JPWO2020080218A1 - Coloring composition, film, color filter, manufacturing method of color filter, solid-state image sensor and image display device - Google Patents

Abstract

It contains a colorant containing a compound represented by the formula (1), a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin, and is polymerized in the total solid content of the coloring composition. A coloring composition containing 0.1 to 6.0% by mass of a sex monomer. A film using a coloring composition, a color filter, a method for manufacturing a color filter, a solid-state image sensor, and an image display device.

Description

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

In recent years, with the widespread use of digital cameras, camera-equipped mobile phones, and the like, demand for solid-state image sensors such as charge-coupled device (CCD) image sensors has increased significantly. Color filters are used as key devices for displays and optical elements. A color filter usually includes pixels of the three primary colors of red, green, and blue, and plays a role of decomposing transmitted light into the three primary colors.

The color filter is manufactured, for example, by using a coloring composition containing a colorant and forming a pattern by a photolithography method. Further, in performing pattern formation by the photolithography method, 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.

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

JP-A-2015-063593 Japanese Unexamined Patent Publication No. 2016-170370 Japanese Unexamined Patent Publication No. 2013-171063

When the present inventor diligently studied a coloring composition containing a coloring agent containing an aluminum phthalocyanine compound, it was found that color unevenness was likely to occur in the film obtained by using this coloring composition. In particular, it was found that when a compound represented by the formula (1) or a compound represented by the formula (2) described later is used as the aluminum phthalocyanine compound, color unevenness tends to occur.

Therefore, an object of the present invention is to provide a coloring composition which is excellent in photolithography and can form a film in which color unevenness is suppressed. Another object of the present invention is to provide a film using a coloring composition, a color filter, a method for manufacturing a color filter, a solid-state image sensor, 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 diligently studied a coloring composition containing an aluminum phthalocyanine compound, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin. It was considered that the reason why color unevenness is likely to occur in the film obtained by using the composition 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, the content of the polymerizable monomer having an ethylenically unsaturated bond group is set within a predetermined range while using the compound represented by the formula (1) or the compound represented by the formula (2) described later. It has been found that a film in which color unevenness is suppressed can be formed while having excellent photolithography by adjusting to the above, and the present invention has been completed. Therefore, the present invention provides the following.
<1> A coloring composition containing a colorant, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin.
The colorant contains at least one selected from the compound represented by the following formula (1) and the compound 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 independently represent substituents;
Z ¹ represents a hydroxy group, a halogen atom, -OP (= O) R ¹ R ² , or -O-Si R ^{3 R 4} R ⁵ , and R ^{1 to} R ⁵ are independent hydrogen atoms, hydroxy groups, respectively. Representing an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a ring;
m1~m4 are each independently a 0-4 integer, when m1~m4 is 2 or ^more, X 1 to X ⁴ may be different from each other in the same;

In formula (2), X ^{5 to} X ¹² each independently represent a substituent;
L ^{A is, -O-SiR 6 R 7 -O} -, - O-SiR 6 R 7 -O-SiR 8 R 9 -O-, or ^{-O-P (= O) R} 10 -O- and represents, R ^{6 to} R ¹⁰ independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
m5~m12 are each independently a 0-4 integer, when m5~m12 is 2 or ^more, X 5 ^{to X 12} may have respectively the same or different.
<2> The coloring composition according to <1>, wherein the colorant 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 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. 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 the formula (3), Ry ^{1 to Ry 13} are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, sulfo group, sulfo group salt, carboxyl group, carboxyl group salt and phthalimidomethyl. Represents a group, or sulfamoyl group;
Two adjacent groups of Ry ^{1 to Ry 4} may be bonded to each other to form a ring, and two adjacent groups of Ry ^{10 to Ry 13} may be bonded to each other to form a ring. good.
<5> Any of <1> to <4> in which the total content of the compound represented by the formula (1) and the compound represented by the formula (2) in the colorant is 30% by mass or more. The coloring composition according to one.
<6> The coloring composition according to any one of <1> to <5>, wherein the resin contains a resin having an ethylenically unsaturated bond group.
<7> The coloring 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);

In the formula, Xi ¹ represents O or NH and represents
Ri ¹ represents a hydrogen atom or a methyl group
Li ¹ represents a divalent linking group
Ri ¹⁰ represents a substituent and represents
m represents an integer from 0 to 2
p represents an integer greater than or equal to 0.
<8> The coloring composition according to <7>, wherein the resin containing the repeating unit derived from the compound represented by the formula (I) further contains the repeating unit derived from the 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 to the mass B ^{1 of the} resin contained in the coloring composition, is 0.03 to 0.15. The coloring 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> to. The coloring composition according to any one of <9>.
<11> A film obtained from the coloring 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 coloring composition layer on a support using the coloring composition according to any one of <1> to <10>, and a pattern on the coloring composition layer by a photolithography method. A process of forming a color filter and a method for manufacturing a color filter.
<14> A solid-state image sensor having the film according to <11>.
<15> An image display device having the film according to <11>.

According to the present invention, it is possible to provide a coloring composition which is excellent in photolithography and can form a film in which color unevenness is suppressed. Further, it is possible to provide a film using a coloring composition, a color filter, a method for manufacturing a color filter, a solid-state image sensor, and an image display device.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Acryloyl "represents both acryloyl and / or methacryloyl.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent.
As used herein, the term pigment means a compound that is difficult to dissolve in a solvent.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired 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, and the coloring agent is a coloring composition described later. It contains at least one selected from the compound represented by 1) and the compound represented by the formula (2), and contains 0.1 to 6.0% by mass of the polymerizable monomer in the total solid content of the coloring composition. It is characterized by that.

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

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, it is derived from the polymerizable monomer that scatters from the film even if the carbon-carbon bond is broken over time. It is also possible to suppress the film shrinkage of the obtained film over time due to the small amount of the components. In particular, even when the film is exposed to a high humidity environment for a long period of time, the film shrinkage can be effectively suppressed. Therefore, it is possible to suppress the generation of voids between the film formed by using the coloring composition of the present invention and the member adjacent to the film. For example, a pixel of another color is formed between pixels of another color using the coloring composition of the present invention, or a pixel of another color is formed between pixels formed using the composition of the present invention to form a structure such as a color filter. Even when such a structure is exposed to a high humidity environment for a long period of time, it is possible to suppress the generation of voids between adjacent pixels. Further, when a structure such as a color filter is manufactured by forming pixels in a region partitioned by a partition wall using the coloring composition of the present invention, such a structure is used for a long period of time in a high humidity environment. Even when exposed, it is possible to suppress the generation of voids between the pixel and the partition wall.

The coloring composition of the present invention can be preferably used as a coloring composition for a color filter. Specifically, it can be preferably used as a coloring composition for forming pixels of a color filter. Further, the coloring composition of the present invention can be preferably used as a coloring composition for a solid-state image sensor, and more preferably as a coloring composition for forming pixels of a color filter used for a solid-state image sensor. Further, the coloring composition of the present invention can be preferably used as a coloring composition for a display device, and more preferably as a coloring composition for forming pixels of a color filter used in a display device. Further, the coloring composition of the present invention can also be used as a composition for forming a color microlens. Examples of the method for manufacturing a color microlens include the methods described in JP-A-2018-010162.

Hereinafter, the coloring composition of the present invention will be described in detail.

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

In formula (1), X ^{1 to} X ⁴ independently represent substituents. Examples of the substituent represented by X ^{1 to X 4} include a substituent T described later. The ^{substituent represented by X 1 to} X ⁴ is preferably a halogen atom, a nitro group, an alkyl group, an aryl group, a heterocyclic group, -ORt ¹ , -SRt ¹ , -SO ₂ NRt ¹ Rt ² , preferably a halogen atom or an alkyl group. Is more preferable, and a halogen atom is further preferable. Rt ¹ and Rt ² independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group is preferable.

In formula (1), Z ¹ represents a hydroxy group, a halogen atom, -OP (= O) R ¹ R ² , or -O-Si R ^{3 R 4} R ⁵ , and R ^{1 to} R ⁵ are independent of each other. It 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 be bonded to each other to form a ring.

Z ¹ is preferably a hydroxy group, -OP (= O) R ¹ R ² or -O-Si R ^{3 R 4} R ^5, more preferably -OP (= O) R ¹ R ² , and R ¹ and R ² are. -OP (= O) R ¹ R ² which are independently aryl groups are more preferable. Examples of the halogen atom represented by Z ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The ^{alkyl and alkoxy groups represented by R 1 to} R ⁵ preferably have 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and 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 even 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 a substituent T described later.

