JP7233518B2 - Coloring composition, cured film, pattern forming method, color filter, solid-state imaging device, and image display device - Google Patents

Description

The present invention relates to coloring compositions containing diketopyrrolopyrrole pigments. The present invention also relates to a cured film using the coloring composition, a pattern forming method, a color filter, a solid-state imaging device and an image display device.

Demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors is greatly increasing due to the spread of digital cameras, camera-equipped mobile phones, and the like. Color filters are used as key devices for displays and optical elements. A color filter usually has pixels (coloring patterns) of three primary colors of red, green, and blue, and serves to decompose transmitted light into three primary colors. A color filter is formed using a coloring composition containing a coloring material such as a pigment. In addition, a diketopyrrolopyrrole pigment or the like is used as a coloring material in a coloring composition for forming red pixels.

For example, in Examples of Patent Documents 1 and 2, Color Index Pigment Red 254 (a compound in which R ¹ and R ² in the following structural formula are chlorine atoms) and Color Index Pigment Red 264 are used as diketopyrrolopyrrole pigments. (Compounds in which R ¹ and R ² in the following structural formula are phenyl groups) or colored compositions using compounds in which R ¹ and R ² in the following structural formulas are bromine atoms are described.

JP 2016-065115 A JP 2017-066377 A

In recent years, there have been increasing demands for various properties of cured films used in color filters and the like. As one of such required properties, further improvement in heat resistance is desired.

When the present inventor examined the colored compositions described in Patent Documents 1 and 2, it was found that there is room for further improvement in the heat resistance of the resulting cured film.

Accordingly, an object of the present invention is to provide a colored composition capable of forming a cured film having excellent heat resistance. Another object of the present invention is to provide a cured film using the colored composition, a pattern forming method, a color filter, a solid-state imaging device and an image display device.

式中、Ｒ^１は置換基を表し、Ｒ^２は電子供与性基を表し、ｎは０～４の整数を表し、波線はジケトピロロピロール骨格との結合部位を表す。
＜５＞ 上記顔料Ａは、下記式（１）で表される化合物である、＜１＞～＜４＞のいずれか１つに記載の着色組成物；

式中、Ｒ^１１およびＲ^１２はそれぞれ独立して置換基を表し、Ｒ^２１およびＲ^２２はそれぞれ独立して電子供与性基を表し、ｎ１１およびｎ１２はそれぞれ独立して０～４の整数を表す。
＜６＞ 上記顔料Ａは、下記式（２）で表される化合物である、＜１＞～＜５＞のいずれか１つに記載の着色組成物；

式中、Ｒ^１１およびＲ^１２はそれぞれ独立して置換基を表し、Ｒ^２１およびＲ^２２はそれぞれ独立して電子供与性基を表し、ｎ１１およびｎ１２はそれぞれ独立して０～４の整数を表す。
＜７＞ 上記顔料Ａは赤色顔料である、＜１＞～＜６＞のいずれか１つに記載の着色組成物。
＜８＞ 上記マゼンタ色染料は、キナクリドン化合物、キサンテン化合物、トリアリールメタン化合物、シアニン化合物、アントラキノン化合物およびジピロメテン化合物からなる群から選択される少なくとも１種を含む、＜１＞～＜７＞のいずれか１つに記載の着色組成物。
＜９＞ 上記マゼンタ色染料は、カチオン性シアニン発色団とイミドアニオンとの塩を含む、＜１＞～＜７＞のいずれか１つに記載の着色組成物。
＜１０＞ 上記顔料Ａの１００質量部に対して、上記マゼンタ色染料を１～５０質量部含む、＜１＞～＜９＞のいずれか１つに記載の着色組成物。
＜１１＞ 更に、黄色着色剤を含む、＜１＞～＜１０＞のいずれか１つに記載の着色組成物。
＜１２＞ 上記硬化性基を有する化合物は、エチレン性不飽和基を有する化合物を含み、上記着色組成物は更に光重合開始剤を含む、＜１＞～＜１１＞のいずれか１つに記載の着色組成物。
＜１３＞ 上記着色組成物の全固形分中における上記顔料Ａの含有量が４０質量％以上である、＜１＞～＜１２＞のいずれか１つに記載の着色組成物。
＜１４＞ 上記ジケトピロロピロール顔料は、上記顔料Ａを２種以上含む、＜１＞～＜１３＞のいずれか１つに記載の着色組成物。
＜１５＞ 上記ジケトピロロピロール顔料は、更に、上記顔料Ａ以外のジケトピロロピロール顔料を含む、＜１＞～＜１４＞のいずれか１つに記載の着色組成物。
＜１６＞ 固体撮像素子用である、＜１＞～＜１５＞のいずれか１つに記載の着色組成物。
＜１７＞ カラーフィルタ用である、＜１＞～＜１６＞のいずれか１つに記載の着色組成物。
＜１８＞ ＜１＞～＜１７＞のいずれか１つに記載の着色組成物から得られる硬化膜。
＜１９＞ ＜１＞～＜１７＞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またはドライエッチング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、を有するパターン形成方法。
＜２０＞ ＜１８＞に記載の硬化膜を有するカラーフィルタ。
＜２１＞ ＜１８＞に記載の硬化膜を有する固体撮像素子。
＜２２＞ ＜１８＞に記載の硬化膜を有する画像表示装置。As a result of intensive studies, the present inventors have found that the above-described objects can be achieved with the coloring composition described below, and have completed the present invention. Accordingly, the present invention provides the following.
<1> containing a diketopyrrolopyrrole pigment, a magenta dye, and a compound having a curable group,
The diketopyrrolopyrrole pigment is a coloring composition comprising a pigment A having a structure in which an aromatic ring group having an electron-donating group introduced into the aromatic ring is bonded to a diketopyrrolopyrrole skeleton.
<2> The coloring composition according to <1>, wherein the electron-donating group possessed by the pigment A is at least one selected from a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group and an amino group. thing.
<3> The coloring composition according to <1>, wherein the electron-donating group of the pigment A is an alkyl group having 1 to 3 carbon atoms.
<4> The coloring composition according to any one of <1> to <3>, wherein the aromatic ring group possessed by the pigment A is a group represented by the following formula (AR-1);

