Compound (3) can be preferably used as a yellow colorant.

In formula (3), Ry ¹ to Ry ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group, a salt of a sulfo group, a carboxyl group, a salt of a carboxyl group, phthalimidomethyl or a sulfamoyl group, preferably a halogen atom.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom and a bromine atom, more preferably a chlorine atom. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1-30, more preferably 1-15, even more preferably 1-8. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12. Regarding the sulfo group salt and the carboxyl group salt, the atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ etc.), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ etc.), ammonium ion, imidazolium ion, pyridinium ion, phosphonium ion and the like.

In formula (3), two adjacent groups among Ry ¹ to Ry ⁴ may be bonded together to form a ring, and two adjacent groups among Ry ¹⁰ to Ry ¹³ may be bonded together to form a ring. may form In particular, at least one pair of adjacent two groups among Ry ¹ to Ry ⁴ and Ry ¹⁰ to Ry ¹³ preferably combine to form a ring. The ring to be formed may be an aliphatic ring, an aromatic ring, or a heterocyclic ring, preferably an aromatic ring. Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles, with aromatic hydrocarbon rings being preferred. The aromatic hydrocarbon ring includes benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, and benzene ring is preferred.

Compound (3) is preferably a compound represented by any one of the following formulas (3a) to (3c).

In formulas (3a) to (3c), Ry ¹ to Ry ¹³ and Ry ¹⁰¹ to Ry ¹⁰⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group, or a sulfo group. It represents a salt, a carboxyl group, a salt of a carboxyl group, a phthalimidomethyl group, or a sulfamoyl group, and preferably represents a halogen atom.

Specific examples of compound (3) include the compounds described in Examples below and the compounds described in paragraph number 0073 of International Publication No. 2012/128233.

When the colorant used in the present invention further contains compound (3), the content thereof is 5 to 60 parts by mass with respect to the total 100 parts by mass of compound (1) and compound (2) described above. is preferred. The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more.

The coloring agent used in the present invention can further contain coloring agents other than the compounds described above (hereinafter, also referred to as other coloring agents). Other colorants include, for example:

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, orange pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184, 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279,294, etc. , red pigment),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigments),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61, etc. (the above are purple pigments),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. (above , blue pigment).

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used. Specific examples include compounds described in International Publication No. 2015/118720. Further, as a green pigment, a compound described in CN106909027A, a phthalocyanine compound having a phosphoric acid ester as a ligand, and the like can also be used.

As red pigments, diketopyrrolopyrrole-based pigments in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and diketopyrrolopyrrole-based pigments described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 Pigments and the like can also be used. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.

Dyes can also be used as other colorants. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used. Further, thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can also be preferably used. Further, an intramolecular imide-type xanthene dye described in JP-A-2018-012863 can also be used.

A pigment multimer can also be used as another coloring agent. The dye multimer is preferably a dye that is dissolved in a solvent and used, but the dye multimer may form particles, and when the dye multimer is particles, it is usually dispersed in the solvent. Used. The particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682. A dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. A plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.

The content of the coloring agent is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and particularly preferably 50% by mass or more, based on the total solid content of the coloring composition. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less.

In the coloring composition of the present invention, the total content of compound (1) and compound (2) is preferably 25% by mass or more in the total solid content of the coloring composition, more preferably 30% by mass or more , more preferably 35% by mass or more, and particularly preferably 40% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.

<<Pigment derivative>>
The coloring composition of the present invention can contain pigment derivatives. Pigment derivatives include compounds having a structure in which a portion of the chromophore is substituted with an acid group, a basic group, or a phthalimidomethyl group. Chromophores constituting pigment derivatives include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, iso Examples thereof include indoline skeleton, isoindolinone skeleton, quinophthalone skeleton, threne skeleton, metal complex skeleton, and the like, and quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, quinophthalone skeleton, isoindoline skeleton and phthalocyanine skeleton. Preferred are an azo skeleton and a benzimidazolone skeleton. The acid group possessed by the pigment derivative is preferably a sulfo group or a carboxyl group, more preferably a sulfo group. The basic group possessed by the pigment derivative is preferably an amino group, more preferably a tertiary amino group.

In the present invention, a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) may be contained as a pigment derivative. The maximum value (εmax) of the molar extinction coefficient of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L·mol ⁻¹ ·cm ⁻¹ or less, and 1000 L·mol ⁻¹ ·cm ⁻¹ or less. is more preferable, and 100 L·mol ⁻¹ ·cm ⁻¹ or less is even more preferable. The lower limit of εmax is, for example, 1 L·mol ⁻¹ ·cm ⁻¹ or more, and may be 10 L·mol ⁻¹ ·cm ⁻¹ or more.

Specific examples of pigment derivatives include compounds described in paragraphs 0162 to 0183 of JP-A-2011-252065 and compounds described in JP-A-2003-081972. Specific examples of transparent pigment derivatives include compounds having the following structures.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of compound (1) and compound (2). In addition, the total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and 50% by mass of the total solid content of the coloring composition. More than % by mass is particularly preferred. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<<Resin>>
The coloring composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the purpose of binder. A resin mainly used for dispersing particles and the like in a composition is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

Examples of resins include (meth)acrylic resins, (meth)acrylamide resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, and polyarylene resins. ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins and the like.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

The coloring composition of the present invention can use a resin having an acid group as the resin. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. A resin having an acid group can also be used as an alkali-soluble resin or a dispersant. The acid value of the resin having acid groups is preferably 30-500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

The coloring composition of the present invention is a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) as a resin (hereinafter, these compounds are sometimes referred to as "ether dimers"). It is possible to use a resin containing repeating units derived from

式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。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 formula (ED1), 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.

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

Specific examples of the ether dimer can be referred to paragraph number 0317 of JP-A-2013-029760, the content of which is incorporated herein.

The coloring composition of the present invention can also use a resin having a maleimide structure as the resin. In addition, in this specification, the maleimide structure means a structure derived from a maleimide compound. Maleimide compounds include maleimides and N-substituted maleimides. N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide and the like.

The resin having a maleimide structure is preferably a resin containing repeating units having a maleimide structure. The maleimide structure may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The maleimide structure is preferably contained in the main chain of the repeating unit because it facilitates the formation of a film with suppressed color unevenness.

The coloring composition of the present invention contains a resin i (hereinafter also referred to as resin i) containing a repeating unit (hereinafter also referred to as repeating unit i1-1) derived from the compound represented by formula (I) as a resin. is also preferred. When the colored composition of the present invention contains the resin i, it is easy to obtain a film in which color unevenness is suppressed. The content of repeating unit i1-1 in all repeating units of resin i is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 15 mol % or more.

In the formula, Xi ¹ represents O or NH, preferably O.
Ri ¹ represents a hydrogen atom or a methyl group.
Li ¹ represents a divalent linking group. Divalent linking groups include hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S- and these A group formed by combining two or more of Examples of hydrocarbon groups include alkyl groups and aryl groups. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5- or 6-membered ring. Types of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of heteroatoms constituting the heterocyclic group is preferably 1-3. The heterocyclic group may be monocyclic or condensed. A hydrocarbon group and a heterocyclic group may have a substituent. Examples of substituents include alkyl groups, aryl groups, hydroxy groups, and halogen atoms.
Ri ¹⁰ represents a substituent. Examples of the substituent represented by Ri ¹⁰ include the substituent Ti shown below, which is preferably a hydrocarbon group, more preferably an alkyl group optionally having an aryl group as a substituent.
m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.
p represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 1.

(substituent Ti)
The substituent Ti includes a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORti ¹ , -CORti ¹ , -COORti ¹ , -OCORti ¹ , -NRti ¹ Rti ² , -NHCORti ¹ , - CONRti ¹ Rti ² , -NHCONRti ¹ Rti ² , -NHCOORti ¹ , -SRti ¹ , -SO ₂ Rti ¹ , -SO ₂ ORti ¹ , -NHSO ₂ Rti ¹ or -SO ₂ NRti ¹ Rti ² . Rti ¹ and Rti ² each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rti ¹ and Rti ² may combine to form a ring.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-15, even more preferably 1-8. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably branched.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched.
The alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, preferably linear or branched.
The number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12.
The heterocyclic group may be monocyclic or condensed. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3. A heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12.
A hydrocarbon group and a heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the substituent Ti described above.

The compound represented by formula (I) is preferably a compound represented by formula (I-1) below.

Xi ¹ represents O or NH, preferably O.
Ri ¹ represents a hydrogen atom or a methyl group.
Ri ² , Ri ³ and Ri ¹¹ each independently represent a hydrocarbon group.
The hydrocarbon group represented by Ri ² and Ri ³ is preferably an alkylene group or an arylene group, more preferably an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. The hydrocarbon group represented by Ri ¹¹ is preferably an alkyl group optionally having an aryl group as a substituent, more preferably an alkyl group having an aryl group as a substituent. The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-10, even more preferably 1-5. When the alkyl group has an aryl group as a substituent, the number of carbon atoms in the alkyl group means the number of carbon atoms in the alkyl moiety.
Ri ¹² represents a substituent. The substituent represented by Ri ¹² includes the substituent Ti described above.
n represents an integer of 0-15, preferably an integer of 0-5, more preferably an integer of 0-4, and even more preferably an integer of 0-3.
m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0;
p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, even more preferably 0 to 1, and particularly preferably 0.
q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1.

式中、Ｒｉ^１は水素原子またはメチル基を表し、Ｒｉ^２１およびＲｉ^２２はそれぞれ独立してアルキレン基を表し、ｎは０～１５の整数を表す。Ｒｉ^２１およびＲｉ^２２が表すアルキレン基の炭素数は１～１０であることが好ましく、１～５であることがより好ましく、１～３であることが更に好ましく、２または３であることが特に好ましい。ｎは０～１５の整数を表し、０～５の整数であることが好ましく、０～４の整数であることがより好ましく、０～３の整数であることが更に好ましい。The compound represented by Formula (I) is preferably a compound represented by Formula (III) below.

In the formula, Ri ¹ represents a hydrogen atom or a methyl group, Ri ²¹ and Ri ²² each independently represent an alkylene group, and n represents an integer of 0-15. The number of carbon atoms in the alkylene group represented by Ri ²¹ and Ri ²² is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.

Examples of the compound represented by formula (I) include ethylene oxide- or propylene oxide-modified (meth)acrylates of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

Resin i preferably further contains a repeating unit derived from an alkyl (meth)acrylate (hereinafter also referred to as repeating unit i1-2). In the case where the resin i further has repeating units i1-2, the effect of improving solvent solubility can be obtained. The number of carbon atoms in the alkyl moiety of the alkyl (meth)acrylate is preferably 3-10, more preferably 3-8, even more preferably 3-6. Preferred specific examples of alkyl (meth) acrylates include n-butyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl acrylate and the like. Butyl (meth)acrylate is preferred. The content of repeating units i1-2 in all repeating units of resin i is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 15 mol % or more.