R ¹ and R ² and R ³ and R ⁴ may be combined 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 be combined with each other to form a ring. Further, when Z ¹ is −O—SiR ³ R ⁴ R ⁵ , R ³ and R ⁴ may be bonded to each other to form a ring. The ring formed by bonding these groups to each other may be an aliphatic ring, an aromatic ring, or a heterocycle.

In the formula (1), m1 to m4 each independently represent an integer of 0 to 4, and 0 or 1 is preferable, and 0 is more preferable. When m1~m4 is 2 or ^more, X 1 to X ⁴ may have respectively the same or different.

In formula (2), X ^{5 to} X ¹² each independently represent a substituent. Examples of the substituent represented by X ^{5 to X 12} include a substituent T described later. The ^{substituent represented by X 5 to} X ¹² is preferably a halogen atom, a nitro group, an alkyl group, an aryl group, a heterocyclic group, -ORt ¹ , -SRt ¹ , -SO ₂ NRt ¹ Rt ² , preferably a halogen atom or an alkyl group. Is more preferable, and a halogen atom is further preferable. Rt ¹ and Rt ² independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group is preferable.

L ^{A is, -O-SiR 6 R 7 -O} -, - O-SiR 6 R 7 -O-SiR 8 R 9 -O-, or ^{-O-P (= O) R} 10 -O- and represents, R ^{6 to} R ¹⁰ independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group.

L ^A is, ^{-O-SiR 6} R 7 -O- or ^{-O-P (= O) R} 10 -O- is ^{preferable, -O-P (= O)} R 10 -O- and more ^{preferably, R 10 -OP (= O) R 10-} O- in which is an aryl group is more preferred.

The ^{alkyl and alkoxy groups represented by R 6 to} R ¹⁰ preferably have 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and 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 even 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 a substituent T described later.

In the formula (2), m5 to m12 each independently represent an integer of 0 to 4, and 0 or 1 is preferable, and 0 is more preferable. When m5~m12 is 2 or ^more, X 5 ^{to X 12} may have respectively the same or different.

(Substituent T)
As the substituent T, 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 can be mentioned. Rt ¹ and Rt ² independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, respectively. Rt ¹ and Rt ² may be combined to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 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 aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
The heterocyclic group may be a monocyclic ring or a condensed ring. The heterocyclic group is preferably a single ring or a fused ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom 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 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent described in the above-mentioned Substituent T.

Specific examples of the compound (1) and the compound (2) include a compound having the following structure, a compound described in paragraphs 0046 to 0053 of JP2015-063593A, and paragraph number 0151- of JP2013-171063A. Examples thereof include the compound described in 0169 and the compound described in paragraphs 0251 to 0258 of JP2016-170370A. 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 the compound (1) and the compound (2) in the colorant is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. Is more preferable. 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 above-mentioned compound (1) and compound (2). According to this aspect, it is easy to form a film having spectral characteristics suitable for green pixels. The content of the yellow colorant in the coloring composition is preferably 5 to 60 parts by mass with respect to 100 parts by mass in total of the above-mentioned compound (1) and compound (2). The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and further 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 further preferably 20 parts by mass or more.

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

As the yellow pigment, Color Index (CI) 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, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-054339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-026228, and the like 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 the above-mentioned compounds (1) and (2). It is preferable to contain at least one of these. 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 the above-mentioned compound (1) and compound (2). The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and further 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 further 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 above-mentioned compound (1) and compound (2). Compound (3) can be preferably used as a yellow colorant.

In the formula (3), Ry ^{1 to Ry 13} are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, sulfo group, sulfo group salt, carboxyl group, carboxyl group salt and phthalimidomethyl. It represents a group or a sulfamoyl group, preferably a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable. The alkyl group and the alkoxy group preferably have 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms. 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.) and 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 of Ry 1 to Ry 4} may be bonded to each other to form a ring, and two adjacent groups of Ry ^{10 to Ry 13} may be bonded to each other to form a ring. May be formed. Among them, it is preferable that at least one set of two adjacent groups of ^{Ry 1 to Ry 4} and Ry ^{10 to Ry 13 are bonded to form a ring.} The ring formed may be any of an aliphatic ring, an aromatic ring, and a heterocycle, and is preferably an aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocycle, and an aromatic hydrocarbon ring is preferable. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and a benzene ring is preferable.

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

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

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

When the colorant used in the present invention further contains compound (3), the content thereof shall be 5 to 60 parts by mass with respect to 100 parts by mass in total of the above-mentioned compound (1) and compound (2). Is preferable. The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and further 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 further preferably 20 parts by mass or more.

The colorant used in the present invention can further contain a colorant other than the above-mentioned compound (hereinafter, also referred to as another colorant). 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. (The above is 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 pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42,60,61 etc. (above, purple pigment),
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. , Blue pigment).

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Can also be used. Specific examples include the compounds described in WO 2015/118720. Further, as the green pigment, the compound described in CN106909027A, a phthalocyanine compound having a phosphoric acid ester as a ligand, and the like can also be used.

As a red pigment, a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in JP-A-2017-2013384, and a diketopyrrolopyrrole-based pigment described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838. Pigments and the like can also be used. Further, as the red pigment, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. can.

Moreover, a dye can also be used as another colorant. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo system, anilino azo system, triarylmethane system, anthraquinone system, anthraquinone system, benzylidene system, oxonol system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolopyrazole azomethine system, xanthene system, Examples thereof include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes. Further, the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, and the azo compound described in JP-A-2011-145540 can also be preferably used. Further, the intramolecular imide type xanthene dye described in JP-A-2018-012863 can also be used.

In addition, a dye multimer can be used as another colorant. The dye multimer is preferably a dye that is used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is a particle, it is usually dispersed in a solvent. Used. The pigment multimer in the particle state can be obtained by, for example, emulsion polymerization, and specific examples thereof include the compounds and production methods described in JP-A-2015-214682. The 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. The plurality of dye structures contained in one molecule may have the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 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, International Publication No. 2016/031442, and the like. Compounds can also be used.

The content of the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, further 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 the compound (1) and the compound (2) is preferably 25% by mass or more, more preferably 30% by mass or more, based on the total solid content of the coloring composition. , 35% by mass or more is more preferable, and 40% by mass or more is particularly preferable. 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 a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is replaced with an acid group, a basic group or a phthalimide methyl group. The chromogens constituting the pigment derivative include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthracinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, and iso. Indoline skeleton, isoindolinone skeleton, quinophthalone skeleton, slene skeleton, metal complex skeleton, etc. Preferably, the azo skeleton and the benzoimidazolone skeleton are more preferred. As the acid group contained in the pigment derivative, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As the basic group contained in the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable.

In the present invention, a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be contained as the pigment derivative. The maximum value of the molar extinction coefficient at the wavelength region of 400~700nm transparent pigment derivative (.epsilon.max) is that it is preferable, 1000L ^· mol ^{-1 · cm} -1 or less is not more than 3000L ^· mol ^{-1 · cm} -1 Is more preferable, and 100 L · mol ^-1 · cm ^-1 or less is further 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 the pigment derivative include the compounds described in paragraphs 0162 to 0183 of JP2011-52065A and the compounds described in JP2003-081972. Specific examples of the transparent pigment derivative 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, based on 100 parts by mass of the total of the compound (1) and the compound (2). 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, based on the total solid content of the coloring composition. Mass% or more is particularly preferable. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. Only one type of pigment derivative may be used, or two or more types 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 a binder. The resin mainly used for dispersing particles and the like in the composition is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for purposes other than such an application.

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

The weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and even more preferably 5000 or more.

As the coloring composition of the present invention, a resin having an acid group can be used as the resin. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. The resin having an acid group can also be used as an alkali-soluble resin or a dispersant. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further 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 resin represented by a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). A resin containing the derived repeating unit can be used.

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 the formula (ED1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or 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.

For a specific example of the ether dimer, paragraph number 0317 of JP2013-209760A can be referred to, and the content thereof is incorporated in the present specification.

As the coloring composition of the present invention, a resin having a maleimide structure can also be used as the resin. In addition, in this specification, a maleimide structure is a structure derived from a maleimide compound. Examples of the maleimide compound include maleimide and N-substituted maleimide. Examples of the N-substituted maleimide include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide and the like.