In the formula, R ¹ represents a substituent, R ² represents an electron-donating group, n represents an integer of 0 to 4, and the wavy line represents a bonding site with the diketopyrrolopyrrole skeleton.
<5> The coloring composition according to any one of <1> to <4>, wherein the pigment A is a compound represented by the following formula (1);

In the formula, R ¹¹ and R ¹² each independently represent a substituent, R ²¹ and R ²² each independently represent an electron-donating group, and n11 and n12 each independently represent an integer of 0 to 4. .
<6> The coloring composition according to any one of <1> to <5>, wherein the pigment A is a compound represented by the following formula (2);

In the formula, R ¹¹ and R ¹² each independently represent a substituent, R ²¹ and R ²² each independently represent an electron-donating group, and n11 and n12 each independently represent an integer of 0 to 4. .
<7> The colored composition according to any one of <1> to <6>, wherein the pigment A is a red pigment.
<8> Any of <1> to <7>, wherein the magenta dye contains at least one selected from the group consisting of quinacridone compounds, xanthene compounds, triarylmethane compounds, cyanine compounds, anthraquinone compounds and dipyrromethene compounds. or the coloring composition according to one.
<9> The colored composition according to any one of <1> to <7>, wherein the magenta dye contains a salt of a cationic cyanine chromophore and an imide anion.
<10> The colored composition according to any one of <1> to <9>, which contains 1 to 50 parts by mass of the magenta dye with respect to 100 parts by mass of the pigment A.
<11> The colored composition according to any one of <1> to <10>, further comprising a yellow colorant.
<12> The compound having a curable group includes a compound having an ethylenically unsaturated group, and the colored composition further includes a photopolymerization initiator, according to any one of <1> to <11> coloring composition.
<13> The coloring composition according to any one of <1> to <12>, wherein the content of the pigment A in the total solid content of the coloring composition is 40% by mass or more.
<14> The coloring composition according to any one of <1> to <13>, wherein the diketopyrrolopyrrole pigment contains two or more of the pigments A.
<15> The coloring composition according to any one of <1> to <14>, wherein the diketopyrrolopyrrole pigment further contains a diketopyrrolopyrrole pigment other than the pigment A.
<16> The colored composition according to any one of <1> to <15>, which is for a solid-state imaging device.
<17> The colored composition according to any one of <1> to <16>, which is used for color filters.
<18> A cured film obtained from the colored composition according to any one of <1> to <17>.
<19> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <17>; and forming a pattern on the pattern.
<20> A color filter having the cured film according to <18>.
<21> A solid-state imaging device comprising the cured film according to <18>.
<22> An image display device comprising the cured film according to <18>.

ADVANTAGE OF THE INVENTION According to this invention, the coloring composition which can form the cured film excellent in heat resistance can be provided. Moreover, the present invention can provide a cured film using the colored composition, a pattern forming method, a color filter, a solid-state imaging device, and an image display device.

The contents of the present invention will be described in detail below.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to acryloyl and/or methacryloyl.
As used herein, the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
As used herein, a pigment means a compound that is difficult to dissolve in a solvent. For example, the pigment preferably has a solubility of less than 0.1 g in 100 g of water at 23° C. and a solubility in 100 g of propylene glycol monomethyl ether acetate at 23° C., more preferably 0.01 g or less.
As used herein, a dye means a compound that is easily soluble in a solvent. For example, the dye preferably has a solubility of 0.1 g or more in 100 g of water at 23° C. or a solubility in 100 g of propylene glycol monomethyl ether acetate at 23° C., more preferably 1 g or more.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .

<Coloring composition>
The coloring composition of the present invention contains a diketopyrrolopyrrole pigment, a magenta dye, and a compound having a curable group, and the diketopyrrolopyrrole pigment has an electron-donating group introduced into an aromatic ring. It is characterized by containing a pigment A having a structure in which an aromatic ring group is bonded to a diketopyrrolopyrrole skeleton.

By using the coloring composition of the present invention, a cured film having excellent heat resistance can be formed. In general, the higher the pigment concentration in the film, the more the heat resistance tends to decrease. A cured film having excellent properties can be formed. Although the detailed mechanism is unknown, by using the pigment A and the magenta dye together, the magenta dye is adsorbed on the surface of the pigment A, which suppresses the crystal growth accompanying heating of the pigment A, resulting in excellent heat resistance. It is presumed that a hardened film can be formed.

In addition, when a red pigment is used as the pigment A, the combined use of the pigment A and a magenta dye can improve the light shielding property of light with a wavelength of about 500 nm (for example, a wavelength of 500 to 550 nm), and the green color It is possible to form a cured film suitable for red pixels having spectral characteristics excellent in color separation from blue and the like. In addition, since Pigment A has a red color value higher than that of conventional red pigments, a cured film having desired spectral characteristics can be formed even if it is a thin film. Pigment A has a structure in which the above aromatic ring group is bonded to a diketopyrrolopyrrole skeleton, so that the HOMO (Highest Occupied Molecular Orbital)-LUMO (Lowest Unoccupied Molecular Orbital) transition is extended to increase the transition moment. As a result, the molar extinction coefficient ε in the red wavelength region (for example, 450 to 600 nm) of Pigment A increased, so it is presumed that the red color value is high. In addition, since Pigment A has a higher red color value than conventional red pigments, the desired spectral properties can be obtained with a blending amount smaller than that required to achieve spectral characteristics equivalent to those of conventional red pigments. Since this can be achieved, the blending amount of components other than the pigment can be increased, and the degree of freedom in prescription design is high.

The coloring composition of the present invention can be preferably used as a coloring composition for solid-state imaging devices. Moreover, the coloring composition of this invention can be preferably used as a coloring composition for color filters. Specifically, it can be preferably used as a coloring composition for forming pixels of a color filter, and more preferably used as a coloring composition for forming red pixels. Moreover, the coloring composition of the present invention can be more preferably used as a coloring composition for pixel formation of color filters used in solid-state imaging devices.

When the colored composition of the present invention has a film thickness of 0.5 to 1.0 μm after drying, at least one of the above film thicknesses has a transmittance of light with a wavelength of 650 to 700 nm. It is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. In at least one of the film thicknesses described above, the transmittance of light having a wavelength of 400 to 550 nm is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less. .

Each component used in the coloring composition of the present invention is described below.

<<Diketopyrrolopyrrole pigment>>
The coloring composition of the present invention contains a diketopyrrolopyrrole pigment. The diketopyrrolopyrrole pigment used in the coloring composition of the present invention is preferably a red pigment. In addition, the diketopyrrolopyrrole pigment preferably has a solubility in 100 g of water at 23° C. and a solubility in 100 g of propylene glycol monomethyl ether acetate at 23° C. of less than 0.1 g, more preferably 0.01 g or less. preferable.

(Pigment A)
The coloring composition of the present invention is, as a diketopyrrolopyrrole pigment, a pigment A having a structure in which an aromatic ring group having an electron-donating group introduced into the aromatic ring is bonded to a diketopyrrolopyrrole skeleton (hereinafter, pigment A ).

An electron-donating group is an atomic group that donates electrons to a substituted atomic group by an inductive effect or a resonance effect in the theory of organic electrons. Examples of the electron-donating group include those having a negative Hammett's rule substituent constant (σp (para)). Hammett's rule substituent constant (σp (para)) can be quoted from Kagaku Handan Basic Edition 5th Revised Edition (page II-380). Specific examples of electron donating groups include hydroxy groups, alkyl groups, alkoxy groups, alkylthio groups, aryloxy groups and amino groups.
The number of carbon atoms in the alkyl group, alkoxy group and alkylthio group is preferably 1-10, more preferably 1-5, even more preferably 1-3. These groups may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
The aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
The amino group includes groups represented by —NRa ¹ Ra ² . Ra ¹ and Ra ² each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Ra ¹ and Ra ² may combine to form a ring. The number of carbon atoms in the alkyl group represented by Ra ¹ and Ra ² is preferably 1-30, more preferably 1-15, even more preferably 1-8. The alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear. The aryl group represented by Ra ¹ and Ra ² preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The heterocyclic group represented by Ra ¹ and Ra ² may be monocyclic or condensed. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3. A heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12.

As the electron-donating group, an alkyl group, an alkoxy group, and an amino group are preferable because the effects of the present invention can be obtained more remarkably. Alkyl groups and alkoxy groups are more preferable, alkyl groups are still more preferable, and alkyl groups having 1 to 3 carbon atoms are particularly preferable because they are easy to use.