It is also preferred that the resin i further contains a repeating unit having an acid group. According to this aspect, the effect of improving developability can be obtained. The content of repeating units having an acid group in all repeating units of Resin i is preferably 5 mol % or more, more preferably 10 mol % or more, and still more preferably 15 mol % or more. The upper limit is preferably 60 mol % or less, more preferably 50 mol % or less.

It is also preferred that Resin i further contains a repeating unit having an ethylenically unsaturated bond group. Examples of the repeating unit having an ethylenically unsaturated bond group include repeating units represented by formula (A-1-1) described later. The content of repeating units having an ethylenically unsaturated bond group in all repeating units of Resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and 15 mol% or more. is more preferred. The upper limit is preferably 50 mol % or less, more preferably 40 mol % or less.

The coloring composition of the present invention can contain a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol% is preferable. A resin consisting only of acid groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, it is possible to further suppress the generation of development residues when forming a pattern by photolithography.

It is also preferable that the resin used as the dispersant is a graft resin. Details of the graft resin can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

It is also preferable that the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. A resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion. Such resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in its side chain. The content of repeating units having an ethylenically unsaturated bond group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70 mol, of the total repeating units of the resin. % is more preferred.

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by BYK Chemie (e.g., Disperbyk-111, 2001, etc.), Solsperse series manufactured by Nippon Lubrizol Co., Ltd. ( For example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine-Techno Co., Inc., and the like can be mentioned. In addition, the product described in paragraph number 0129 of JP-A-2012-137564 and the product described in paragraph number 0235 of JP-A-2017-194662 can also be used as a dispersant.

The resin used in the present invention preferably contains a resin having an ethylenically unsaturated bond group (hereinafter also referred to as a polymerizable resin). According to this aspect, film shrinkage over time can be more effectively suppressed.

The ethylenically unsaturated bond value (hereinafter also referred to as C=C value) of the polymerizable resin is preferably 0.05 to 5.0 mmol/g. The upper limit is more preferably 4.0 mmol/g or less, still more preferably 3.0 mmol/g or less, even more preferably 2.0 mmol/g or less, and 1.0 mmol/g or less. It is particularly preferred to have The lower limit is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more. The C=C value of the polymerizable resin is a numerical value representing the molar amount of C=C groups per 1 g of the solid content of the polymerizable resin. The C=C value of the polymerizable resin is obtained by removing the low-molecular component (a) of the C=C group site from the polymerizable resin by alkali treatment, measuring the content by high performance liquid chromatography (HPLC), and using the following formula. can be calculated. In addition, when the C═C group site cannot be extracted from the polymerizable resin by alkali treatment, the value measured by the NMR method (nuclear magnetic resonance) is used.
C value of polymerizable resin = C value [mmol/g] = (content of low-molecular-weight component (a) [ppm]/molecular weight of low-molecular-weight component (a) [g/mol])/(weighing value of polymerizable resin [g] x (solid concentration of polymerizable resin [mass%]/100) x 10)

The polymerizable resin preferably contains a repeating unit having an ethylenically unsaturated bond group in its side chain, and more preferably contains a repeating unit represented by the following formula (A-1-1). Further, in the polymerizable resin, the repeating unit having an ethylenically unsaturated bond group preferably contains 10 mol% or more of the total repeating units of the polymerizable resin, more preferably 10 to 80 mol%, and 20 It is more preferable to contain up to 70 mol %.

In formula (A-1-1), X ¹ represents a main chain of repeating units, L ¹ represents a single bond or a divalent linking group, and Y ¹ represents an ethylenically unsaturated bond group.

In formula (A-1-1), the main chain of the repeating unit represented by X ¹ is not particularly limited. There is no particular limitation as long as it is a linking group formed from a known polymerizable monomer. For example, poly(meth)acrylic linking group, polyalkyleneimine linking group, polyester linking group, polyurethane linking group, polyurea linking group, polyamide linking group, polyether linking group, polystyrene linking group, etc. Poly(meth)acrylic linking groups and polyalkyleneimine linking groups are preferred, and poly(meth)acrylic linking groups are more preferred, from the viewpoint of availability of raw materials and production suitability.

In formula (A-1-1), the divalent linking group represented by L ¹ includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkylene group having 1 to 12 carbon atoms). oxy group), oxyalkylenecarbonyl group (preferably oxyalkylenecarbonyl group having 1 to 12 carbon atoms), arylene group (preferably arylene group having 6 to 20 carbon atoms), —NH—, —SO—, —SO ₂ — , -CO-, -O-, -COO-, -OCO-, -S- and groups formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and preferably linear or branched. An alkylene group, an alkylene group in an alkyleneoxy group, and an alkylene group in an oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group, and a hydroxy group is preferable from the viewpoint of production suitability.

In formula (A-1-1), the ethylenically unsaturated bond group represented by Y ¹ includes a vinyl group, an allyl group, a methallyl group, a (meth)acryloyl group and a styrene group, a (meth)acryloyl group, A styrene group is preferred, a (meth)acryloyl group is more preferred, and an acryloyl group is particularly preferred.

Specific examples of the repeating unit represented by the formula (A-1-1) include repeating units represented by the following formula (A-1-1a) and repeating units represented by the following formula (A-1-1b). unit, etc.

In formula (A-1-1a), R ^a1 to R ^a3 each independently represent a hydrogen atom or an alkyl group, and Q ^1a is -CO-, -COO-, -OCO-, -CONH- or phenylene group, L ¹ represents a single bond or a divalent linking group, and Y ¹ represents an ethylenically unsaturated bond group. The number of carbon atoms in the alkyl groups represented by R ^a1 to R ^a3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Q ^1a is preferably -COO- or -CONH-, more preferably -COO-.

In formula (A-1-1b), R ^a10 and R ^a11 each independently represent a hydrogen atom or an alkyl group, m1 represents an integer of 1 to 5, L ¹ is a single bond or a divalent linkage group, and Y ¹ represents an ethylenically unsaturated bond group. The number of carbon atoms in the alkyl group represented by R ^a10 and R ^a11 is preferably 1-10, more preferably 1-3.

Preferably, the polymerizable resin further contains a repeating unit having a graft chain. When the polymerizable resin contains a repeating unit having a graft chain, it is possible to more effectively suppress aggregation of the compound (1) or compound (2) due to steric hindrance caused by the graft chain. Further, when forming a cured film, the polymerizable resin can be polymerized in the vicinity of the compound (1) or the compound (2) to firmly hold the compound (1) or the compound (2) in the film. It is also possible to more effectively suppress thermal diffusion of these compounds by heating to form a cured film having excellent heat resistance. The polymerizable resin preferably contains 1.0 to 60 mol %, more preferably 1.5 to 50 mol %, of repeating units having a graft chain in the total repeating units of the polymerizable resin. A polymerizable resin containing a repeating unit having a graft chain is preferably used as a dispersant.

In the present invention, the graft chain means a polymer chain branching from the main chain of the repeating unit. The length of the grafted chain is not particularly limited, but the longer the grafted chain, the higher the steric repulsion effect, which can enhance the dispersibility of compound (1), compound (2), and the like. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and 60 to 60 atoms excluding hydrogen atoms. 500 is more preferred.

上記式において、Ｒ^Ｇ１およびＲ^Ｇ２は、それぞれアルキレン基を表す。Ｒ^Ｇ１およびＲ^Ｇ２で表されるアルキレン基としては特に制限されないが、炭素数１～２０の直鎖状又は分岐状のアルキレン基が好ましく、炭素数２～１６の直鎖状又は分岐状のアルキレン基がより好ましく、炭素数３～１２の直鎖状又は分岐状のアルキレン基が更に好ましい。
上記式において、Ｒ^Ｇ３は、水素原子またはメチル基を表す。
上記式において、Ｑ^Ｇ１は、－Ｏ－または－ＮＨ－を表し、Ｌ^Ｇ１は、単結合または２価の連結基を表す。２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アルキレンオキシ基（好ましくは炭素数１～１２のアルキレンオキシ基）、オキシアルキレンカルボニル基（好ましくは炭素数１～１２のオキシアルキレンカルボニル基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ_２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。
Ｒ^Ｇ４は、水素原子または置換基を表す。置換基としては、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基等が挙げられる。The graft chain preferably contains repeating units having at least one structure selected from polyester repeating units, polyether repeating units, poly(meth)acrylic repeating units, polyurethane repeating units, polyurea repeating units, and polyamide repeating units. It more preferably contains repeating units having at least one structure selected from repeating units, polyether repeating units and poly(meth)acrylic repeating units, and more preferably contains polyester repeating units. Examples of polyester repeating units include repeating units having a structure represented by the following formula (G-1), formula (G-4), or formula (G-5). Further, the polyether repeating unit includes a repeating unit having a structure represented by the following formula (G-2). Examples of poly(meth)acrylic repeating units include repeating units having a structure represented by the following formula (G-3).

In the above formula, R ^G1 and R ^G2 each represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 2 to 16 carbon atoms. is more preferred, and a straight or branched alkylene group having 3 to 12 carbon atoms is even more preferred.
In the above formula, ^RG3 represents a hydrogen atom or a methyl group.
In the above formula, Q ^G1 represents -O- or -NH-, and L ^G1 represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an alkyleneoxy group having 1 to 12 carbon atoms). to 12 oxyalkylenecarbonyl groups), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO -, -S-, and groups formed by combining two or more of these.
^RG4 represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable from the viewpoint of improving the dispersibility of pigments. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.

In the present invention, the graft chain has a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a). Preferably.

In the above formula, R ^G1 and R ^G2 each represent an alkylene group, R ^G3 represents a hydrogen atom or a methyl group, Q ^G1 represents —O— or —NH—, and L ^G1 is a single bond or represents a divalent linking group, ^RG4 represents a hydrogen atom or a substituent, and ^W100 represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. R ^G1 to R ^G4 , Q ^G1 and L ^G1 have the same meanings as R ^G1 to R ^G4 , Q ^G1 and L ^G1 described in formulas (G-1) to (G-5), and the preferred ranges are also the same. be.

In formulas (G-1a) to (G-5a), W ¹⁰⁰ is preferably a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable from the viewpoint of improving the dispersibility of pigments. The alkyl group and alkoxy group may be linear, branched or cyclic, preferably linear or branched.

In formulas (G-1a) to (G-5a), each of n1 to n5 is preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and even more preferably an integer of 8 to 60.

In formula (G-1a), R ^{1 G1} in each repeating unit when n1 is 2 or more may be the same or different. In addition, when ^RG1 includes two or more different repeating units, the arrangement of each repeating unit is not particularly limited, and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-5a).