The resin having a maleimide structure is preferably a resin containing a repeating unit having a maleimide structure. The maleimide structure may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. The maleimide structure is preferably contained in the main chain of the repeating unit because it is easy to form a film in which color unevenness is suppressed.

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 a compound represented by the formula (I) as a resin. Is also preferable. When the coloring 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 the repeating unit i1-1 in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more.

In the formula, Xi ¹ represents O or NH, and is 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 consisting of a combination of two or more of the above can be mentioned. Examples of the hydrocarbon group include an alkyl group and an aryl group. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxy group, a halogen atom and the like.
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, and more preferably an alkyl group which may have 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, even more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 1.

(Substituent Ti)
As the substituent Ti, 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 ,- Included are 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 independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group, respectively. Rti ¹ and Rti ² may be combined to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 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 aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
The heterocyclic group may be a monocyclic ring or a condensed ring. The heterocyclic group is preferably a single ring or a fused ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom 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 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent described in the above-mentioned Substituent Ti.

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

Xi ¹ represents O or NH, and is 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, and more preferably an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further 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 which may have an aryl group as a substituent, and more preferably an alkyl group having an aryl group as a substituent. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. When the alkyl group has an aryl group as a substituent, the carbon number of the alkyl group means the carbon number of the alkyl moiety.
Ri ¹² represents a substituent. Examples of the ^{substituent represented by Ri 12} include the above-mentioned substituent Ti.
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.
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, even 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, further 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 the formula (I) is preferably a compound represented by the following formula (III).

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 from 0 to 15. The ^{alkylene group represented by Ri 21} and Ri ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. 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 the formula (I) include ethylene oxide of paracumylphenol or propylene oxide-modified (meth) acrylate. Examples of commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

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

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

The resin i also preferably contains a repeating unit having an ethylenically unsaturated bond group. Examples of the repeating unit having an ethylenically unsaturated bond group include a repeating unit represented by the formula (A-1-1) described later. The content of the repeating unit having an ethylenically unsaturated bond group in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 15 mol% or more. Is more preferable. 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. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger 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 is preferable, and substantially, when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. A resin consisting only of an acid group is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups exceeds 50 mol% is preferable when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group contained in the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. Since the resin used as the dispersant contains a repeating unit having an acid group, the generation of development residue can be further suppressed when the pattern is formed by the photolithography method.

The resin used as the dispersant is also preferably a graft resin. For details of the graft resin, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.

The resin used as the dispersant is also preferably 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 of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. The resin to have is preferable. 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 JP2012-255128A can be referred to, and this content is incorporated in the present specification.

The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such a resin include dendrimers (including star-shaped polymers). Specific examples of the dendrimer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.

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

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by Big Chemie (for example, Disperbyk-111, 2001, etc.) and the Solsparse series manufactured by Nippon Lubrizol Co., Ltd. (for example, Disperserbyk-111, 2001). For example, Solsparse 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd.'s Ajispar series and the like can be mentioned. Further, the product described in paragraph number 0129 of JP2012-137564A and the product described in paragraph number 0235 of JP2017-194662 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, the film contraction over time can be suppressed more effectively.

The ethylenically unsaturated bond base 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, further preferably 3.0 mmol / g or less, further preferably 2.0 mmol / g or less, and 1.0 mmol / g or less. It is particularly preferable to have. The lower limit is preferably 0.1 mmol / g or more, and 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 determined by extracting the low molecular weight component (a) having a C = C group moiety from the polymerizable resin by alkaline treatment, measuring the content thereof by high performance liquid chromatography (HPLC), and using the following formula. Can be calculated. When the C = C group site cannot be extracted from the polymerizable resin by alkaline treatment, the value measured by the NMR method (nuclear magnetic resonance) is used.
C = C value [mmol / g] = (content of small molecule component (a) [ppm] / molecular weight of low molecular component (a) [g / mol]) / (weighed value of polymerizable resin) [G] x (solid content concentration of polymerizable resin [mass%] / 100) x 10)

The polymerizable resin preferably contains a repeating unit having an ethylenically unsaturated bond group in the 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 is preferably contained in an amount of 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 in all the repeating units of the polymerizable resin. It is more preferably contained in an amount of ~ 70 mol%.

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

In the 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 groups, polyalkyleneimine-based linking groups, polyester-based linking groups, polyurethane-based linking groups, polyurea-based linking groups, polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, etc. From the viewpoint of availability of raw materials and production suitability, poly (meth) acrylic-based linking groups and polyalkyleneimine-based linking groups are preferable, and poly (meth) acrylic-based linking groups are more preferable.

In the 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) and an alkyleneoxy group (preferably an alkylene group having 1 to 12 carbon atoms). Oxy group), oxyalkylene carbonyl group (preferably oxyalkylene carbonyl 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 consisting of a combination of 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 are preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the 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 the formula (A-1-1), ^{examples of the ethylenically unsaturated bonding group represented by Y 1} include a vinyl group, an allyl group, a metallicyl group, a (meth) acryloyl group and a styrene group, and the (meth) acryloyl group, A styrene group is preferable, a (meth) acryloyl group is more preferable, and an acryloyl group is particularly preferable.

Specific examples of the repeating unit represented by the formula (A-1-1) include a repeating unit represented by the following formula (A-1-1a) and a repeating unit represented by the following formula (A-1-1b). Units and the like can be mentioned.

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

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

The polymerizable resin preferably 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 the aggregation of the above-mentioned compound (1) and compound (2) due to steric hindrance caused by the graft chain. Further, at the time of forming the cured film, the polymerizable resin can be polymerized in the vicinity of the compound (1) and the compound (2) to firmly hold the compound (1) and the compound (2) in the film. It is also possible to more effectively suppress the 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 the repeating units having a graft chain in all the 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 that branches and extends from the main chain of a repeating unit. The length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, and the dispersibility of the compound (1) and the compound (2) can be enhanced. The graft chain preferably has 40 to 10000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and 60 to 60 to 2000 atoms excluding hydrogen atoms. It is more preferably 500.

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 at least one structural repeating unit selected from polyester repeating units, polyether repeating units, poly (meth) acrylic repeating units, polyurethane repeating units, polyurea repeating units and polyamide repeating units, preferably polyester. It is more preferred to include at least one structural repeating unit selected from repeating units, polyether repeating units and poly (meth) acrylic repeating units, and even more preferably polyester repeating units. Examples of the polyester repeating unit include a repeating unit having a structure represented by the following formula (G-1), formula (G-4) or formula (G-5). Further, as the polyether repeating unit, a repeating unit having a structure represented by the following formula (G-2) can be mentioned. Further, as the poly (meth) acrylic repeating unit, a repeating unit having a structure represented by the following formula (G-3) can be mentioned.

In the above formula, ^RG1 and ^RG2 each represent an alkylene group. It is not particularly restricted but includes alkylene groups represented by R ^G1 and R ^G2, preferably a linear or branched alkylene group having 1 to 20 carbon atoms, 2 to 16 carbon atoms linear or branched alkylene A group is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is further preferable.
In the above formula, ^RG3 represents a hydrogen atom or a methyl group.
In the above formula, Q ^G1 represents -O- or -NH-, and LG ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include 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), and an oxyalkylenecarbonyl group (preferably 1 to 12 carbon atoms). ~ 12 oxyalkylene carbonyl group), arylene group (preferably arylene group having 6 to 20 carbon atoms), _{-NH-, -SO-, -SO 2-} , -CO-, -O-, -COO-, OCO Examples thereof include groups consisting of −, −S− and a combination of two or more of these.
^RG4 represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group 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 the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable, from the viewpoint of improving the dispersibility of pigments and the like. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and are 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). It is preferable to have.

In the above ^formula, and ^{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-, L G1} represents a single bond or It represents a divalent linking group, R ^G4 represents a hydrogen atom or a substituent, W ¹⁰⁰ represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. For ^{R G1 ~R G4, Q G1,} L G1 , Formula (G1) ~ (G-5 ) has the same meaning as ^{R G1 ~R G4, Q G1,} L G1 described in, the preferred range is also the same be.

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

In the formulas (G-1a) to (G-5a), n1 to n5 are preferably integers of 2 to 100, more preferably integers of 2 to 80, and even more preferably integers of 8 to 60.