式中、Ｒ^１は置換基を表し、Ｒ^２は電子供与性基を表し、ｎは０～４の整数を表し、波線はジケトピロロピロール骨格との結合部位を表す。The aromatic ring group is preferably a group represented by formula (AR-1).

In the formula, R ¹ represents a substituent, R ² represents an electron-donating group, n represents an integer of 0 to 4, and the wavy line represents a bonding site with the diketopyrrolopyrrole skeleton.

In formula (AR-1), the substituent represented by R ¹ includes the groups exemplified for the substituent T described later and the electron-donating groups described above, and is preferably an electron-donating group. When n is 2 or more, n R ^1s may be the same or different.

In formula (AR-1), the electron-donating group represented by R ² includes the electron-donating groups described above, and the preferred range is also the same.

In formula (AR-1), n represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1 , 1 is particularly preferred.

In formula (AR-1), the wavy line represents the binding site with the diketopyrrolopyrrole skeleton. The diketopyrrolopyrrole skeleton means the following structure. A wavy line represents a bonding position with a substituent such as the group represented by formula (AR-1). Substituents other than the group represented by formula (AR-1) include an aryl group and the like. The aryl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.

Pigment A is preferably a compound represented by the following formula (1), and more preferably a compound represented by the following formula (2), since more excellent heat resistance can be easily obtained.

In the above formula, R ¹¹ and R ¹² each independently represent a substituent,
R ²¹ and R ²² each independently represent an electron-donating group;
n11 and n12 each independently represents an integer of 0 to 4;

Substituents represented by R ¹¹ and R ¹² include the groups exemplified for the substituent T described later and the electron-donating groups described above, and are preferably electron-donating groups. When n11 is 2 or more, n11 R ¹¹ may be the same or different. When n12 is 2 or more, n12 R ¹² may be the same or different.

The electron-donating groups represented by R ²¹ and R ²² include the electron-donating groups described above, and the preferred ranges are also the same.

n11 and n12 each independently represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, more preferably 0 or 1, 1 is particularly preferred.

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

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

Specific examples of Pigment A include compounds having the following structures.

The diketopyrrolopyrrole pigment used in the coloring composition of the present invention may contain only one type of pigment A, or may contain two or more types. When only one type of pigment A is contained, it is easy to form a cured film with little color unevenness. When two or more pigments A are contained, it is easy to adjust the spectral characteristics of the cured film.

Pigment A used in the present invention is preferably a red pigment. Combined use of Pigment A, which is a red pigment, and a magenta color dye, forms a cured film suitable for red pixels having excellent heat resistance and spectral characteristics with excellent color separation from green, blue, etc. can do.

(other diketopyrrolopyrrole pigments)
The coloring composition of the present invention can contain diketopyrrolopyrrole pigments other than pigment A (hereinafter also referred to as other diketopyrrolopyrrole pigments). The other diketopyrrolopyrrole pigment is preferably a red pigment. Other diketopyrrolopyrrole pigments include compounds represented by the following formula (10).

In the formula, R ³¹ and R ³² each independently represent a hydrogen atom, a halogen atom or a phenyl group. Halogen atoms represented by R ³¹ and R ³² include fluorine, chlorine and bromine atoms.

Further, as other diketopyrrolopyrrole pigments, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838. diketopyrrolopyrrole compounds, diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, and the like can also be used.

Specific examples of other diketopyrrolopyrrole pigments include the following compounds.

The content of pigment A is preferably 35% by mass or more in the total solid content of the coloring composition, more preferably 40% by mass or more, more preferably 45% by mass or more, 50% by mass The above is even more preferable. The upper limit can be 80% by mass or less.

The diketopyrrolopyrrole pigment contained in the coloring composition may be substantially only pigment A, or may further contain other diketopyrrolopyrrole pigments. When the diketopyrrolopyrrole pigment is substantially only the pigment A, it is easy to form a cured film with little color unevenness. Incidentally, the case where the diketopyrrolopyrrole pigment is substantially only the pigment A means that the proportion of the pigment A in the total weight of the diketopyrrolopyrrole pigment contained in the coloring composition is 99% by mass or more. The content is preferably 99.5% by mass or more, more preferably 99.9% by mass or more, and particularly preferably composed of Pigment A only. Further, when the diketopyrrolopyrrole pigment further contains other diketopyrrolopyrrole pigment in addition to Pigment A, it is easy to adjust the spectral properties of the cured film. When Pigment A and another diketopyrrolopyrrole pigment are used in combination, the content of the other diketopyrrolopyrrole pigment is preferably 0.1 to 50 parts by weight per 100 parts by weight of Pigment A. , more preferably 1 to 35 parts by mass, more preferably 5 to 20 parts by mass.

The content of the diketopyrrolopyrrole pigment (the total amount thereof if other diketopyrrolopyrrole pigments are included in addition to pigment A) is preferably 25% by mass or more in the total solid content of the coloring composition, It is more preferably 30% by mass or more, still more preferably 35% by mass or more, and even more preferably 40% by mass or more. The upper limit can be 80% by mass or less.