Repeating units having a graft chain include repeating units represented by the following formula (A-1-2).

In formula (A- ^1-2 ), X2 represents the main chain of the repeating unit, L2 represents a single bond or a ^divalent linking group, and W1 represents ^a graft chain.

Examples of the main chain of the repeating unit represented by X ² in formula (A-1-2) include the structures described for X ¹ in formula (A-1-1), and the preferred range is also the same. The divalent linking group represented by L ² in formula (A-1-2) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, OCO—, —S—, and groups formed by combining two or more of these. Examples of the graft chain represented by W ¹ in formula (A-1-2) include the graft chains described above.

Specific examples of the repeating unit represented by the formula (A-1-2) include repeating units represented by the following formula (A-1-2a) and repeating units represented by the following formula (A-1-2b). unit, etc.

In formula (A-1-2a), R ^b1 to R ^b3 each independently represent a hydrogen atom or an alkyl group, and Q ^b1 is -CO-, -COO-, -OCO-, -CONH- or phenylene group, L2 represents a single bond or a ^divalent linking group, and W1 represents ^a graft chain. The number of carbon atoms in the alkyl group represented by R ^b1 to R ^b3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Q ^b1 is preferably -COO- or -CONH-, more preferably -COO-.

In formula (A-1-2b), R ^b10 and R ^b11 each independently represent a hydrogen atom or an alkyl group, m2 represents an integer of 1 to 5, L ² is a single bond or a divalent linkage group and W ¹ represents the graft chain. The number of carbon atoms in the alkyl group represented by R ^b10 and R ^b11 is preferably 1-10, more preferably 1-3.

When the polymerizable resin contains a repeating unit having a graft chain, the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, more preferably 1000 to 7500. is more preferable. In addition, in the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for polymerization of the same repeating unit. For example, a repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer means a polymer compound in which a polymerizable group is introduced at the terminal of the polymer. When a repeating unit having a graft chain is formed using a macromonomer, the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.

It is also preferred that the polymerizable resin further contains a repeating unit having an acid group. When the polymerizable resin further contains a repeating unit having an acid group, the dispersibility of compound (1), compound (2), etc. can be further improved. Furthermore, developability can also be improved. Examples of acid groups include carboxyl groups, sulfo groups, and phosphoric acid groups.

Repeating units having an acid group include repeating units represented by the following formula (A-1-3).

In formula (A-1-3), X ³ represents the main chain of the repeating unit, L ³ represents a single bond or a divalent linking group, and A ¹ represents an acid group. Examples of the main chain of the repeating unit represented by X ³ in formula (A-1-3) include the structures described for X ¹ in formula (A-1-1), and the preferred range is also the same. The divalent linking group represented by L ³ in formula (A-1-3) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an alkenylene group (preferably an alkenylene group having 2 to 12 carbon atoms). , an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms) ), —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, OCO—, —S—, and groups formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and preferably linear or branched. An alkylene group, an alkylene group in an alkyleneoxy group, and an alkylene group in an oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. A hydroxy group etc. are mentioned as a substituent. Examples of the acid group represented by A ¹ in formula (A-1-3) include a carboxyl group, a sulfo group and a phosphoric acid group.

Specific examples of the repeating unit represented by the formula (A-1-3) include repeating units represented by the following formula (A-1-3a) and repeating units represented by the following formula (A-1-3b). unit, etc.

In formula (A-1-3a), R ^c1 to R ^c3 each independently represent a hydrogen atom or an alkyl group, and Q ^c1 is -CO-, -COO-, -OCO-, -CONH- or phenylene group ^, L3 represents a single bond or a divalent linking group, and A1 represents ^an acid group. The number of carbon atoms in the alkyl groups represented by R ^c1 to R ^c3 is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Q ^c1 is preferably -COO- or -CONH-, more preferably -COO-.

In formula (A-1-3b), R ^c10 and R ^c11 each independently represent a hydrogen atom or an alkyl group, m3 represents an integer of 1 to 5, L ³ is a single bond or a divalent linkage group and A ¹ represents an acid group. The number of carbon atoms in the alkyl group represented by R ^c10 and R ^c11 is preferably 1-10, more preferably 1-3.

When the polymerizable resin contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 80 mol% or less in the total repeating units of the polymerizable resin, and 10 to 80 mol%. more preferred. When the polymerizable resin contains a repeating unit having an acid group, the acid value of the polymerizable resin is preferably 20 to 150 mgKOH/g. More preferably, the upper limit is 100 mgKOH/g or less. The lower limit is preferably 30 mgKOH/g or more, more preferably 35 mgKOH/g or more. If the acid value of the polymerizable resin is within the above range, particularly excellent dispersibility is likely to be obtained. Furthermore, excellent developability is likely to be obtained.

式（ｂ－１０）中、Ａｒ^１０は芳香族カルボキシル基を含む基を表し、Ｌ^１１は、－ＣＯＯ－または－ＣＯＮＨ－を表し、Ｌ^１２は３価の連結基を表し、Ｐ^１０は（メタ）アクリロイル基を有するポリマー鎖を表す。The polymerizable resin is also preferably a resin containing a repeating unit represented by formula (b-10).

In formula (b-10), Ar ¹⁰ represents a group containing an aromatic carboxyl group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, P ¹⁰ represents ( Represents a polymer chain with meth)acryloyl groups.

Examples of the aromatic carboxyl group-containing group represented by Ar ¹⁰ in formula (b-10) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like. Aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds having the following structures.

In the above formula, Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

Specific examples of the aromatic tricarboxylic anhydride include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.) , Naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalene tricarboxylic anhydride, etc.), 3,4,4′-benzophenonetricarboxylic anhydride, 3,4,4′-biphenyl ether tricarboxylic anhydride, 3,4,4′-biphenyltricarboxylic anhydride, 2,3 ,2′-biphenyltricarboxylic anhydride, 3,4,4′-biphenylmethanetricarboxylic anhydride, or 3,4,4′-biphenylsulfonetricarboxylic anhydride. Specific examples of aromatic tetracarboxylic acid anhydrides include pyromellitic dianhydride, ethylene glycol dianhydride trimellitic ester, propylene glycol dianhydride trimellitic ester, butylene glycol dianhydride trimellitic ester, 3,3 ',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic acid acid dianhydride, 3,3′,4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis(3, 4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether anhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3 ,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, or 3,4-dicarboxy-1, 2,3,4-tetrahydro-6-methyl-1-naphthalenesuccinic dianhydride and the like.

Specific examples of the group containing an aromatic carboxyl group represented by Ar ¹⁰ include a group represented by formula (Ar-1), a group represented by formula (Ar-2), and a group represented by formula (Ar-3). and the like.

In formula (Ar-1), n1 represents an integer of 1 to 4, preferably an integer of 1 to 2, more preferably 2.
In formula (Ar-2), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 to 2, even more preferably 2.
In formula (Ar-3), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 to 2, preferably 1 More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In formula (Ar-3), Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, the above formula (Q- 1) or a group represented by the above formula (Q-2).

In formula (b-10), L ¹¹ represents -COO- or -CONH-, preferably -COO-.

The trivalent linking group represented by L ¹² in formula (b-10) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included. Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10. The hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1) below, more preferably a group represented by formula (L12-2).

L ^12a and L ^12b each represent a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (b-10), *2 represents formula (b-10) represents the binding position with ^P10 .

The trivalent linking group represented by L ^12a and L ^12b is selected from a hydrocarbon group; a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH- and -S- Groups in which at least one of them is combined, and the like.

In formula (b-10), P ¹⁰ represents a polymer chain having a (meth)acryloyl group. The polymer chain represented by ^P10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units. The weight average molecular weight of the polymer chain P10 is preferably ^500-20,000 . The lower limit is preferably 600 or more, more preferably 1000 or more. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of ^P10 is within the above range, the dispersibility of the pigment in the composition is good. This resin is preferably used as a dispersant.

上記式において、Ｒ^Ｐ１およびＲ^Ｐ２は、それぞれアルキレン基を表す。Ｒ^Ｐ１およびＲ^Ｐ２で表されるアルキレン基としては、炭素数１～２０の直鎖状又は分岐状のアルキレン基が好ましく、炭素数２～１６の直鎖状又は分岐状のアルキレン基がより好ましく、炭素数３～１２の直鎖状又は分岐状のアルキレン基が更に好ましい。
上記式において、Ｒ^Ｐ３は、水素原子またはメチル基を表す。
上記式において、Ｌ^Ｐ１は、単結合またはアリーレン基を表し、Ｌ^Ｐ２は、単結合または２価の連結基を表す。Ｌ^Ｐ１は、単結合であることが好ましい。Ｌ^Ｐ２が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ_２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－、－ＮＨＣＯ－、－ＣＯＮＨ－、およびこれらの２以上を組み合わせてなる基が挙げられる。
Ｒ^Ｐ４は、水素原子または置換基を表す。置換基としては、ヒドロキシ基、カルボキシル基、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、（メタ）アクリロイル基等が挙げられる。In formula (b-10), the polymer chain represented by P ¹⁰ is preferably a polymer chain containing repeating units represented by the following formulas (P-1) to (P-5), and (P-5) More preferably, it is a polymer chain containing a repeating unit represented by.

In the above formula, R ^P1 and R ^P2 each represent an alkylene group. The alkylene group represented by R ^P1 and R ^P2 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms. , a linear or branched alkylene group having 3 to 12 carbon atoms is more preferable.
In the above formula, R ^P3 represents a hydrogen atom or a methyl group.
In the above formula, ^LP1 represents a single bond or an arylene group, and ^LP2 represents a single bond or a divalent linking group. L ^P1 is preferably a single bond. The divalent linking group represented by L ^P2 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), —NH—, —SO—, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO-, -CONH-, and groups consisting of combinations of two or more of these.
R ^P4 represents a hydrogen atom or a substituent. Substituents include hydroxy group, carboxyl group, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, (meth)acryloyl and the like.

Moreover, the polymer chain represented by ^P10 is more preferably a polymer chain having a repeating unit containing a (meth)acryloyl group in the side chain. Further, the proportion of repeating units containing a (meth)acryloyl group in a side chain in all repeating units constituting P10 is preferably 5% by mass or more, more preferably ¹⁰ % by mass or more, It is more preferably 20% by mass or more. The upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.

The polymer chain represented by ^P10 also preferably has a repeating unit containing an acid group. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. According to this aspect, the dispersibility of the pigment in the composition can be further improved. Furthermore, the developability can be further improved. The proportion of repeating units containing an acid group is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, even more preferably 3 to 10% by mass.