In the formula (G-1a), R ^G1 each other in each repeating unit in the case of n1 is 2 or more, may be the same or may be different. When the ^RG1 contains 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 the formulas (G-2a) to (G-5a).

Examples of the repeating unit having a graft chain include a repeating unit represented by the following formula (A-1-2).

In formula (A-1-2), X ² represents the main chain of the repeating unit, L ² represents a single bond or a divalent linking group, and W ¹ represents a graft chain.

As the main chain of the repeating unit represented by ^{X 2} in the formula (A-1-2), ^{the structure described by X 1} in the formula (A-1-1) can be mentioned, and the preferable range is also the same. ^{The divalent linking group represented by L 2} in the 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 consisting of a combination of two or more of these. ^{Examples of the graft chain represented by W 1} in the formula (A-1-2) include the above-mentioned graft chain.

Specific examples of the repeating unit represented by the formula (A-1-2) include a repeating unit represented by the following formula (A-1-2a) and a repeating unit represented by the following formula (A-1-2b). Units and the like can be mentioned.

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

In formula (A-1-2b), R ^b10 and R ^b11 independently represent a hydrogen atom or an alkyl group, m2 represents an integer of 1 to 5, and L ² is a single bond or a divalent link. Represents a group and W ¹ represents a graft chain. The ^{number of carbon atoms of the alkyl group represented by R b10} and R ^b11 is preferably 1 to 10, and more preferably 1 to 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, and 1000 to 7500. Is more preferable. 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 the polymerization of the repeating unit. For example, repeating units with graft chains can be formed by polymerizing macromonomers. Here, the macromonomer means a polymer compound in which a polymerizable group is introduced at the polymer terminal. 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.

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

Examples of the repeating unit having an acid group include a repeating unit 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. As the main chain of the repeating unit represented by ^{X 3} in the formula (A-1-3), ^{the structure described by X 1} in the formula (A-1-1) can be mentioned, and the preferable range is also the same. ^{The divalent linking group represented by L 3} in the 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 a group consisting of a combination of 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 are preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and the like. ^{Examples of the acid group represented by A 1} in the 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 a repeating unit represented by the following formula (A-1-3a) and a repeating unit represented by the following formula (A-1-3b). Units and the like can be mentioned.

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

In formula (A-1-3b), R ^c10 and R ^c11 independently represent a hydrogen atom or an alkyl group, m3 represents an integer of 1 to 5, and L ³ is a single bond or a divalent link. It represents a group, and A ¹ represents an acid group. The ^{number of carbon atoms of the alkyl group represented by R c10} and R ^c11 is preferably 1 to 10, and more preferably 1 to 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, preferably 10 to 80 mol%, based on all the repeating units of the polymerizable resin. 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. The upper limit is more preferably 100 mgKOH / g or less. The lower limit is preferably 30 mgKOH / g or more, and more preferably 35 mgKOH / g or more. When the acid value of the polymerizable resin is within the above range, particularly excellent dispersibility can be easily obtained. Furthermore, excellent developability can be easily 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 the 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, and P ¹⁰ is ( Meta) Represents a polymer chain having an acryloyl group.

^{Examples of the group containing an aromatic carboxyl group represented by Ar 10} in the formula (b-10) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like. Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.

In the above formula, Q ¹ is represented by a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO _2- , -C (CF ₃ ) _2- , and the following formula (Q-1). Represents a group to be used or a group represented by the following formula (Q-2).

Specific examples of aromatic tricarboxylic acid anhydrides include benzenetricarboxylic acid anhydrides (1,2,3-benzenetricarboxylic acid anhydrides, trimellitic acid anhydrides [1,2,4-benzenetricarboxylic acid anhydrides], etc.). , Naphthalenetricarboxylic acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalene Tricarboxylic acid anhydride, etc.), 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2,3 , 2'-biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenylsulfonetricarboxylic acid anhydride. Specific examples of aromatic tetracarboxylic acid anhydrides include pyromellitic dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3. ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic Acid dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-frantetracarboxylic acid 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'-perfluoroisopropyridendiphthalic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid 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 dianhydride Anhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene hydride, 9,9-bis [4- (3) , 4-Dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic hydride, or 3,4-dicarboxy-1, Examples thereof include 2,3,4-tetrahydro-6-methyl-1-naphthalene succinic hydride and the like.

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

In the formula (Ar-1), n1 represents an integer of 1 to 4, preferably an integer of 1 to 2, and more preferably 2.
In the formula (Ar-2), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 to 2, and even more preferably 2.
In the 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, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
In the 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-). It represents a group represented by 1) or a group represented by the above formula (Q-2).

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

Hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two of these are the trivalent linking groups represented by ^{L 12} in the formula (b-10). Groups that combine species and above can be mentioned. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and the like. The ^{trivalent linking group represented by L 12} is preferably a group represented by the following formula (L12-1), and more preferably a group represented by the 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} in the formula (b-10), and * 2 represents the bonding position with L 11 in the formula (b-10). It represents a bonding position to ^{P 10} of.

The ^{trivalent linking group represented by L 12a} and L ^12b is selected from a hydrocarbon group; a hydrocarbon group and -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which at least one type is combined.

In formula (b-10), P ¹⁰ represents a polymer chain having a (meth) acryloyl group. The ^{polymer chain represented by P 10} 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 ^{P 10} is preferably 500 to 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 5000 or less, and even more preferably 3000 or less. When ^{the weight average molecular weight of P 10} is in 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 the formula (b-10), the ^{polymer chain represented by P 10} is preferably a polymer chain containing a repeating unit 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, ^RP1 and ^RP2 each represent an alkylene group. The alkylene group represented by R ^P1 and R ^P2, 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, ^RP3 represents a hydrogen atom or a methyl group.
In the above formula, L ^P1 represents a single bond or an arylene group, L ^P2 represents a single bond or a divalent linking group. L ^P1 is preferably a single bond. ^Examples of the divalent linking group represented by LP2 include 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-, and -SO-. _{-SO 2 -, - CO -,} - O -, - COO -, - OCO -, - S -, - NHCO -, - CONH-, and include a group formed by combining two or more of these.
^RP4 represents a hydrogen atom or a substituent. Substituents include hydroxy groups, carboxyl groups, alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, and (meth) acryloyl. The group etc. can be mentioned.

Further, the ^{polymer chain represented by P 10} is more preferably a polymer chain having a repeating unit containing a (meth) acryloyl group in the side chain. The proportion of the repeating unit containing the total repeating units constituting the P ^10, the (meth) acryloyl group in a side chain is preferably 5 mass% or more, more preferably 10 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.

It is also preferable that the polymer chain represented by P ¹⁰ has a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. 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 the repeating unit containing an acid group is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass.

The resin containing the repeating unit represented by the formula (b-10) reacts at least one acid anhydride selected from aromatic tetracarboxylic acid anhydride and aromatic tricarboxylic acid anhydride with a hydroxy group-containing compound. It can be manufactured by letting it. Examples of the aromatic tetracarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride include those described above. The hydroxy group-containing compound is not particularly limited as long as it has a hydroxy group in the molecule, but is preferably a polyol having two or more hydroxy groups in the molecule. Further, as the hydroxy group-containing compound, it is also preferable to use a compound having two hydroxy groups and one thiol group in the molecule. Examples of compounds having two hydroxy groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 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- Examples thereof include mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like. Examples of other hydroxy group-containing compounds include the compounds described in paragraphs 0084 to 0995 of JP-A-2018-101039, the contents of which are incorporated in the present specification.

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 the repeating unit represented by the formula (b-10) is preferably 2000 to 35000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.

The acid value of the resin containing the repeating unit represented by the 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。As the polymerizable resin, it is also preferable to use a compound represented by the following formula (OP1).

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

The number average molecular weight of Rp ⁴ is more preferably 400 to 10000, still more preferably 400 to 3000. When ^{the number average molecular weight of Rp 4} is in the above range, the dispersibility of the pigment is good, and such a resin is preferably used as a dispersant.

Examples of the polyether residue and / or polyester residue having an ethylenically unsaturated bonding group represented by Rp ⁴ include a polyether residue having a styrene group, a (meth) acryloyl group, a cyanoacryloyl group, a vinyl ether group, and / or Polyester residues can be 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. Further, from the viewpoint of pigment dispersibility, s is preferably 2 or more. In this case, Rp ¹⁴ may use different groups from each other. s is more preferably 2 to 5, and particularly preferably 2.