<<Magenta dye>>
The coloring composition of the present invention contains a magenta dye. Here, in this specification, the magenta color is a complementary hue of green. Complementary colors are a combination of colors that are opposite to each other on the color circle. A magenta dye is a dye that exhibits a magenta hue.

Examples of the magenta dye used in the present invention include dyes that have a high absorbance of green wavelength light and low absorbance of red and blue wavelength light, and have a light absorbance in the wavelength range of 500 to 550 nm. It is preferable that the dye has a high absorbance of light in the wavelength range of 400 to 480 nm and a low absorbance of light in the wavelength range of 600 to 700 nm.

The magenta dye used in the present invention preferably has a Δλ represented by the following formula (1) of 150 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less.

Δλ=λ2−λ1 (1)
In the formula, λ1 is a wavelength shorter than the maximum absorption wavelength at which the absorbance is 0.5 when the absorbance at the maximum absorption wavelength of the magenta dye is 1, and λ2 is the maximum absorption wavelength of the magenta dye. is a wavelength on the longer wavelength side than the maximum absorption wavelength at which the absorbance is 0.5 when the absorbance of is 1.

The maximum absorption wavelength of the magenta dye is preferably in the wavelength range of 450 to 600 nm, more preferably in the range of 475 to 575 nm, even more preferably in the range of 500 to 550 nm.

The magenta dye used in the present invention has a ratio (A1/A2) of the maximum light absorbance value A1 in the wavelength range of 400 to 480 nm and the light absorbance minimum value A2 in the wavelength range of 500 to 550 nm to 0. 0.2 to 0.8, more preferably 0.3 to 0.7, even more preferably 0.4 to 0.6. In addition, the magenta dye has a ratio (A3/A2) of the maximum absorbance A3 of light in the wavelength range of 600 to 700 nm and the minimum absorbance A2 of light in the wavelength range of 500 to 550 nm (A3/A2) of 0.3 or less. is preferably 0.2 or less, and even more preferably 0.1 or less. In addition, the magenta dye has a ratio (A3/A1) of the maximum absorbance A3 of light in the wavelength range of 600 to 700 nm and the maximum absorbance of light in the wavelength range of 400 to 480 nm (A3/A1) of 0.1 or less. It is preferably 0.03 or less, and even more preferably 0.02 or less.

The magenta dye used in the present invention has a ratio of the absorbance A ₄₄₀ of light at a wavelength of 440 nm to the absorbance A ₅₂₅ of light at a wavelength of 525 nm (A ₄₄₀ /A ₅₂₅ ) of 0.001 to 0.15. It is preferably 0.005 to 0.10, even more preferably 0.01 to 0.05. In addition, the magenta dye preferably has a ratio of the absorbance A ₆₅₀ of light at a wavelength of 650 nm to the absorbance A ₅₂₅ of light at a wavelength of 525 nm (A ₆₅₀ /A ₅₂₅ ) of 0.2 or less, and 0.1 or less. is more preferably 0.05 or less. In addition, the magenta dye preferably has a ratio (A ₆₅₀ /A 440 ) between the absorbance A 650 of light at a wavelength of 650 nm and the absorbance A ₄₄₀ of light at a wavelength of 440 nm (A ₆₅₀ /A ₄₄₀ ) of 0.1 or less, and 0.03 or less. It is more preferably 0.02 or less.

The absorbance and maximum absorption wavelength of the magenta dye are measured by forming a film using a composition containing the magenta dye and a resin, and measuring the spectral characteristics of the film using a spectrophotometer. It can be dissolved to prepare a dye solution, and the spectral properties of the dye solution can be measured using a spectrophotometer.

The magenta dye used in the present invention preferably has a solubility in 100 g of water at 23° C. or a solubility in 100 g of propylene glycol monomethyl ether acetate at 23° C. of 0.1 g or more, more preferably 1 g or more. preferable.

The magenta dye used in the present invention preferably contains at least one selected from the group consisting of quinacridone compounds, xanthene compounds, triarylmethane compounds, cyanine compounds, anthraquinone compounds and dipyrromethene compounds, and xanthene compounds and cyanine compounds. It is more preferable to contain at least one selected from the group consisting of, and it is still more preferable to contain a cyanine compound. Moreover, the cyanine compound is preferably a salt of a cationic cyanine chromophore and a counter anion.

(Cationic cyanine chromophore)
Cationic cyanine chromophores include structures represented by the following formula (Cy1).

In formula (Cy1), R ^c1 to R ^c3 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group, ring Z ¹ and ring Z ² each independently represent a heterocyclic ring, and p is , 1 or 2. However, when p is 2, a plurality of R ^c1 and R ^c2 may be the same or different.