A resin containing a repeating unit represented by formula (b-10) is obtained by reacting at least one acid anhydride selected from aromatic tetracarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides with a hydroxy group-containing compound. It can be manufactured by Examples of the aromatic tetracarboxylic anhydride and the aromatic tricarboxylic anhydride include those described above. The hydroxy group-containing compound is not particularly limited as long as it has a hydroxy group in its molecule, but it is preferably a polyol having two or more hydroxy groups in its molecule. It is also preferable to use a compound having two hydroxy groups and one thiol group in the molecule as the hydroxy group-containing compound. Compounds having two hydroxy groups and one thiol group in the molecule include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2- Propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like. Other hydroxy group-containing compounds include compounds described in paragraphs 0084 to 0095 of JP-A-2018-101039, the contents of which are incorporated herein.

The molar ratio of the acid anhydride group in the acid anhydride to the hydroxy group in the hydroxy group-containing compound (acid anhydride group/hydroxy group) is preferably 0.5 to 1.5.

The weight-average molecular weight of the resin containing repeating units represented by formula (b-10) is preferably 2,000 to 35,000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less. The lower limit is preferably 4,000 or more, more preferably 6,000 or more, and even more preferably 7,000 or more.

The acid value of the resin containing repeating units represented by formula (b-10) is preferably 5 to 200 mgKOH/g. The upper limit is preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, and even more preferably 80 mgKOH/g or less. The lower limit is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and even more preferably 20 mgKOH/g or more.

式中、Ｒｐ^４は数平均分子量４００～３００００であり、エチレン性不飽和結合基を有するポリエーテル残基および／またはポリエステル残基を表し、ｙは１～２の数を表す。It is also preferable to use a compound represented by the following formula (OP1) as the polymerizable resin.

In the formula, Rp ⁴ has a number average molecular weight of 400-30,000, represents a polyether residue and/or polyester residue having an ethylenically unsaturated bond group, and y represents a number of 1-2.

The number average molecular weight of Rp ⁴ is more preferably 400-10000, more preferably 400-3000. If the number average molecular weight of Rp ⁴ is within the above range, the dispersibility of the pigment is good, and such a resin is preferably used as a dispersant.

Polyether residues and/or polyester residues having an ethylenically unsaturated bond group represented by Rp ⁴ include polyether residues and/or Polyester residues are mentioned.

Rp ⁴ is preferably a group represented by the following formula (Rp-1).
-Rp ¹² -O-Rp ¹³ -(O-Rp ¹⁴ ) _S
In the formula, Rp ¹² represents an alkylene group, Rp ¹³ represents a trihydric or higher polyhydric alcohol residue, Rp ¹⁴ represents a (meth)acryloyl group or a cyanoacryloyl group, and s represents 2 or more.

Rp ¹² is preferably an alkylene group having 8 or less carbon atoms. From the viewpoint of pigment dispersibility, s is preferably 2 or more. In this case, different groups may be used for Rp ¹⁴ . s is more preferably 2 to 5, and particularly preferably 2.

Examples of polyhydric alcohols having a valence of 3 or higher for Rp ¹³ include glycerin, propyl alcohol, pentaerythritol, and dipentaerythritol. Trivalent to hexavalent ones are particularly preferred.

The compound represented by the formula (OP1) may be a phosphate ester with a single Rp ⁴ or a plurality of phosphate esters with different Rp ^4s . Further, the compound where y=1 may be used alone, or a mixture of the compound where y=1 and the compound where y=2 may be used. In the compound represented by the formula (OP1), it is preferable that the ratio of the compound having y=1 and the compound having y=2 is 100:0 to 100:30 because the dispersibility of the pigment is improved. Further, when Rp ⁴ of the compound represented by the formula (OP1) is a polycaprolactone residue having a number average molecular weight of 400 to 10,000 (more preferably 400 to 3,000), pigment dispersibility is improved, which is preferable.

The resin content in the total solid content of the coloring composition is preferably 25 to 60% by mass. The upper limit is preferably 55% by mass or less, more preferably 50% by mass or less. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more.

Further, in the present invention, the content of the resin having an ethylenically unsaturated bond group in the total amount of the resin contained in the coloring composition of the present invention is preferably 50 to 100% by mass, preferably 60 to 100% by mass. and more preferably 70 to 100% by mass.

Moreover, in the present invention, it is also preferable to use a resin having an ethylenically unsaturated bond group and a resin having no ethylenically unsaturated bond group together. According to this aspect, color unevenness can be suppressed more effectively. In this case, the mass ratio of the resin having an ethylenically unsaturated bond group and the resin having no ethylenically unsaturated bond group is the resin having an ethylenically unsaturated bond group: having an ethylenically unsaturated bond group. free resin = 1: 0.001 to 0.800 is preferred, 1: 0.002 to 0.700 is more preferred, and 1: 0.003 to 0.600 is even more preferred.

<<polymerizable monomer>>
The coloring composition of the present invention contains a polymerizable monomer having an ethylenically unsaturated bond group (hereinafter referred to as a polymerizable monomer). Examples of ethylenically unsaturated bond groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. The polymerizable monomer is preferably a radically polymerizable compound (radical polymerizable monomer).

The polymerizable monomer is preferably a compound containing 3 or more ethylenically unsaturated bond groups. The upper limit of the ethylenically unsaturated bond groups is preferably 15 or less, more preferably 10 or less, even more preferably 6 or less. Further, the polymerizable monomer is preferably a trifunctional or higher (meth)acrylate compound, more preferably a tri- to fifteen-functional (meth)acrylate compound, and a tri- to ten-functional (meth)acrylate compound. is more preferred, and tri- to hexa-functional (meth)acrylate compounds are particularly preferred.

The molecular weight of the polymerizable monomer is preferably 100-2000. The upper limit is preferably 1500 or less, more preferably 1000 or less, still more preferably 450 or less, and particularly preferably 400 or less. The lower limit is preferably 150 or more.

The ethylenically unsaturated bond value (hereinafter referred to as C=C value) of the polymerizable monomer should be 2 to 14 mmol/g from the viewpoint of the stability of the composition over time and the resistance to discoloration of the resulting film. is preferred. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more. The upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less. The C=C value of the polymerizable monomer was calculated by dividing the number of ethylenically unsaturated bond groups contained in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

The polymerizable monomer used in the present invention is preferably a compound having a molecular weight of 450 or less containing 3 or more ethylenically unsaturated bond groups, and a compound having a molecular weight of 450 or less containing 3 ethylenically unsaturated bond groups. is more preferred, and a trifunctional (meth)acrylate compound having a molecular weight of 450 or less is even more preferred. According to this aspect, the solvent resistance of the resulting film can be further improved. Although the detailed reason why such an effect is obtained is not clear, it is presumed that it is because a very dense network structure could be formed by exposure. Examples of the polymerizable monomer having a molecular weight of 450 or less and containing three ethylenically unsaturated bond groups include trimethylolpropane tri(meth)acrylate.

The polymerizable monomer used in the invention is also preferably a compound having an isocyanurate skeleton. Specific examples of polymerizable monomers having an isocyanurate skeleton include tris(2-acryloyloxyethyl) isocyanurate and ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate. Commercially available products include Fancryl FA-731A (manufactured by Hitachi Chemical Co., Ltd.), NK Ester A9300, A9300-1CL, A9300-3CL (manufactured by Shin-Nakamura Chemical Co., Ltd., Aronix M-315 (Toagosei Co., Ltd. ) made) and the like.

In the present invention, as the polymerizable monomer, dipentaerythritol triacrylate (as a commercial product KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product KAYARAD D-320; Nippon Kayaku Yaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer) can also be used. Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) is also preferably used as the polymerizable monomer.

In the present invention, it is also preferable to use a polymerizable monomer having an acid group as the polymerizable monomer. By using a polymerizable monomer having an acid group, the colored composition layer in the unexposed areas can be easily removed during development, and generation of development residues can be suppressed. The acid group includes a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferred. Examples of the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta(meth)acrylate. Commercially available polymerizable monomers having an acid group include Aronix M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The acid value of the polymerizable monomer having an acid group is preferably 0.1-40 mgKOH/g, more preferably 5-30 mgKOH/g. When the acid value of the polymerizable monomer is 0.1 mgKOH/g or more, the solubility in the developing solution is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling.

In the present invention, it is also preferable to use a compound having a caprolactone structure as the polymerizable monomer. Polymerizable monomers having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60 and DPCA-120.

Polymerizable monomers, JP 2017-048367, JP 6057891, compounds described in JP 6031807, compounds described in JP 2017-194662, 8UH-1006, 8UH -1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like are also preferably used.

The polymerizable monomer used in the present invention contains at least one selected from succinic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate. preferable. According to this aspect, more excellent photolithography is likely to be obtained.

The content of the polymerizable monomer in the total solid content of the coloring composition is 0.1 to 6.0% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more. The upper limit is preferably 5.5% by mass or less, more preferably 5.0% by mass or less, and even more preferably 4.5% by mass or less.

Further, the total content of the resin and the polymerizable monomer in the total solid content of the coloring composition is preferably 25.5 to 65.5% by mass. The upper limit is preferably 60.0% by mass or less, more preferably 54.5% by mass or less. The lower limit is preferably 31.0% by mass or more, more preferably 36.5% by mass or more.

Further, the total content of the photopolymerization initiator and the polymerizable monomer in the total solid content of the coloring composition is preferably 1.4 to 12.5% by mass. The upper limit is preferably 11.0% by mass or less, more preferably 9.5% by mass or less. The lower limit is preferably 2.2% by mass or more, more preferably 3.0% by mass or more.

Further, the ratio (M ¹ /B ¹ ) of the mass M ¹ of the polymerizable monomer contained in the coloring composition and the mass B ¹ of the resin contained in the coloring composition is 0.03 to 0.15. is preferred. The lower limit of the above ratio is preferably 0.035 or more, more preferably 0.040 or more, and even more preferably 0.045 or more. The upper limit is preferably 0.13 or less, more preferably 0.11 or less, even more preferably 0.9 or less. If the aforementioned ratio is 0.03 or more, the pattern formability by photolithography is good, and if it is 0.15 or less, the generation of residues can be more effectively suppressed during pattern formation by photolithography. .

Further, the ratio of the mass M ¹ of the polymerizable monomer contained in the coloring composition to the mass I ¹ of the photopolymerization initiator contained in the coloring composition (M ¹ /I ¹ ) is 0.013 to 12.000. is preferably The lower limit of the above ratio is preferably 0.071 or more, more preferably 0.167 or more, and even more preferably 0.300 or more. The upper limit is preferably 6.111 or less, more preferably 4.167 or less, even more preferably 3.000 or less. A ratio of 0.013 or more indicates good line width sensitivity, and a ratio of 12.000 or less indicates good pattern formability in photolithography.