Examples of the ^{trihydric or higher polyhydric alcohol used in Rp 13} include glycerin, propyl alcohol, pentaerythritol, dipentaerythritol and the like. In particular, those having a valence of 3 to 6 are preferable.

As the compound represented by the formula (OP1), a phosphoric acid ester having a single type of ^{Rp 4} may be used, or a plurality of types of phosphoric acid esters having ^{different Rp 4 may be used.} Further, the compound of y = 1 may be used alone, or a mixture of the compound of y = 1 and the compound of y = 2 may be used. In the compound represented by the formula (OP1), when the abundance ratio of the compound with y = 1 and the compound with y = 2 is 100: 0 to 100:30, the pigment dispersibility is good, which is preferable. ^{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 10000 (more preferably 400 to 3000), the pigment dispersibility is improved, which is preferable.

The content of the resin 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, and more preferably 50% by mass or less. The lower limit is preferably 30% by mass or more, and 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. Is more preferable, and 70 to 100% by mass is further preferable.

Further, 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 in combination. 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 to the resin having no ethylenically unsaturated bond group has a resin having an ethylenically unsaturated bond group: having an ethylenically unsaturated bond group. No resin = 1: 0.001 to 0.800, more preferably 1: 0.002 to 0.700, even more preferably 1: 0.003 to 0.600.

<< 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 the ethylenically unsaturated bonding group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable monomer is preferably a compound that can be polymerized by radicals (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 group is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less. The polymerizable monomer is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3 to 15 functional (meth) acrylate compound, and a 3 to 10 functional (meth) acrylate compound. It is more preferable to have a (meth) acrylate compound having 3 to 6 functions, and it is particularly preferable to use a (meth) acrylate compound.

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

The ethylenically unsaturated bond base value (hereinafter referred to as C = C value) of the polymerizable monomer shall be 2 to 14 mmol / g from the viewpoint of the stability of the composition over time and the color loss resistance of the obtained film. Is preferable. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further 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 three or more ethylenically unsaturated bonding groups, and is a compound having a molecular weight of 450 or less containing three ethylenically unsaturated bonding groups. Is more preferable, and a trifunctional (meth) acrylate compound having a molecular weight of 450 or less is further preferable. According to this aspect, the solvent resistance of the obtained film can be further improved. The detailed reason for obtaining such an effect is not clear, but it is presumed that it was possible to form a very dense network structure by exposure. Examples of the polymerizable monomer having a molecular weight of 450 or less containing three ethylenically unsaturated bonding groups include trimethylolpropane tri (meth) acrylate.

The polymerizable monomer used in the present invention is also preferably a compound having an isocyanurate skeleton. Specific examples of the polymerizable monomer having an isocyanurate skeleton include trisocyanurate (2-acryloyloxyethyl), εcaprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, and the like. Commercially available products include Funkrill FA-731A (manufactured by Hitachi Kasei Co., Ltd.), NK Ester A9300, A93001CL, A9300-3CL (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix M-315 (Toagosei Co., Ltd.) ), Etc.

In the present invention, as the polymerizable monomer, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Japan). Yakuhin Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. Compounds having such a structure (for example, SR454, SR499 commercially available from Sartmer) and the like can also be used. It is also preferable to use Aronix M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate manufactured by Toagosei Co., Ltd.) 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 portion can be easily removed during development, and the generation of development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable. Examples of the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate. Examples of commercially available products of the polymerizable monomer having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when it is 40 mgKOH / g or less, it is advantageous in 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. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

The polymerizable monomer is a compound described in JP-A-2017-048367, JP-A-6057891 and Patent No. 6031807, a compound described in JP-A-2017-194662, 8UH-1006, 8UH. It is also preferable to use -1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

The polymerizable monomer used in the present invention may contain 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, better photolithography can be easily 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 further 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, still more preferably 4.5% by mass or less.

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, and more preferably 54.5% by mass or less. The lower limit is preferably 31.0% by mass or more, and more preferably 36.5% by mass or more.

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, and more preferably 9.5% by mass or less. The lower limit is preferably 2.2% by mass or more, and more preferably 3.0% by mass or more.

The ratio (M ¹ / B ^{1 ) of the mass M 1} of the polymerizable monomer contained in the coloring composition to the mass B ^{1 of the} resin contained in the coloring composition shall be 0.03 to 0.15. Is preferable. The lower limit of the above-mentioned ratio value 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, and even more preferably 0.9 or less. If the above ratio is 0.03 or more, the pattern forming property in the photolithography method is good, and if it is 0.15 or less, the generation of residue during pattern forming in the photolithography method can be suppressed more effectively. ..

The ratio (M ¹ / I ^{1 ) 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 is 0.013 to 12.000. Is preferable. The lower limit of the above-mentioned ratio value 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, and even more preferably 3,000 or less. If the above ratio is 0.013 or more, the line width sensitivity is good, and if it is 12,000 or less, the pattern formability by the photolithography method is good.

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. When two or more kinds of polymerizable monomers are used, the total amount thereof is preferably in the above range.

<< Photopolymerization Initiator >>
The coloring composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, and thio. Examples thereof include compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and phenylglycolate compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and further preferably an oxime compound. .. Regarding the photopolymerization initiator, the descriptions in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489 can be referred to, and these contents are incorporated in the present specification.

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

Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Phototherapy Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in Japanese Patent Application Laid-Open No. 2004-534977, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Japanese Patent Application Laid-Open No. 6065596, International Publication No. 2015 / 152153, the compound described in International Publication No. 2017/051680, the compound described in JP-A-2017-198865, the compound described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, etc. Can be mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, 2-acetoxyimiminopentane-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), and ADEKA PTOMER N-1919. (A Photopolymerization Initiator 2) manufactured by ADEKA Corporation and described in JP2012-014502A. Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and being hard to discolor. Examples of commercially available products include ADEKA ARKULS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a fluorene ring can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein by reference.

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

In the present invention, an oxime compound having a nitro group can be used as the 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 paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

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

In the present invention, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used as the photopolymerization initiator. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the coloring composition with time can be improved. .. Specific examples of the bifunctional or trifunctional or higher functional photoradical polymerization initiators include JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, and JP-A-2016-532675. Dimerics of oxime compounds described in paragraphs 0412 to 0417, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds described in JP2013-522445. G), Cmpd 1 to 7 described in International Publication No. 2016/034963, Oxime Esters Photoinitiator described in paragraph No. 0007 of JP-A-2017-523465, JP-A-2017-167399. Examples thereof include the photoinitiator described in paragraphs 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the like.

In the present invention, as the photopolymerization initiator, the photopolymerization initiator 1 extinction coefficient of wavelength 365nm is not less than 1.0 × ¹⁰ 4 mL / gcm in methanol, the absorption coefficient of wavelength 365nm in methanol 1. It is also preferable to use in combination with the photopolymerization initiator 2 having an extinction coefficient of 0 × 10 ² mL / gcm or less and a wavelength of 254 nm of 1.0 × 10 ^{3 mL / gcm or more.} According to this aspect, it is easy to sufficiently cure the coloring composition by exposure, and it is easy to obtain better photolithography. As the photopolymerization initiator 1 and the photopolymerization initiator 2, it is preferable to select and use a compound having the above-mentioned extinction coefficient from the above-mentioned 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 extinction coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the above-mentioned measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrum meter (Cary5000) manufactured by Agilent Technologies. The absorbance coefficient (mL / gcm) at 254 nm was calculated.

In the above formula, ε represents the extinction coefficient (mL / gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g / mL), and l represents 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, preferably 1.2 × 10 ^{4 to} 1.0 × 10 ⁵ mL / gcm. It is more preferably 1.3 × 10 ^{4 to} 5.0 × 10 ⁴ mL / gcm, and more preferably 1.5 × 10 ^{4 to} 3.0 × 10 ⁴ mL / gcm. Especially preferable.
The absorption coefficient of the light 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, preferably 1.5 × 10 ⁴ to 1.5 × 10 4 to g cm. It is more preferably 9.5 × 10 ⁴ mL / gcm, and even more preferably 3.0 × 10 ^{4 to} 8.0 × 10 ⁴ mL / gcm.