The heterocyclic ring represented by ring Z ¹ and ring Z ² may be a monocyclic ring or a condensed ring. A heterocyclic ring may be an unsaturated ring or a saturated ring. In addition, the condensed ring may have two or more heteroatoms of the same or different type (eg, nitrogen atom, oxygen atom, sulfur atom) in the ring. Specific examples of the heterocycle include nitrogen-containing alicyclic heterocycles such as pyrrolidine ring, pyrazoline ring, morpholine ring, thiomorpholine ring, piperidine ring, piperazine ring, homopiperazine ring, and tetrahydropyrimidine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinoxaline ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, benzothiazole ring, oxazole ring, indole ring, indazole ring, benzimidazole ring, Examples include nitrogen-containing aromatic heterocycles such as benzoxazole and phthalimide rings, and other aromatic heterocycles such as thienyl rings, furan rings, and purine rings. Among them, a nitrogen-containing aromatic heterocyclic ring is preferred, an indole ring, a benzoxazole ring, and a benzothiazole ring are more preferred, and an indole ring is even more preferred.

p represents 1 or 2, preferably 1;

Halogen atoms represented by R ^c1 to R ^c3 include fluorine, chlorine, bromine and iodine atoms.
Examples of hydrocarbon groups represented by R ^c1 to R ^c3 include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. Here, the term "alicyclic hydrocarbon group" as used herein is a concept excluding aliphatic hydrocarbon groups that do not have a cyclic structure.

The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include linear or branched alkyl groups, alkenyl groups and alkynyl groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, still more preferably 1-12. Specific examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hexyl, heptyl and octyl groups. group, nonyl group, decyl group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group , hexadecyl group, octadecyl group and the like. Specific examples of linear or branched alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1,3-butadienyl, 1-pentenyl, 2- pentenyl group, 1-hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl)-5-hexenyl group, 2-decenyl group and the like. Further, specific examples of linear or branched alkynyl groups include ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl and 2-ethyl-2-butynyl. group, 2-octynyl group, (4-ethynyl)-5-hexynyl group, 2-decynyl group and the like.

Examples of alicyclic hydrocarbon groups include cyclic alkyl groups (cycloalkyl groups), cyclic alkenyl groups (cycloalkenyl groups), condensed polycyclic hydrocarbon groups, bridged ring hydrocarbon groups, spiro hydrocarbon groups, A cyclic terpene hydrocarbon group and the like can be mentioned. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3-30, more preferably 3-20, still more preferably 3-12. Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, t-butylcyclohexyl, cycloheptyl, and cyclooctyl groups. Specific examples of cycloalkenyl groups include 1 -cyclohexenyl group and the like. Specific examples of condensed polycyclic hydrocarbon groups include tricyclodecanyl, decahydro-2-naphthyl, and adamantyl groups. Specific examples of the bridged ring hydrocarbon group include tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, pentacyclopentadecanyl group, isobornyl group, dicyclopentenyl group, tricyclopentenyl and the like. Specific examples of spirohydrocarbon groups include monovalent groups obtained by removing one hydrogen atom from spiro[3,4]heptane and spiro[3,4]octane. Specific examples of the cyclic terpene hydrocarbon group include monovalent groups obtained by removing one hydrogen atom from p-menthane, thujan, karane, and the like.

Examples of aromatic hydrocarbon groups include aryl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-20, more preferably 6-14, still more preferably 6-10.

R ^c1 to R ^c3 are preferably hydrogen atoms.

The heterocycle represented by ring Z ¹ and ring Z ² and the hydrocarbon group represented by R ^c1 to R ^c3 may have a substituent. Substituents include halogen atoms, hydroxy groups, cyano groups, formyl groups, carboxyl groups, nitro groups, amino groups, dialkylamino groups, diarylamino groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, alkylthio groups, and arylthio groups. , a trialkylsilyl group, a mercapto group, an allyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an aliphatic hydrocarbon group, a heterocyclic group, an aromatic hydrocarbon group and an organic group having a crosslinkable group. These substituents may further have a substituent.

The organic group having a crosslinkable group indicates a group composed of an atomic group that includes a crosslinkable group, includes a carbon atom-hydrogen atom bond as a whole, and optionally includes an atom other than carbon. Specific examples include groups represented by the following formula (P-1).
−L ^p1 −R ^p1 (P−1)
In the formula, L ^p1 represents a single bond or a linking group, and R ^p1 represents a crosslinkable group. The linking group represented by L ^p1 includes an alkylene group, an arylene group, -O-, -CO-, -NH-, -COO-, -OCO-, -CONH-, -NHCO-, and a group formed by combining these. mentioned. Examples of the crosslinkable group represented by R ^p1 include a (meth)acryloyl group, vinyl group, epoxy group, and isocyanate group.

The structure represented by formula (Cy1) is preferably a structure represented by formula (Cy2) below.

In formula (Cy2), R ^c1 to R ^c3 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group, and Ring Z ^1A and Ring Z ^2A each independently represent an aromatic hydrocarbon ring. , T ¹ and T ² each independently represent —O—, —S— or —CR ^c6 R ^c7 —, and R ^c4 to R ^c7 each independently represent a hydrocarbon group.