In the coloring composition of the present invention, only one type of polymerizable monomer may be used, or two or more types may be used. Moreover, when using 2 or more types of polymerizable monomers, it is preferable that the total amount thereof falls within the above range.

<<Photoinitiator>>
The coloring composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, phenylglyoxylate compounds and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is more preferably a compound selected from oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, more preferably an oxime compound. . Regarding the photopolymerization initiator, paragraphs 0065 to 0111 of JP-A-2014-130173 and Japanese Patent No. 6301489 can be referred to, and the contents thereof are incorporated herein.

Commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF). Commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No. 2015 / 152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017/164127, etc. is mentioned. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), and Adeka Optomer N-1919. (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-014052). As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A-2014-137466. The contents of which are incorporated herein.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of. The contents of which are incorporated herein.

In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in WO 2015/036910.

Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.

In the present invention, as the photopolymerization initiator, a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is reduced, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the colored composition can be improved. . Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0412 to 0417, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, and the like.

In the present invention, a photopolymerization initiator 1 having an absorption coefficient of 1.0×10 ⁴ mL/gcm or more at a wavelength of 365 nm in methanol and a photopolymerization initiator having an absorption coefficient of 1.0×10 4 mL/gcm or more at a wavelength of 365 nm in methanol are used as the photopolymerization initiator. It is also preferable to use together a photopolymerization initiator 2 having an absorption coefficient of 0×10 ² mL/gcm or less and an absorption coefficient of 1.0×10 ³ mL/gcm or more at a wavelength of 254 nm. According to this aspect, the colored composition can be sufficiently cured by exposure, and more excellent photolithography properties can be easily obtained. As the photopolymerization initiator 1 and the photopolymerization initiator 2, it is preferable to select and use a compound having the above absorption coefficient from among the above compounds.

上記式においてεは吸光係数（ｍＬ／ｇｃｍ）、Ａは吸光度、ｃは光重合開始剤の濃度（ｇ／ｍＬ）、ｌは光路長（ｃｍ）を表す。In the present invention, the absorption coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, it was calculated by dissolving a photopolymerization initiator in methanol to prepare a measurement solution and measuring the absorbance of the above-mentioned measurement solution. Specifically, the measurement solution described above is placed in a glass cell with a width of 1 cm, the absorbance is measured using an Agilent Technologies UV-Vis-NIR spectrometer (Cary 5000), and the following formula is applied to the wavelength 365 nm and the wavelength The extinction coefficient (mL/gcm) at 254 nm was calculated.

In the above formula, ε is the extinction coefficient (mL/gcm), A is the absorbance, c is the concentration of the photopolymerization initiator (g/mL), and 1 is the optical path length (cm).

The absorption coefficient of the photopolymerization initiator 1 in methanol at a wavelength of 365 nm is preferably 1.1×10 ⁴ mL/gcm or more, and is 1.2×10 ⁴ to 1.0×10 ⁵ mL/gcm. more preferably 1.3×10 ⁴ to 5.0×10 ⁴ mL/gcm, even more preferably 1.5×10 ⁴ to 3.0×10 ⁴ mL/gcm Especially preferred.
Further, the absorption coefficient of the photopolymerization initiator 1 in methanol at a wavelength of 254 nm is preferably 1.0×10 ⁴ to 1.0×10 ⁵ mL/gcm, and preferably 1.5×10 ⁴ to 1.0×10 4 mL/gcm. More preferably 9.5×10 ⁴ mL/gcm, even more preferably 3.0×10 ⁴ to 8.0×10 ⁴ mL/gcm.

As the photopolymerization initiator 1, oxime compounds, α-aminoketone compounds, and acylphosphine compounds are preferred, oxime compounds and acylphosphine compounds are more preferred, oxime compounds are still more preferred, and oxime compounds containing a fluorine atom and oximes having a benzofuran skeleton are preferred. Compounds are particularly preferred.
Specific examples of the photopolymerization initiator 1 include (C-13) and (C-15) shown in the above specific examples of the oxime compound.

The absorption coefficient of light with a wavelength of 365 nm in methanol of the photopolymerization initiator 2 is preferably 10 to 1.0×10 ² mL/gcm, more preferably 20 to 1.0×10 ² mL/gcm. is more preferred. Further, the absorption coefficient of light with a wavelength of 254 nm in methanol of the photopolymerization initiator 2 is preferably 1.0×10 ³ to 1.0×10 ⁶ mL/gcm, more preferably 5.0×10 ³ to 1.0×10 6 mL/gcm. More preferably 1.0×10 ⁵ mL/gcm. As the photopolymerization initiator 2, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, and phenylglyoxylate compounds are preferable, α-hydroxyketone compounds and phenylglyoxylate compounds are more preferable, and hydroxyalkylphenone compounds. is more preferred. Specific examples of the photopolymerization initiator 2 include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available products such as IRGACURE-184, manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl ]-2-hydroxy-2-methyl-1-propan-1-one (commercially available products include, for example, IRGACURE-2959, manufactured by BASF).

The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.5 to 8.0% by mass. The lower limit is preferably 0.9% by mass or more, more preferably 1.2% by mass or more, and even more preferably 1.5% by mass or more. The upper limit is preferably 7.0% by mass or less, more preferably 6.0% by mass or less, and even more preferably 5.0% by mass or less. In the coloring composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<<Compound having an epoxy group>>
The coloring composition of the present invention can contain a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound preferably has 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably two or more. As the epoxy compound, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408. Compounds, compounds described in JP-A-2017-179172 can also be used. The contents of these are incorporated herein.

Epoxy compounds may be low molecular weight compounds (e.g. molecular weight less than 2000, further molecular weight less than 1000) or macromolecules (e.g. molecular weight 1000 or more, weight average molecular weight 1000 or more in the case of polymers). Either The weight average molecular weight of the epoxy compound is preferably 200-100,000, more preferably 500-50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

Examples of commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Corporation) and EPICLON N-695 (manufactured by DIC Corporation).

The content of the epoxy compound in the total solid content of the coloring composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, more preferably 10% by mass or less. One type of epoxy compound may be contained in the coloring composition, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

<<Silane coupling agent>>
The coloring composition of the present invention can contain a silane coupling agent. According to this aspect, the adhesion of the obtained membrane to the support can be further improved. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred. Specific examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. the contents of which are incorporated herein.

The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.1 to 5 wt%. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The number of silane coupling agents may be one, or two or more. When two or more kinds are used, the total amount is preferably within the above range.

<<Organic solvent>>
The coloring composition of the present invention contains an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the coloring composition. Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a mass ppt (parts per trillion) level organic solvent may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The content of the organic solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 30 to 90% by mass.

<<Curing accelerator>>
A curing accelerator may be added to the coloring composition of the present invention for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. Curing accelerators include methylol compounds (for example, compounds exemplified as cross-linking agents in paragraph number 0246 of JP-A-2015-034963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, JP-A Curing agent described in paragraph number 0186 of 2013-041165), base generator (e.g., ionic compound described in JP-A-2014-055114), cyanate compound (e.g., JP-A-2012-150180 Compounds described in paragraph number 0071), alkoxysilane compounds (e.g., alkoxysilane compounds having an epoxy group described in JP-A-2011-253054), onium salt compounds (e.g., paragraph numbers of JP-A-2015-034963 0216 as examples of acid generators, compounds described in JP-A-2009-180949), and the like can also be used.

When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9 wt% in the total solid content of the coloring composition, 0.8 to 6.4 % by mass is more preferred.

<<polymerization inhibitor>>
The coloring composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors 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-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.

<<Surfactant>>
The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicon surfactants can be used. For surfactants, reference can be made to paragraphs 0238-0245 of WO 2015/166779, the contents of which are incorporated herein.

In the present invention, the surfactant is preferably a fluorosurfactant. By including a fluorine-based surfactant in the coloring composition, the liquid properties (particularly fluidity) can be further improved, and the liquid saving property can be further improved. In addition, it is also possible to form a film with less unevenness in thickness.

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

As the fluorine-based surfactant, JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- 132503, paragraphs 0117-0132, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. .

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant. For such fluorine-based surfactants, the description in JP-A-2016-216602 can be referred to, the content of which is incorporated herein.

上記の化合物の重量平均分子量は、好ましくは３０００～５００００であり、例えば、１４０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。A block polymer can also be used as the fluorosurfactant. Examples thereof include compounds described in JP-A-2011-089090. The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorosurfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol %.

A fluoropolymer having an ethylenically unsaturated bond group in a side chain can also be used as the fluorosurfactant. Specific examples include the compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, such as Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorine-based surfactant.

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Ultraviolet absorber>>
The coloring composition of the present invention can contain an ultraviolet absorber. A conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used as the ultraviolet absorber. For details of these, paragraph numbers 0052 to 0072 of JP 2012-208374, paragraph numbers 0317 to 0334 of JP 2013-068814, paragraph numbers 0061 to 0080 of JP 2016-162946 are described. The contents of which can be referred to are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). Further, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as the ultraviolet absorber. The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Antioxidant>>
The coloring composition of the present invention can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants.

The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Other Ingredients>>
The coloring composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. In addition, the coloring composition of the present invention may contain a latent antioxidant, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available products include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.). In addition, the coloring composition of the present invention may contain a light fastness improver.

The water content of the coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

The coloring composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (such as flatness) and adjusting the film thickness. The viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa·s to 50 mPa·s, more preferably 0.5 mPa·s to 20 mPa·s at 25°C. As a method for measuring the viscosity, for example, a viscometer RE85L manufactured by Toki Sangyo Co., Ltd. (rotor: 1 ° 34' × R24, measurement range 0.6 to 1200 mPa s) is used, and the temperature is adjusted to 25 ° C. can be measured.

The coloring composition of the present invention can be preferably used as a coloring composition for forming colored pixels in a color filter. Colored pixels include, for example, green pixels and blue pixels, and can be used more preferably as a coloring composition for forming green pixels or blue pixels, and more preferably used as a coloring composition for forming green pixels. can.

When the coloring composition of the present invention is used as a color filter for a liquid crystal display device, the voltage holding ratio of the liquid crystal display element provided with the color filter is preferably 70% or more, more preferably 90% or more. . Known means for obtaining a high voltage holding ratio can be appropriately incorporated, and typical means are the use of highly pure materials (e.g., reduction of ionic impurities) and the control of the amount of acidic functional groups in the composition. are mentioned. The voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of JP-A-2011-008004 and paragraphs 0123 to 0129 of JP-A-2012-224847.

The container for the coloring composition of the present invention is not particularly limited, and known containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351. In addition, the colored composition of the present invention and the composition used for manufacturing the image sensor are stored in a container for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the composition, and suppressing deterioration of components. It is also preferable that the inner wall of the container is made of glass, stainless steel, or the like.