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

Extinction coefficient of light of wavelength 365nm at in methanol photoinitiator 2 is preferably 10~1.0 × ¹⁰ 2 mL / gcm, it is 20~1.0 × ¹⁰ 2 mL / gcm Is more preferable. The extinction coefficient of light of the photopolymerization initiator 2 in methanol at a wavelength of 254 nm ^{is preferably 1.0 × 10 3 to} 1.0 × 10 ⁶ mL / gcm, preferably 5.0 × 10 ³ to 5.0 × 10 3 to 1.0 × 10 6 mL / g cm. More preferably, it is 1.0 × 10 ^{5 mL / gcm.} As the photopolymerization initiator 2, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound and phenylglycilate compound are preferable, α-hydroxyketone compound and phenylglioxylate compound are more preferable, and hydroxyalkylphenone compound is more preferable. Is more preferable. Specific examples of the photopolymerization initiator 2 include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl). ] -2-Hydroxy-2-methyl-1-propane-1-one (commercially available products include, for example, IRGACURE-2959, manufactured by BASF) and the like.

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 further 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, still 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 with 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 preferable. The epoxy compound preferably has 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably two or more. Examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP2014-043556, and paragraph numbers 0085-0092 of JP2014-089408. Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein by reference.

The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). It may be any of. The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 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, and more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less. The epoxy compound contained in the coloring composition may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount thereof is 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 film to the support can be further improved. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group. , A phenyl group and the like, preferably an amino group, a (meth) acryloyl group and an epoxy group. Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703A and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. The contents of are incorporated herein by reference.

The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, and more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in 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 coatability of the coloring composition. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like. For these details, paragraph No. 0223 of WO 2015/166779 can be referred to, the contents of which are incorporated herein by reference. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent 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 need to be reduced for environmental reasons (for example, 50 mass ppm (parts) with respect to the total amount of organic solvent. Per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per tension) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015). Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter 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 filter material 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, and even more preferably 30 to 90% by mass.

<< Curing Accelerator >>
In the coloring composition of the present invention, a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. The curing accelerator is a methylol-based compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-034963), amines, a phosphonium salt, an amidin salt, and an amide compound (for example, JP-A-2015). Hardener described in paragraph No. 0186 of Japanese Patent Application Laid-Open No. 2013-041165), base generator (for example, ionic compound described in Japanese Patent Application Laid-Open No. 2014-055141), cyanate compound (for example, Japanese Patent Application Laid-Open No. 2012-150180). Paragraph number of paragraph No. 0071), alkoxysilane compound (for example, alkoxysilane compound having an epoxy group described in JP-A-2011-253504), onium salt compound (eg, JP-A-2015-034963). A compound exemplified as an acid generator in 0216, a compound 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% by mass, preferably 0.8 to 6.4% by mass, based on the total solid content of the coloring composition. More preferably by mass.

<< Polymerization inhibitor >>
The coloring composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferable. 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 a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. For surfactants, paragraphs 0238 to 0245 of WO 2015/166779 can be referred to, the contents of which are incorporated herein by reference.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the coloring composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.

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

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

Further, as the fluorine-based surfactant, 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. For such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the content thereof is incorporated in the present specification.

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。As the fluorine-based surfactant, a block polymer can also be used. For example, the compounds described in Japanese Patent Application Laid-Open No. 2011-0899090 can be mentioned. The fluorine-based surfactant 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) (meth). 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 the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compounds is preferably 3000 to 50000, for example 14000. Among the above compounds,% indicating the ratio of the repeating unit is mol%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond group in the side chain can also be used. As specific examples, the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.

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 to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.

<< UV absorber >>
The coloring composition of the present invention can contain an ultraviolet absorber. As the 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 indol compound, a triazine compound and the like can be used. For details thereof, refer to paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-068814, and paragraph numbers 0061 to 0080 of JP2016-162946. These contents can be taken into consideration and are incorporated herein by reference. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used. 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 type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

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

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 type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<< Other ingredients >>
The coloring compositions of the present invention, as required, include sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (eg, conductive particles, fillers, defoamers, etc.). It may contain a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension modifier, a chain transfer agent, etc.). By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 and subsequent paragraphs of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraphs of JP-A-2008-250074. The descriptions of Nos. 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. In addition, the coloring composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like. Further, the coloring composition of the present invention may contain a light resistance improving agent.

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, and 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 (flatness, etc.), adjusting the film thickness, and the like. The viscosity value can be appropriately selected as needed, but for example, at 25 ° C., 0.3 mPa · s to 50 mPa · s is preferable, and 0.5 mPa · s to 20 mPa · s is more preferable. As a method for measuring the viscosity, for example, a viscometer RE85L (rotor: 1 ° 34'× R24, measuring range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd. 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. Examples of the colored pixel include a green pixel and a blue pixel, which can be more preferably used as a coloring composition for forming a green pixel or a blue pixel, and further preferably used as a coloring composition for forming a green pixel. can.

When the coloring composition of the present invention is used as a color filter for a liquid crystal display device, the voltage retention rate 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 include the use of a high-purity material (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition. Can be mentioned. The voltage retention rate can be measured by, for example, the methods described in paragraphs 0243 of JP2011-008004A and paragraphs 0123 to 0129 of JP2012-224847A.

The container for the colored composition of the present invention is not particularly limited, and a known container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and a bottle in which 6 types of resin are composed of 7 layers are used. It is also preferable to use it. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351. Further, the coloring composition of the present invention and the composition used for producing an image sensor are contained for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the composition, and suppressing the alteration of components. It is also preferable that the inner wall of the container is made of glass or stainless steel.

<Preparation method of coloring composition>
The coloring composition of the present invention can be prepared by mixing the above-mentioned components. In preparing the coloring composition, all the components may be dissolved and / or dispersed in an organic solvent at the same time to prepare the coloring composition, or if necessary, two or more solutions or dispersions of each component may be appropriately prepared. However, these may be mixed at the time of use (at the time of application) to prepare a coloring composition.

In addition, it is preferable to include a process of dispersing the pigment in the preparation of the coloring composition. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes 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. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to process under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industrial application centered on suspension (solid / liquid dispersion system)". The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Practical Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the pigment, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

In preparing the coloring composition, it is preferable to filter the coloring 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, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight). A filter using a material such as (including the polyolefin resin of) is mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.

It is also preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of 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 Co., Ltd.

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

<Membrane>
The film of the present invention is a film obtained from the above-mentioned coloring composition of the present invention. The film of the present invention can be preferably used as a colored pixel of a color filter. Examples of the colored pixel include a green pixel and a blue pixel, and a green pixel is more preferable. The film thickness of the film of the present invention can be appropriately adjusted according to the intended 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 further preferably 0.3 μm or more.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned film of the present invention. 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 a solid-state image sensor such as a CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor), an image display device, or the like.

In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted according to the intended purpose. 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 further 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, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, and more preferably 10.0 μm or less. Further, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

It is preferable that each pixel included in the color filter of the present invention has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. The lower limit is not specified, but it is preferably 0.1 nm or more, for example. The surface roughness of the pixels can be measured using, for example, an AFM (atomic force microscope) Measurement 3100 manufactured by Veeco. Further, 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.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, it is preferred that the volume resistivity value of the pixel is 10 ⁹ Ω · cm or more, and more preferably 10 ¹¹ Ω · cm or more. The upper limit is not specified, but ^{it is preferably 10 14} Ω · cm or less, for example. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).

Further, the color filter of the present invention may be provided with a protective layer on the surface of the film of the present invention. By providing the protective layer, various functions such as oxygen blocking, low reflection, hydrophobicization, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying a resin composition dissolved in an organic solvent to form the protective layer, a chemical vapor deposition method, and a method of attaching the molded resin with an adhesive. The components constituting the protective layer include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide. 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 Examples thereof include resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , and Si ₂ N _4, and two or more of these components may be contained. For example, in the case of a protective layer for the purpose of blocking oxygen, the protective layer preferably contains a polyol resin, SiO ₂ , and Si ₂ N ₄ . Further, in the case of a protective layer for the purpose of reducing reflection, the protective layer preferably contains a (meth) acrylic resin or a fluororesin.

When the resin composition is applied to form the protective layer, known methods such as a spin coating method, a casting method, a screen printing method, and an inkjet method can be used as the application method of the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by a chemical vapor deposition method, the chemical vapor deposition method is a known chemical vapor deposition method (thermochemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method). Can be used.