<Method for preparing coloring composition>
The coloring composition of the present invention can be prepared by mixing the aforementioned ingredients. In preparing the coloring composition, all components may be dissolved and / or dispersed in an organic solvent at the same time to prepare a coloring composition, and if necessary, each component may be appropriately mixed into two or more solutions or dispersions. These may be mixed at the time of use (at the time of application) to prepare a colored composition.

Moreover, it is preferable that a process of dispersing the pigment is included in the preparation of the coloring composition. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In pulverizing the pigment in a sand mill (bead mill), it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing pigments are described in ``Dispersion Technology Encyclopedia, Information Organization Co., Ltd., July 15, 2005'' and ``Dispersion Technology Centered on Suspension (Solid/Liquid Dispersion System) and Industrial Applications'' The process and disperser described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the pigment, the particles may be made finer in the salt milling step. Materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.

In preparing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyethylene, polyolefin resins such as polypropylene (PP) (high density, ultra high molecular weight including polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01-7.0 μm, more preferably 0.01-3.0 μm, even more preferably 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, reference can be made to the filter manufacturer's nominal value. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like can be used as filters.

It is also preferable to use a fibrous filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.

<Membrane>
The film of the present invention is a film obtained from the coloring composition of the present invention described above. The film of the present invention can be preferably used as a colored pixel of a color filter. Colored pixels include green pixels, blue pixels, and the like, and green pixels are more preferable. The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

<Color filter>
Next, the color filter of the present invention will be explained. The color filter of the invention has the film of the invention described above. More preferably, it has the film of the present invention as a pixel of a color filter. The color filter of the present invention can be used for solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), image display devices, and the like.

In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

The color filter of the present invention preferably has a pixel width of 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, more preferably 10.0 μm or less. Also, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco. Also, the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.). Moreover, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω·cm or more, more preferably 10 ¹¹ Ω·cm or more. Although the upper limit is not specified, it is preferably 10 ¹⁴ Ω·cm or less, for example. The volume resistance value of the pixel can be measured using, for example, a super-high resistance meter 5410 (manufactured by Advantest).

Also, in the color filter of the present invention, a protective layer may be provided on the surface of the film of the present invention. By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01-10 μm, more preferably 0.1-5 μm. Examples of the method of forming the protective layer include a method of applying a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides. Resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ and the like, and two or more of these components may be contained. For example, in the case of a protective layer intended to block oxygen, the protective layer preferably contains a _polyol resin, _SiO2 , _Si2N4 . In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin or a fluororesin.

When a resin composition is applied to form a protective layer, known methods such as spin coating, casting, screen printing, and ink-jetting can be used as methods for applying the resin composition. Known organic solvents (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When the protective layer is formed by a chemical vapor deposition method, the chemical vapor deposition method includes known chemical vapor deposition methods (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method). can be used.

If necessary, the protective layer contains organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain. Examples of organic/inorganic fine particles include polymeric fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like. A known absorber can be used as the absorber for the specific wavelength. Examples of the ultraviolet absorbent and the near-infrared absorbent include the materials described above. The content of these additives can be appropriately adjusted, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total weight of the protective layer.

As the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each color pixel. Moreover, the partition wall may be formed with the configuration described in US2018/0040656.

<Manufacturing method of color filter>
Next, a method for manufacturing the color filter of the present invention will be described. The color filter of the present invention comprises a step of forming a colored composition layer on a support using the above-described colored composition of the present invention, a step of forming a pattern on the colored composition layer by photolithography, can be manufactured through

Pattern formation by photolithography includes the steps of forming a colored composition layer on a support using the colored composition of the present invention, a step of patternwise exposing the colored composition layer, and a step of exposing the colored composition layer. forming a pattern (pixels) by developing and removing the exposed portion. If necessary, a step of baking the coloring composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.

In the step of forming the colored composition layer, the colored composition of the present invention is used to form the colored composition layer on the support. The support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. In some cases, the silicon substrate is formed with a black matrix that isolates each pixel. In addition, the silicon substrate may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the substrate surface.

A known method can be used as a method for applying the coloring composition. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the method of applying the coloring composition, the descriptions of WO2017/030174 and WO2017/018419 can be referred to, and the contents thereof are incorporated herein.

The coloring composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process. When pre-baking is performed, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher. The pre-bake time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, even more preferably 80 to 2200 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

Next, the colored composition layer is patternwise exposed (exposure step). For example, the colored composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.

Radiation (light) that can be used for exposure includes g-line, i-line, and the like. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable. A long-wave light source of 300 nm or more can also be used.

The dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be selected as appropriate, and in addition to exposure in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free) or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m ² to 100000 W/m ² (eg, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). can be done. The oxygen concentration and exposure illuminance may be appropriately combined. For example, the illuminance may be 10000 W/m ² at an oxygen concentration of 10% by volume and 20000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed portion of the colored composition layer is removed by development to form a pattern (pixels). The development and removal of the unexposed portion of the colored composition layer can be performed using a developer. As a result, the unexposed portion of the colored composition layer in the exposure step is eluted into the developer, leaving only the photocured portion. As the developer, an organic alkaline developer is desirable which does not damage the underlying elements and circuits. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

The developer is preferably an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene. Alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate. A compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. Examples of surfactants include the surfactants described above, and nonionic surfactants are preferred. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinsing solution to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support. At this time, when moving the nozzle from the center of the support to the periphery, the moving speed of the nozzle may be gradually decreased. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. A similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.

After development, it is preferable to carry out additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Further, the additional exposure processing may be performed by the method described in KR1020170122130A.

<Solid-state image sensor>
The solid-state imaging device of the present invention has the film of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device.

A plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). 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. and a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.

<Image display device>
The image display device of the present invention has the film of the present invention described above. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. For a definition of an image display device and details of each image display device, see, for example, "Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.), issued in 1989), etc. Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to liquid crystal display devices of various systems described in the above-mentioned "next generation liquid crystal display technology".

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas described in the examples below, Me represents a methyl group.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the measurement sample was measured by gel permeation chromatography (GPC) under the following conditions.
Column type: Column connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 Developing solvent: Tetrahydrofuran Column temperature: 40°C
Flow rate (sample injection volume): 1.0 μL (sample concentration 0.1% by mass)
Apparatus name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve Base resin: Polystyrene resin

<Method for measuring acid value>
A measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and the resulting solution was measured using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry) at 25°C. , neutralization titration with a 0.1 mol/L sodium hydroxide aqueous solution. Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated by the following formula.
A = 56.11 x Vs x 0.5 x f/w
A: Acid value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L aqueous sodium hydroxide solution required for titration
f: titer of 0.1 mol / L sodium hydroxide aqueous solution w: mass of measurement sample (g) (converted to solid content)

<Preparation of dispersion>
After mixing the raw materials listed in the table below, after mixing and dispersing for 3 hours using a bead mill (zirconia beads 0.1 mm diameter), a high-pressure disperser NANO-3000-10 with a pressure reduction mechanism (manufactured by Nippon BEE Co., Ltd.) ) under the conditions of a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a dispersion. In the table below, the numerical value described in the column of parts by mass of the dispersant is the value in terms of solid content. In addition, the numerical value described in the column of parts by mass of the solvent is a value including the amount of the solvent contained in the dispersant.

着色剤Ｂ１：Ｃ．Ｉ．ピグメントイエロー１３８
着色剤Ｂ２：Ｃ．Ｉ．ピグメントイエロー１３９
着色剤Ｂ３：Ｃ．Ｉ．ピグメントイエロー１５０
着色剤Ｂ４：Ｃ．Ｉ．ピグメントイエロー２３１
着色剤Ｂ５～Ｂ７：下記構造の化合物

着色剤Ｃ１：Ｃ．Ｉ．ピグメントレッド２５４The raw materials listed in the above table are as follows.
(coloring agent)
Colorant A1: C.I. I. Pigment Green 62 (aluminum phthalocyanine compound, a compound represented by formula (1))
Colorants A2 to A4: compounds having the following structures Colorant A5: C.I. I. Pigment Green 63 (aluminum phthalocyanine compound, a compound represented by formula (1))

Colorant B1: C.I. I. pigment yellow 138
Colorant B2: C.I. I. pigment yellow 139
Colorant B3: C.I. I. pigment yellow 150
Colorant B4: C.I. I. pigment yellow 231
Colorants B5 to B7: compounds having the following structures

Colorant C1: C.I. I. pigment red 254

(pigment derivative)
Derivative N1: a compound having the following structure

分散剤Ｄ２：以下の方法で製造した分散剤
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、１－チオグリセロール１０８質量部、ピロメリット酸二無水物１７４質量部、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）６５０質量部、触媒としてモノブチルスズオキシド０．２質量部を仕込み、窒素ガスで置換した後、１２０℃で５時間反応させた（第一工程）。酸価の測定で９５％以上の酸無水物がハーフエステル化していることを確認した。次に、第一工程で得られた化合物を固形分換算で１６０質量部、２－ヒドロキシプロピルメタクリレート２００質量部、エチルアクリレート２００質量部、ｔ－ブチルアクリレート１５０質量部、２－メトキシエチルアクリレート２００質量部、メチルアクリレート２００質量部、メタクリル酸５０質量部、ＰＧＭＥＡ６６３質量部を仕込み、反応容器内を８０℃に加熱して、２，２’－アゾビス（２，４－ジメチルバレロニトリル）１．２質量部を添加し、１２時間反応した（第二工程）。固形分測定により９５％が反応したことを確認した。最後に、第二工程で得られた化合物の５０％ＰＧＭＥＡ溶液を５００質量部、２－メタクリロイルオキシエチルイソシアネート（ＭＯＩ）２７．０質量部、ヒドロキノン０．１質量部を仕込み、イソシアネート基に基づく２２７０ｃｍ^－１のピークの消失を確認するまで反応を行った（第三工程）。ピーク消失の確認後、反応溶液を冷却し、ＰＧＭＥＡを加えて固形分濃度を５０質量％に調整して、酸価６８ｍｇＫＯＨ／ｇ、Ｃ＝Ｃ価０．６２ｍｍｏｌ／ｇ、重量平均分子量（Ｍｗ）１３０００の樹脂の樹脂溶液（分散剤Ｄ２）を得た。
分散剤Ｄ３：下記構造の樹脂（主鎖に付記した数値は繰り返し単位のモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ：２００００、酸価：７０ｍｇＫＯＨ／ｇ、Ｃ＝Ｃ価：０．４ｍｍｏｌ／ｇ）

分散剤Ｄ４：下記構造の樹脂（主鎖に付記した数値は繰り返し単位のモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ：２００００、酸価：７５ｍｇＫＯＨ／ｇ）

(dispersant)
Dispersant D1: Dispersant (phosphate ester) produced by the following method
300 g of 2-hydroxyethyl methacrylate, 1315 g of ε-caprolactone monomer, 0.33 g of methyl hydroquinone, and 0.01 g of monobutyltin oxide were charged in a reaction vessel equipped with an air inlet tube, a condenser and a stirrer, and heated to 120°C while flowing dry air. The temperature was raised and held for 2 hours. After confirming the disappearance of the caprolactone monomer, cool to 40° C. or less, mix 111 g of polyphosphoric acid with an orthophosphoric acid conversion content of 118%, gradually raise the temperature, and heat at 80° C. for 6 hours while stirring. A phosphate (dispersant D1) having a number average molecular weight of 700 at Rp ⁴ in the following formula and a ratio of y=1 and y=2 of 100:12 was obtained. The acid value of the resulting phosphate ester was 100 mgKOH/g.

Dispersant D2: Dispersant produced by the following method Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic dianhydride, and propylene glycol monomethyl 650 parts by mass of ether acetate (PGMEA) and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged, and after purging with nitrogen gas, reaction was carried out at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts by mass of the compound obtained in the first step in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, 200 parts by mass of 2-methoxyethyl acrylate 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA were charged, and the inside of the reaction vessel was heated to 80° C. to add 1.2 mass of 2,2′-azobis(2,4-dimethylvaleronitrile). was added and reacted for 12 hours (second step). Solid content measurement confirmed that 95% had reacted. Finally, 500 parts by mass of a 50% PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part by mass of hydroquinone were charged, and 2270 cm based on the isocyanate group. The reaction was continued until disappearance of the ^-1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled, PGMEA was added to adjust the solid content concentration to 50% by mass, and the acid value was 68 mg KOH / g, C = C value 0.62 mmol / g, weight average molecular weight (Mw). A resin solution of 13000 resin (dispersant D2) was obtained.
Dispersant D3: Resin having the following structure (the numerical value attached to the main chain is the molar ratio of the repeating unit, and the numerical value attached to the side chain is the number of repeating units. Mw: 20000, acid value: 70 mgKOH/g, C = C value: 0.4 mmol/g)

Dispersant D4: Resin having the following structure (the numerical value attached to the main chain is the molar ratio of the repeating unit, and the numerical value attached to the side chain is the number of repeating units. Mw: 20000, acid value: 75 mgKOH/g)

(solvent)
Solvent J1: propylene glycol monomethyl ether acetate (PGMEA)
Solvent J2: Cyclohexanone Solvent J3: Cyclohexyl acetate

<Preparation of coloring composition>
After mixing and stirring the raw materials shown in the table below, G compositions 1 to 25, P compositions 1 and 2, and R composition were filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm. A coloring composition of No. 1 was prepared. Note that R composition 1 is a colored composition for evaluation of reliability.

The raw materials listed in the above table are as follows.

(dispersion liquid)
Dispersions K1-K9, L1-L8, M1: Dispersions K1-K9, L1-L8, M1 as described above

樹脂Ｅ２：下記構造の樹脂（主鎖に付記した数値は繰り返し単位のモル比である。Ｍｗ：１４０００、酸価：７８ｍｇＫＯＨ／ｇ）

樹脂Ｅ３：メチルメタクリレート５０質量部、ｎ－ブチルメタクリレート５０質量部、ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）４５．４質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した。反応容器内を７０℃に加熱して、３－メルカプト－１，２－プロパンジオール６質量部を添加して、さらにＡＩＢＮ（アゾビスイソブチロニトリル）０．１２質量部を加え、１２時間反応させた。固形分測定により９５％が反応したことを確認した。次に、ピロメリット酸二無水物９．７質量部、ＰＧＭＥＡ７０．３質量部、触媒としてＤＢＵ（１，８－ジアザビシクロ－［５．４．０］－７－ウンデセン）０．２０質量部を追加し、１２０℃で７時間反応させた。酸価の測定で９８％以上の酸無水物がハーフエステル化していることを確認し反応を終了させて下記構造の樹脂を得た。得られた樹脂は、酸価４３ｍｇＫＯＨ／ｇ、重量平均分子量（Ｍｗ）９０００であった。

樹脂Ｅ４：下記構造の樹脂（主鎖に付記した数値は繰り返し単位のモル比である。Ｍｗ：３００００、酸価：１１０ｍｇＫＯＨ／ｇ）

樹脂Ｅ５：下記構造の樹脂（主鎖に付記した数値は繰り返し単位のモル比である。Ｍｗ：１１０００、酸価：３０ｍｇＫＯＨ／ｇ）

(resin)
Resin E1: Resin having the following structure (the numerical value attached to the main chain is the molar ratio of the repeating unit, and the numerical value attached to the side chain is the number of repeating units. Mw: 10000)

Resin E2: A resin having the following structure (numerical values attached to the main chain are molar ratios of repeating units, Mw: 14000, acid value: 78 mgKOH/g)

Resin E3: 50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into a reaction vessel, and the atmospheric gas was replaced with nitrogen gas. Heat the inside of the reaction vessel to 70° C., add 6 parts by mass of 3-mercapto-1,2-propanediol, add 0.12 parts by mass of AIBN (azobisisobutyronitrile), and react for 12 hours. let me Solid content measurement confirmed that 95% had reacted. Next, add 9.7 parts by mass of pyromellitic dianhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst. and reacted at 120° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a resin having the following structure. The resulting resin had an acid value of 43 mgKOH/g and a weight average molecular weight (Mw) of 9,000.

Resin E4: A resin having the following structure (numerical values attached to the main chain are molar ratios of repeating units, Mw: 30000, acid value: 110 mgKOH/g)

Resin E5: A resin having the following structure (numerical values attached to the main chain are molar ratios of repeating units; Mw: 11,000; acid value: 30 mgKOH/g)

重合性モノマーＦ２：下記構造の化合物

重合性モノマーＦ３：コハク酸変性ジペンタエリスリトールペンタアクリレート(Polymerizable monomer)
Polymerizable monomer F1: a mixture of compounds having the following structure (containing 30 to 40 mol% of the compound on the right)

Polymerizable monomer F2: a compound having the following structure

Polymerizable monomer F3: succinic acid-modified dipentaerythritol pentaacrylate

開始剤Ｇ４：ＩＲＧＡＣＵＲＥ ＯＸＥ０１（ＢＡＳＦ社製）(Photoinitiator)
Initiators G1 to G3: compounds having the following structures

Initiator G4: IRGACURE OXE01 (manufactured by BASF)

(Surfactant)
Surfactant H1: BYK-379 (manufactured by BYK-Chemie)

(Polymerization inhibitor)
Polymerization inhibitor I1: p-methoxyphenol

(solvent)
Solvent J1: Propylene glycol monomethyl ether acetate Solvent J2: Cyclohexanone Solvent J3: Cyclohexyl acetate

<Evaluation of color unevenness>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied on a glass substrate by spin coating so that the film thickness was 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. A stratum was formed. Each coloring composition (G composition or P composition) was applied onto the glass substrate with the underlayer by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to form a coating having a thickness of 0.5. A composition layer of 5 μm was obtained.
This composition layer was exposed to light with a wavelength of 365 nm at an exposure dose of 500 mJ/cm ² . Then, using a hot plate, post-baking was performed at 220° C. for 300 seconds to form a film. Using the glass substrate (evaluation substrate) on which this film was formed, the luminance distribution was analyzed by the following method, and color unevenness was evaluated based on the number of pixels with a deviation from the average of ±10% or more.
A method for measuring the luminance distribution will be described. The substrate for evaluation is installed between the observation lens of an optical microscope and a light source, and the observation lens is irradiated with light, and the state of the transmitted light is observed using an optical microscope MX-50 (manufactured by Olympus Corporation) equipped with a digital camera. observed using Imaging of the membrane surface was performed on five arbitrarily selected regions. The brightness of the photographed image was quantified as a density distribution of 256 gradations from 0 to 255 and stored. The luminance distribution was analyzed from this image, and color unevenness was evaluated based on the number of pixels with a deviation of more than ±10% from the average. Evaluation criteria are as follows.
5: The number of pixels exceeding ±10% deviation from the average is 1000 or less.
4: The number of pixels with a deviation of more than ±10% from the average is more than 1000 and 3000 or less.
3: The number of pixels with a deviation of more than ±10% from the average is more than 3000 and 5000 or less.
2: The number of pixels in which deviation from the average exceeds ±10% is more than 5000 and 15000 or less.
1: The number of pixels with deviation from the average exceeding ±10% exceeds 15,000.

<Evaluation of photolithography (adhesion)>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied on a silicon wafer by a spin coating method so that the film thickness was 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. A stratum was formed. Each coloring composition (G composition or P composition) was applied onto the silicon wafer with the underlayer by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to give a thickness of 0.000. A composition layer of 5 μm was obtained.
An i-line stepper exposure apparatus (FPA-3000i5+, manufactured by Canon Inc.) was used for this composition layer, and a mask in which square pixels each having a side of 1.1 μm were arranged in an area of 4 mm×3 mm on the substrate. Light with a wavelength of 365 nm was irradiated through the pattern, and exposure was performed with an exposure amount of 500 mJ/cm ² .
The exposed composition layer was subjected to puddle development at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide. After that, it was rinsed with water in a spin shower, and then washed with pure water. Thereafter, water droplets were blown off with high-pressure air, and the silicon wafer was air-dried, and post-baked at 220° C. for 300 seconds using a hot plate to form a pattern. The resulting pattern was observed using an optical microscope, and the pattern in close contact with the entire pattern was counted to evaluate the photolithographic properties.
5: All patterns are in close contact.
4: Patterns in close contact account for 90% or more and less than 100% of all patterns.
3: Patterns in close contact account for 80% or more and less than 90% of all patterns.
2: Patterns in close contact account for 70% or more and less than 80% of all patterns.
1: Patterns in close contact are less than 70% of all patterns.