The protective layer may be an additive such as organic / inorganic fine particles, an absorber for light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjuster, an antioxidant, an adhesive, a surfactant, etc., if necessary. May be contained. Examples of organic / inorganic fine particles include high molecular weight fine particles (for example, 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 having a specific wavelength. Examples of the ultraviolet absorber and the near-infrared absorber include the above-mentioned materials. The content of these additives can be adjusted as appropriate, 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.

Further, as the protective layer, the protective layer 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 colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each colored pixel. Further, the partition wall may be formed with the configuration described in US2018 / 0040656A.

<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 includes a step of forming a coloring composition layer on a support using the coloring composition of the present invention described above, and a step of forming a pattern on the coloring composition layer by a photolithography method. Can be manufactured via.

Pattern formation by the photolithography method includes a step of forming a coloring composition layer on a support using the coloring composition of the present invention, a step of exposing the coloring composition layer in a pattern, and a step of exposing the coloring composition layer in a pattern. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). 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 coloring composition layer, the coloring composition layer of the present invention is used to form the coloring composition layer on the support. The support is not particularly limited and may be appropriately selected depending on the intended use. For example, a glass substrate, a silicon substrate, and the like can be mentioned, and a silicon substrate is preferable. Further, 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 addition, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with an undercoat layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate.

As a method for applying the coloring composition, a known method can be used. For example, a drop method (drop cast); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nano-imprint method and the like can be mentioned. The method of application to inkjet is not particularly limited, and for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.

The colored composition layer formed on the support may be dried (prebaked). When the film is produced by a low temperature process, it is not necessary to perform prebaking. When prebaking is performed, the prebaking 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, or 80 ° C. or higher. The prebaking time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 2200 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.

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

Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.

Irradiation dose (exposure dose), for example, preferably ^{0.03~2.5J / cm 2, 0.05~1.0J / cm} 2 is more preferable. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment), or may be exposed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, or, 35000W / ^{m 2)} selected from the range of Can be done. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / ^{m 2.}

Next, the unexposed portion of the coloring composition layer is developed and removed to form a pattern (pixel). The unexposed portion of the coloring composition layer can be developed and removed using a developing solution. As a result, the colored composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains. As the developing solution, an organic alkaline developing solution that does not cause damage to the underlying elements and circuits is desirable. The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.

The developing solution is preferably an alkaline aqueous solution (alkaline developing solution) obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, organics such as 1,8-diazabicyclo [5.4.0] -7-undecene. Examples thereof include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms 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. In addition, the developer may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. The developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid 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 rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion to the peripheral portion of the support.

It is preferable to perform additional exposure treatment or heat treatment (post-baking) after development and drying. Additional exposure treatment and post-baking are post-development curing treatments to complete the curing. The heating temperature in the post-baking is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. .. When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in KR1020170122130A.

<Solid image sensor>
The solid-state image sensor of the present invention has the above-mentioned film of the present invention. The configuration of the solid-state image sensor of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image sensor, and examples thereof include the following configurations.

On the substrate, there are a plurality of photodiodes constituting a light receiving area of a solid-state image sensor (CCD (charge coupling element) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to have a light-shielding film in which only the light-receiving part of the photodiode is opened, and to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. The configuration has a color filter on the device protective film. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. There may be. Further, the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each colored pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478, JP-A-2014-179557, and International Publication No. 2018/043654. The image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.

<Image display device>
The image display device of the present invention has the above-mentioned film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For details on the definition of image display devices and the details of each image display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Device (by Junaki Ibuki, Industrial Books)" Co., Ltd. (issued in 1989) ”. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Further, in the structural formulas described in the following examples, 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) according to the following conditions.
Column type: Column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 are linked Developing solvent: tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 1.0 μL (sample concentration 0.1% by mass)
Device name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve base resin: Polystyrene resin

<Measurement method of acid value>
The measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9/1 (mass ratio), and the obtained solution was prepared at 25 ° C. using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo). , 0.1 mol / L sodium hydroxide aqueous solution was neutralized and titrated. The acid value was calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
A = 56.11 x Vs x 0.5 x f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)
f: Titer of 0.1 mol / L sodium hydroxide aqueous solution w: Measurement sample mass (g) (solid content conversion)

<Preparation of dispersion>
After mixing the raw materials listed in the table below, they are mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm diameter), and then a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.). ) Was used to carry out the dispersion treatment under the condition of a flow rate of 500 g / min under a pressure of 2000 kg / cm ^3. This dispersion treatment was repeated 10 times to obtain a dispersion liquid. In the table below, the numerical values described in the column of the mass part of the dispersant are the values in terms of solid content. The numerical value described in the column of the mass part 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.
(Colorant)
Colorant A1: C.I. I. Pigment Green 62 (aluminum phthalocyanine compound, a compound represented by the formula (1))
Colorants A2 to A4: Compounds with the following structure Colorants A5: C.I. I. Pigment Green 63 (aluminum phthalocyanine compound, a compound represented by the 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 with the following structure

Colorant C1: C.I. I. Pigment Red 254

(Pigment derivative)
Derivative N1: Compound with 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
In a reaction vessel equipped with an air introduction tube, a condenser, and a stirrer, 300 g of 2-hydroxyethyl methacrylate, 1315 g of ε-caprolactone monomer, 0.33 g of methylhydroquinone, and 0.01 g of monobutyltin oxide were charged, and the temperature was adjusted to 120 ° C. while flowing dry air. The temperature was raised and held for 2 hours. After confirming the disappearance of the caprolactone monomer, the mixture was cooled to 40 ° C. or lower, mixed with 111 g of polyphosphoric acid having an orthophosphoric acid equivalent content of 118%, gradually heated, and heated at 80 ° C. for 6 hours with stirring. A phosphoric acid ester (dispersant D1) having a number average molecular weight of Rp ⁴ of the following formula and an abundance ratio of y = 1 and y = 2 of 100:12 was obtained. The acid value of the obtained phosphoric acid ester was 100 mgKOH / g.

Dispersant D2: Dispersant produced by the following method In a reaction vessel equipped with a gas introduction 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, replaced with nitrogen gas, and then reacted at 120 ° C. for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, the compound obtained in the first step is 160 parts by mass 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, and 200 parts by mass of 2-methoxyethyl acrylate. Parts, 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 obtain 1.2 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile). Parts were added and reacted for 12 hours (second step). It was confirmed by solid content measurement 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 parts by mass of hydroquinone were charged, and 2270 cm based on the isocyanate group. ^The reaction was carried out until the disappearance of the peak of -1 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, the acid value was 68 mgKOH / g, the C = C value was 0.62 mmol / g, and the weight average molecular weight (Mw). A resin solution of 13000 resins (dispersant D2) was obtained.
Dispersant D3: Resin having the following structure (the numerical value added to the main chain is the molar ratio of the repeating unit, and the numerical value added 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 added to the main chain is the molar ratio of the repeating unit, and the numerical value added 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>
The raw materials shown in the table below are mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to obtain G compositions 1 to 25, P compositions 1, 2, and R compositions. The coloring composition of 1 was prepared. The R composition 1 is a coloring composition for evaluating reliability.

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

(Dispersion)
Dispersions K1 to K9, L1 to L8, M1: Dispersions K1 to K9, L1 to L8, M1 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 added to the main chain is the molar ratio of the repeating unit, and the numerical value added to the side chain is the number of repeating units. Mw: 10000)

Resin E2: Resin having the following structure (the numerical value added to the main chain is the molar ratio of the repeating unit. 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 the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you. It was confirmed by solid content measurement that 95% had reacted. Next, 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) were added as a catalyst. Then, the reaction was carried out at 120 ° C. for 7 hours. It was confirmed by measuring the acid value 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 obtained resin had an acid value of 43 mgKOH / g and a weight average molecular weight (Mw) of 9000.

Resin E4: Resin having the following structure (the numerical value added to the main chain is the molar ratio of the repeating unit. Mw: 30,000, acid value: 110 mgKOH / g)

Resin E5: Resin having the following structure (the numerical value added to the main chain is the molar ratio of the repeating unit. Mw: 11000, 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 30-40 mol% of the right compound)

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）(Photopolymerization initiator)
Initiators G1-G3: Compounds with the following structure

Initiator G4: IRGACURE OXE01 (manufactured by BASF)

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

(Polymerization inhibitor)
Polymerization inhibitor I1: p-methoxyphenol

(solvent)
Solvent J1: Propropylene glycol monomethyl ether acetate Solvent J2: Cyclohexanone Solvent J3: Cyclohexanacetate

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

<Evaluation of photolithography (adhesion)>
CT-4000 (manufactured by Fujifilm Electronics Materials Co., Ltd.) is applied on a silicon wafer by the spin coating method so that the film thickness is 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. Formed a stratum. Each coloring composition (G composition or P composition) is applied onto the silicon wafer with the base layer by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to obtain a thickness of 0. A 5 μm composition layer was obtained.
A mask in which square pixels having a side of 1.1 μm are arranged in a region of 4 mm × 3 mm on a substrate by using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.) for this composition layer. Light having a wavelength of 365 nm was irradiated through the pattern and exposed at an exposure amount of ^{500 mJ / cm 2.}
The exposed composition layer was paddle-developed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Then, it was rinsed with water in a spin shower, and further washed with pure water. Then, the water droplets were blown off with high-pressure air, the silicon wafer was naturally dried, and then post-baked at 220 ° C. for 300 seconds using a hot plate to form a pattern. The obtained pattern was observed using an optical microscope, and the patterns in close contact with each other were counted to evaluate the photolithography property.
5: All patterns are in close contact.
4: The patterns that are in close contact are 90% or more and less than 100% of all patterns.
3: The patterns that are in close contact are 80% or more and less than 90% of all patterns.
2: The patterns that are in close contact are 70% or more and less than 80% of all patterns.
1: The number of patterns that are in close contact is less than 70% of all patterns.

<Evaluation of reliability>
CT-4000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied onto a silicon wafer by a spin coating method so that the film thickness was 0.1 μm. Then, it was heated at 100 ° C. for 2 minutes using a hot plate. Further, the base layer was formed by heating at 230 ° C. for 2 minutes using a hot plate. Each coloring composition (G composition or P composition) is applied onto the silicon wafer with the base layer by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to obtain a thickness of 0. A 5 μm composition layer was obtained.
This composition layer is irradiated with light having a wavelength of 365 nm using an i-line stepper exposure machine (FPA-3000i5 +, manufactured by Canon Inc.) through a mask having a Bayer pattern with a side of 1.0 μm. , 150 mJ / cm ² exposure.
The exposed composition layer was paddle-developed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. Then, it was rinsed with water in a spin shower, and further washed with pure water. Then, water droplets were blown off with high-pressure air, the silicon wafer was naturally dried, and then post-baked at 220 ° C. for 300 seconds using a hot plate to form green pixels.
Subsequently, the same treatment was carried out for the R composition 1 to form a red pixel in the missing portion of the green pixel to form a structure in which the green pixel and the red pixel are adjacent to each other.
The prepared structure was incorporated into a solid-state image sensor, and a constant temperature and humidity test was conducted for 2000 hours in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 85%. The structure is taken out from the solid-state image sensor after the constant temperature and humidity test, and the cross section (20 points) of the structure is observed using a transmission electron microscope (magnification 40,000 times) to check the presence or absence of voids (voids) between pixels. By observing, the occurrence rate of voids (voids) between pixels was examined, and the reliability was judged by the following criteria.
The void (void) generation rate was calculated by the following formula for each combination of pixels in contact with each other.
Occurrence rate of voids = [Number of observed boundaries where voids (voids) have occurred] / [Number of observed boundaries]
Further, in this embodiment, 20 cross sections are randomly selected from the structure, and the presence or absence of voids (voids) is observed in 10 boundary groups arranged continuously for each cross section. The boundaries of 200 points were observed.
5: Occurrence rate of 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 (void) generation rate ≤ 1.0

As shown in the above table, in the examples, the evaluation of color unevenness and photolithography (adhesion) was good. Furthermore, the evaluation of reliability was also good. On the other hand, in the comparative example, evaluation of either color unevenness or photolithography was insufficient. 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. The M / B ratio is the ratio of the mass M of the polymerizable monomer contained in the coloring composition to 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 a spin coating method 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. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) ^{, exposure was performed with an exposure amount of 1000 mJ / cm 2} through a mask with a dot pattern of 2 μm square. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. The Green composition was then patterned using a hot plate by heating at 200 ° C. for 5 minutes. Similarly, the Red composition and the Blue composition were sequentially patterned to form green, red and blue coloring 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 one red element, two green elements, and one blue element as disclosed in US Pat. No. 3,971,065. ) This is a pattern in which a 2 × 2 array of color filter elements having an element is repeated. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had a suitable image recognition ability.

-Red composition-
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm 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-
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole 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 of resin 101 PGMEA solution: 2.1 parts by mass Polymerizable compound 101: 1.5 parts by mass Polymerized compound 102: 0.7 parts by mass Photoinitiator 101: 0.8 parts by mass Polymerizer 101: 4.2 parts by mass PGMEA: 45.8 parts by mass

The raw materials used in the Red composition and the Blue composition are as follows.

Red pigment dispersion C. I. Pigment Red 254 at 9.6 parts by mass, C.I. I. A mixed solution consisting of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter). ) Was mixed and dispersed for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to carry ^{out a dispersion treatment under a pressure of 2000 kg / cm 3} at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion liquid.

Blue pigment dispersion C. I. Pigment Blue 15: 6 at 9.7 parts by mass, C.I. I. A mixed solution consisting of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA, bead mill (zirconia beads 0.3 mm diameter). Was mixed and dispersed for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to carry ^{out a dispersion treatment under a pressure of 2000 kg / cm 3} at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

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: A 40% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Mw = 14000).

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

Photopolymerization Initiator 101: IRGACURE OXE02 (manufactured by BASF)
Surfactant 101: 1% by mass PGMEA solution of the following mixture (Mw = 14000). In the formula below,% indicating the ratio of the repeating unit is mol%.

Claims (15)

A coloring composition containing a colorant, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin.
The colorant contains at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2).
A coloring composition containing 0.1 to 6.0% by mass of the polymerizable monomer in the total solid content of the coloring composition;

In formula (1), X ^{1 to} X ⁴ independently represent substituents;
Z ¹ represents a hydroxy group, a halogen atom, -OP (= O) R ¹ R ² , or -O-Si R ^{3 R 4} R ⁵ , and R ^{1 to} R ⁵ are independent hydrogen atoms, hydroxy groups, respectively. Representing an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a ring;
m1~m4 are each independently a 0-4 integer, when m1~m4 is 2 or ^more, X 1 to X ⁴ may be different from each other in the same;

In formula (2), X ^{5 to} X ¹² each independently represent a substituent;
L ^{A is, -O-SiR 6 R 7 -O} -, - O-SiR 6 R 7 -O-SiR 8 R 9 -O-, or ^{-O-P (= O) R} 10 -O- and represents, R ^{6 to} R ¹⁰ independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
m5~m12 are each independently a 0-4 integer, when m5~m12 is 2 or ^more, X 5 ^{to X 12} may have respectively the same or different. The coloring composition according to claim 1, wherein the colorant contains at least one selected from Color Index Pigment Green 62 and Color Index Pigment Green 63. The coloring composition according to claim 1 or 2, 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, further comprising a compound represented by the following formula (3).

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

In the formula, Xi ¹ represents O or NH and represents
Ri ¹ represents a hydrogen atom or a methyl group
Li ¹ represents a divalent linking group
Ri ¹⁰ represents a substituent and represents
m represents an integer from 0 to 2
p represents an integer greater than or equal to 0. The coloring composition according to claim 7, wherein the resin containing the repeating unit derived from the compound represented by the formula (I) further contains the repeating unit derived from alkyl (meth) acrylate. ^{Claimed that M 1} / B ^1, which is the ratio of ^{the mass M 1} of the polymerizable monomer contained in the ^{coloring composition to the mass B 1 of the} resin contained in the coloring composition, is 0.03 to 0.15. Item 8. The coloring composition according to any one of Items 1 to 8. The polymerizable monomer according to claim 1 to 9, wherein 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. The coloring composition according to any one of the items. A film obtained from the coloring composition according to any one of claims 1 to 10. The color filter having the film according to claim 11. A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 10, and a step of forming a pattern on the colored composition layer by a photolithography method. And, a method of manufacturing a color filter having. The solid-state imaging device having the film according to claim 11. An image display device having the film according to claim 11.