<Evaluation of Reliability>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied onto a silicon wafer by spin coating so as to have a film thickness of 0.1 μm. Then, it was heated at 100° C. for 2 minutes using a hot plate. Further, a hot plate was used to heat the substrate at 230° C. for 2 minutes to form an underlayer. Each coloring composition (G composition or P composition) was applied onto the silicon wafer with the underlayer by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to give a thickness of 0.000. A composition layer of 5 μm was obtained.
Using an i-line stepper exposure machine (FPA-3000i5+, manufactured by Canon Inc.), this composition layer was irradiated with light having a wavelength of 365 nm through a mask having a Bayer pattern of 1.0 μm on a side. , and an exposure dose of 150 mJ/cm ² .
The exposed composition layer was subjected to puddle development at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide. After that, it was rinsed with water in a spin shower, and then washed with pure water. After that, water droplets were blown off with high-pressure air, and the silicon wafer was air-dried, and post-baked at 220° C. for 300 seconds using a hot plate to form green pixels.
Subsequently, the R composition 1 was also subjected to the same treatment, and red pixels were formed in the blank portions of the green pixels to form a structure in which the green pixels and the red pixels were adjacent to each other.
The manufactured structure was incorporated into a solid-state imaging device, and a constant temperature and humidity test was performed for 2000 hours in a constant temperature and humidity chamber at a temperature of 85° C. and a humidity of 85%. After the constant temperature and humidity test, the structure was taken out from the solid-state imaging device, and the cross section (20 points) of the structure was observed using a transmission electron microscope (magnification: 40,000 times) to check for the presence or absence of voids between pixels. The rate of occurrence of voids (spaces) between pixels was examined by observation, and the reliability was determined according to the following criteria.
The occurrence rate of voids (air gaps) was calculated by the following formula for each combination of pixels in contact with each other.
Occurrence rate of voids (voids) = [Number of observed boundaries with voids (voids) occurring]/[Number of observed boundaries]
In addition, in this embodiment, 20 cross sections are randomly selected from the structure, and the presence or absence of voids (air gaps) is observed in 10 boundary groups arranged continuously for each cross section. 200 boundaries were observed.
5: Occurrence rate of voids (voids) = 0
4:0 < occurrence rate of voids ≤ 0.1
3: 0.1 < occurrence rate of voids ≤ 0.2
2: 0.2 < occurrence rate of voids ≤ 0.5
1:0.5<void generation rate≤1.0

As shown in the above table, the examples were good in color unevenness and photolithographic properties (adhesion). Furthermore, the evaluation of reliability was also good. On the other hand, in Comparative Examples, either color unevenness or photolithographic property was evaluated insufficiently. In addition, the numerical value of the content of the polymerizable monomer in the above table is the value of the content of the polymerizable monomer in the total solid content of the coloring composition. Further, the M/B ratio is the ratio between the mass M of the polymerizable monomer contained in the coloring composition and the mass B of the resin contained in the coloring composition. The mass M of the polymerizable monomer is the total mass of the polymerizable monomers F1 to F3 contained in the coloring composition. The mass B of the resin is the total mass of the dispersants D1 to D4 and the resins E1 to E5 contained in the coloring composition.

(Example 100)
The Green composition was applied onto a silicon wafer by spin coating so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ/cm ² through a 2 μm square dot pattern mask. Then, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, the green composition was patterned by heating at 200° C. for 5 minutes using a hot plate. Similarly, the Red composition and the Blue composition were sequentially patterned to form green, red and blue colored patterns (Bayer patterns).
As the Green composition, the coloring composition of G composition 1 was used.
The Red composition and the Blue composition will be described later.
The Bayer pattern is defined as one red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. ) elements. The obtained color filter was incorporated into a solid-state imaging device according to a known method. This solid-state imaging device had a favorable image recognition ability.

- Red composition -
After mixing and stirring the following components, the mixture was filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a red composition.
Red pigment dispersion: 51.7 parts by mass Resin 101: 0.6 parts by mass Polymerizable compound 102: 0.6 parts by mass Photopolymerization initiator 101: 0.3 parts by mass Surfactant 101: 4.2 parts by mass PGMEA : 42.6 parts by mass

-Blue composition-
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.
Blue pigment dispersion: 44.9 parts by mass 40% by mass PGMEA solution of resin 101: 2.1 parts by mass Polymerizable compound 101: 1.5 parts by mass Polymerizable compound 102: 0.7 parts by mass Photopolymerization initiator 101: 0.8 parts by mass Surfactant 101: 4.2 parts by mass PGMEA: 45.8 parts by mass

Raw materials used for the Red composition and the Blue composition are as follows.

Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. Pigment Yellow 139 of 4.3 parts by mass, a dispersing agent (Disperbyk-161, manufactured by BYK Chemie) of 6.8 parts by mass, and PGMEA of 79.3 parts by mass. ) for 3 hours. Thereafter, dispersion treatment was further performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

Blue pigment dispersion C.I. I. Pigment Blue 15:6, 9.7 parts by mass, C.I. I. A mixture of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was prepared in a bead mill (zirconia beads with a diameter of 0.3 mm). was mixed and dispersed for 3 hours. Thereafter, dispersion treatment was further performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reduction mechanism under a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion.

重合性化合物１０１：ＫＡＹＡＲＡＤ ＤＰＨＡ（日本化薬（株）製）
重合性化合物１０２：下記構造の化合物

光重合開始剤１０１：ＩＲＧＡＣＵＲＥ ＯＸＥ０２（ＢＡＳＦ製）
界面活性剤１０１：下記混合物（Ｍｗ＝１４０００）の１質量％ＰＧＭＥＡ溶液。下記の式中、繰り返し単位の割合を示す％はモル％である。

Resin 101: 40% by mass PGMEA solution of a resin having the following structure (numerical values attached to the main chain are molar ratios, Mw = 14000)

Polymerizable compound 101: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound 102: compound having the following structure

Photoinitiator 101: IRGACURE OXE02 (manufactured by BASF)
Surfactant 101: 1 wt% PGMEA solution of the following mixture (Mw = 14000). In the following formulas, % indicating the ratio of repeating units is mol %.

Claims (17)

A coloring composition comprising a coloring agent, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin,
The coloring agent contains at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2), and the compound represented by the formula (1) in the coloring agent and The total content of the compound represented by the formula (2) is 50% by mass or more, and the compound represented by the formula (1) in the total solid content of the coloring composition and the formula (2) The total content with the represented compound is 30 to 60% by mass,
The polymerizable monomer is a tri- to hexa-functional (meth)acrylate compound,
Containing 0.1 to 6.0% by mass of the polymerizable monomer in the total solid content of the coloring composition,
M ¹ / B ¹ , which is the ratio of the mass M ¹ of the polymerizable monomer contained in the coloring composition and the mass B ¹ of the resin contained in the coloring composition, is 0.045 to 0.9,
M ¹ /I ¹ , which is the ratio of the mass M ¹ of the polymerizable monomer contained in the coloring composition and the mass I ¹ of the photopolymerization initiator contained in the coloring composition, is 0.300 to 3.000. is
coloring composition;

In formula (1), X ¹ to X ⁴ are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , —NHSO ₂ Rt ¹ or —SO ₂ NRt ¹ Rt ² , where Rt ¹ and Rt ^{2 each} independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; and Rt ² may combine to form a ring ;
Z ¹ represents a hydroxy group, a halogen atom, —OP(=O)R ¹ R ² , or —O—SiR ³ R ⁴ R ⁵ , and R ¹ to R ⁵ each independently represent a hydrogen atom, a hydroxy group, represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ¹ and R ² , R ³ and R ⁴ may combine with each other to form a ring;
m1 to m4 each independently represent an integer of 0 to 4, and when m1 to m4 are 2 or more, X ¹ to X ⁴ may be the same or different;

In formula (2), X ⁵ to X ¹² are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , —NHSO ₂ Rt ¹ or —SO ₂ NRt ¹ Rt ² , Rt ¹ and Rt ^{2 each} independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; and Rt ² may combine to form a ring ;
L ^A represents -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁶ R ⁷ -O-SiR ⁸ R ⁹ -O-, or -OP(=O)R ¹⁰ -O-; R ⁶ to R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
m5 to m12 each independently represent an integer of 0 to 4, and when m5 to m12 are 2 or more, X ⁵ to X ¹² may be the same or different. 2. The coloring composition according to claim 1, wherein said coloring agent comprises at least one selected from Color Index Pigment Green 62 and Color Index Pigment Green 63. 3. The coloring composition according to claim 1, wherein the colorant comprises at least one selected from Color Index Pigment Yellow 138, Color Index Pigment Yellow 139, Color Index Pigment Yellow 150 and Color Index Pigment Yellow 231. The coloring composition according to any one of claims 1 to 3, wherein the coloring agent further contains a compound represented by the following formula (3);

In formula (3), Ry ¹ to Ry ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group, a salt of a sulfo group, a carboxyl group, a salt of a carboxyl group, phthalimidomethyl group, or represents a sulfamoyl group;
Two adjacent groups among Ry ¹ to Ry ⁴ may be bonded together to form a ring, and two adjacent groups among Ry ¹⁰ to Ry ¹³ may be bonded together to form a ring. good. The colored composition according to any one of claims 1 to 4 , wherein the resin comprises a resin having an ethylenically unsaturated bond group. The resin contains a resin having an ethylenically unsaturated bond group, and the content of the resin having an ethylenically unsaturated bond group in the total amount of the resin contained in the coloring composition is 50 to 100% by mass. The colored composition according to any one of Items 1 to 4. The resin contains a resin containing a repeating unit derived from a compound represented by the following formula (I), the coloring composition according to any one of claims 1 to 6;

wherein Xi ¹ represents O or NH,
Ri ¹ represents a hydrogen atom or a methyl group;
Li ¹ represents a divalent linking group, and the divalent linking group is a hydrocarbon group, a heterocyclic group, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO -, -OCO-, -S- or a group formed by combining two or more thereof,
Ri ¹⁰ is a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORti ¹ , -CORti ¹ , -COORti ¹ , -OCORti ¹ , -NRti ¹ Rti ² , -NHCORti ¹ , -CONRti ¹ Rti ² , —NHCONRti ¹ Rti ² , —NHCOORti ¹ , —SRti ¹ , —SO ₂ Rti ¹ , —SO ₂ ORti ¹ , —NHSO ₂ Rti ¹ or —SO ₂ NRti ¹ Rti ² , Rti ¹ and Rti ² each independently represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Rti ¹ and Rti ² may combine to form a ring,
m represents an integer from 0 to 2,
p represents an integer of 0 or more. The coloring composition according to claim 7, wherein the resin containing repeating units derived from the compound represented by formula (I) further contains repeating units derived from alkyl (meth)acrylate. The polymerizable monomer of claims 1 to 8, comprising at least one selected from succinic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate. A colored composition according to any one of claims 1 to 3. The polymerizable monomer of claims 1 to 8, wherein the polymerizable monomer is at least two selected from succinic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate. A colored composition according to any one of claims 1 to 3. The colored composition according to any one of claims 1 to 10, comprising two or more of the photopolymerization initiators. The coloring composition according to any one of claims 1 to 10, wherein the photopolymerization initiator comprises an oxime compound and an α-hydroxyketone compound. A film obtained from the colored composition according to any one of claims 1-12 . A color filter comprising the film according to claim 13 . A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 12 , and a step of forming a pattern on the colored composition layer by photolithography. and a method for manufacturing a color filter. A solid-state imaging device comprising the film according to claim 13 . An image display device comprising the film according to claim 13 .