The aromatic hydrocarbon ring represented by ring Z ^1A and ring Z ^2A is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and particularly a benzene ring. preferable.

R ^c1 to R ^c3 in formula (Cy2) have the same meanings as R ^c1 to R ^c3 in formula (Cy1), and the preferred ranges are also the same.

T ¹ and T ² in formula (Cy2) are preferably -O- and -CR ^c6 R ^c7 -. The hydrocarbon group represented by R ^c6 and R ^c7 is preferably an aliphatic hydrocarbon group, more preferably a straight-chain or branched alkyl group, more preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms. A linear or branched alkyl group having numbers 1 to 4 is more preferred, and a methyl group or an ethyl group is particularly preferred.

The hydrocarbon groups represented by R ^c4 and R ^c5 include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. Specific examples are the same as those exemplified as the hydrocarbon groups represented by R ^c1 to R ^c3 . Among them, the hydrocarbon group represented by R ^c4 and R ^c5 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, and still more preferably a linear or branched alkyl group having 1 to 12 carbon atoms. , a straight or branched alkyl group having 1 to 8 carbon atoms is more preferred, and a straight or branched alkyl group having 1 to 6 carbon atoms is particularly preferred.

The aromatic hydrocarbon ring represented by ring Z ^1A and ring Z ^2A and the hydrocarbon group represented by R ^c4 to R ^c5 may have a substituent. Substituents include the substituents described above.

Specific examples of the cationic cyanine chromophore include chromophores having structures shown in the examples below, chromophores having structures described in paragraphs 0030 to 0033 of JP-A-2017-066377, and JP-A-2015-232642. Examples thereof include chromophores having structures described in paragraphs 0038 to 0047 of the publication.

(counter anion)
Examples of counter anions include halide anions (fluorine anion, chloride anion, bromine anion, iodine anion, etc.), perhalate anions (ClO ₄ ⁻ , FO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ^{− ,} etc.), thiocyanate anions ( SCN- ^, etc.), sulfate anions, heteropolyacids, carboxylate anions, sulfonate anions, fatty acid anions, fluorine group-containing boron anions, fluorine group-containing phosphorus anions, imide anions, methide anions, resins having anionic groups in side chains, etc. mentioned. Specific examples include the anions described in paragraph numbers 0048 to 0144 of JP-A-2015-232642 and paragraph numbers 0034-0063 of JP-A-2017-066377. Of these, resins and imide anions having an anionic group on the side chain are preferred, and imide anions are more preferred, because they facilitate the formation of a cured film having superior heat resistance. That is, the magenta dye used in the present invention is a salt of a cationic cyanine chromophore and an imide anion, and a cationic cyanine chromophore and an anion because it is easy to obtain a cured film having better heat resistance. It is preferably a salt with a resin having a functional group on its side chain, more preferably a salt with a cationic cyanine chromophore and an imide anion.

[Imide anion]
The imide anion includes an anion represented by formula (AN-1) and an anion represented by formula (AN-2), preferably an anion represented by formula (AN-2). .

式（ＡＮ－１）中、Ｘ^１およびＸ^２は、それぞれ独立に、ハロゲン原子、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、または複素環基を表す。Ｘ^１とＸ^２は結合して環を形成していてもよい。Formula (AN-1)

In formula (AN-1), X ¹ and X ² each independently represent a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group. X ¹ and X ² may combine to form a ring.

Halogen atoms represented by X ¹ and X ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.

Aliphatic hydrocarbon groups represented by X ¹ and X ² include linear or branched alkyl groups, alkenyl groups and alkynyl groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, still more preferably 1-12. Specific examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, and pentadecyl. group, hexadecyl group, octadecyl group, nonadecyl group, pentadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group and the like.

Alicyclic hydrocarbon groups represented by X ¹ and X ² include cyclic alkyl groups (cycloalkyl groups), cyclic alkenyl groups (cycloalkenyl groups), condensed polycyclic hydrocarbon groups, bridged cyclic hydrocarbon groups, A spiro hydrocarbon group, a cyclic terpene hydrocarbon group, and the like can be mentioned. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 3-30, more preferably 3-20, still more preferably 3-12. Specific examples of alicyclic hydrocarbon groups include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl groups.
An aryl group etc. can be mentioned as an aromatic-hydrocarbon group which ^X1 and ^X2 represent. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-20, more preferably 6-14, still more preferably 6-10. Specific examples of the aromatic hydrocarbon group include phenyl group, biphenylyl group, naphthyl group and the like.

The heterocyclic group represented by X ¹ and X ² may be monocyclic or condensed. A heterocyclic ring may be an unsaturated ring or a saturated ring. In addition, the condensed ring may have two or more heteroatoms of the same or different type (eg, nitrogen atom, oxygen atom, sulfur atom) in the ring. Specific examples of heterocyclic rings include indole ring group, benzindole ring group, indolenine ring group, benzindolenine ring group, oxazole ring group, benzoxazole ring group, thiazole ring group, benzothiazole ring group, and benzimidazole ring group. , a quinoline ring group, and the like.

The aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group represented by X ¹ and X ² may have a substituent. Substituents include aliphatic groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and tert-pentyl group. Hydrocarbon group; crosslinkable group such as (meth)acryloyl group, vinylaryl group, vinyloxy group, allyl group, epoxy group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl aromatic hydrocarbon groups such as groups, o-cumenyl groups, m-cumenyl groups, and p-cumenyl groups; methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, isobutoxy groups, sec-butoxy groups, tert- Alkoxy groups such as butoxy group and pentyloxy group; Aryloxy groups such as phenoxy group; Aralkyloxy groups such as benzyloxy group; Ester bonds such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group group; methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl alkylsulfamoyl groups such as diisopropylsulfamoyl group, n-butylsulfamoyl group and di-n-butylsulfamoyl group; -alkylsulfonyl groups such as butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group and tert-butylsulfonyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group and cyano group. .

In formula (AN-1), X ¹ is an optionally substituted aliphatic hydrocarbon group, an optionally substituted alicyclic hydrocarbon group, or an optionally substituted aromatic is preferably a group hydrocarbon group. Moreover, ^X2 is preferably an aromatic hydrocarbon group optionally having a substituent or a heterocyclic group optionally having a substituent.

X ¹ in formula (AN-1) is preferably a fluorine atom-substituted alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and a fluorine atom-substituted alkyl group having 1 to 20 carbon atoms is preferable. More preferably, a trifluoromethyl group is particularly preferred. X ² in formula (AN-1) is preferably an aromatic hydrocarbon group substituted with a fluorine atom, more preferably a p-fluorophenyl group or a pentafluorophenyl group.

Specific examples of the anion represented by formula (AN-1) include anions having structures described in paragraphs 0074 to 0077 of JP-A-2015-232642.

Formula (AN-2)

In formula (AN-2), Y ¹ represents a group having a polymerizable group.
Y ² represents a halogen atom, a halogenated hydrocarbon group, or a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom, a halogen-substituted alkylene group, an alkyl group, or an alicyclic carbonization It represents a group formed by combining a monovalent group selected from a hydrogen group, a heteroaryl group and an aryl group.

The halogen atom represented by ^Y2 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group represented by Y ² include (1) an aliphatic hydrocarbon group, (2) an alicyclic hydrocarbon group, and (3) an alicyclic carbonization group as a substituent. an aliphatic hydrocarbon group having a hydrogen group (hereinafter referred to as an "alicyclic hydrocarbon-substituted aliphatic hydrocarbon group"), (4) an aromatic hydrocarbon group, and (5) an aliphatic hydrocarbon group as a substituent (6) an aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as an "aromatic hydrocarbon group"); (referred to as "hydrogen-substituted aliphatic hydrocarbon group") and the like. From the viewpoint of solubility in organic solvents, the hydrocarbon group forming the skeleton of ^Y2 is preferably the following characteristic group. That is, the (1) aliphatic hydrocarbon group is preferably an alkyl group, and preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. The (2) alicyclic hydrocarbon group may be a 2- to 4-ring bridged alicyclic hydrocarbon group. As the alicyclic hydrocarbon group, an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms is preferable. The (3) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the total carbon number thereof is preferably 4 to 20, particularly 6 to 14. is preferably The (4) aromatic hydrocarbon group is preferably an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and more preferably a phenyl group. As the (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group, an alkyl-substituted phenyl group is preferable, and the total number of carbon atoms thereof is preferably 7-30, particularly preferably 7-20. Specific examples include a tolyl group, a xylyl group, and a mesityl group. The (6) aromatic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an aralkyl group, and the total number of carbon atoms is preferably 7-30, more preferably 7-20. Among these, the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group includes (1) an aliphatic hydrocarbon group, (3) an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, and (4) an aromatic hydrocarbon group. (5) an aliphatic hydrocarbon-substituted aromatic hydrocarbon group or (6) an aromatic hydrocarbon-substituted aliphatic hydrocarbon group, an alkyl group, an alicyclic saturated hydrocarbon-substituted alkyl group, a phenyl group, an alkyl-substituted A phenyl group and an aralkyl group are more preferable, and an alkyl group is particularly preferable. Further, in Y ² , the halogen atom in the halogenated hydrocarbon group is preferably a fluorine atom from the viewpoint of the heat resistance of the magenta dye. That is, the halogenated hydrocarbon group is preferably one in which some or all of the hydrogen atoms in the hydrocarbon group are substituted with fluorine atoms.

Y ² in formula (AN-2) is a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom, a halogen-substituted alkylene group, an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group and a substituted or It may be a group combined with a monovalent group selected from unsubstituted aryl groups. The linking group containing an atom other than a carbon atom, a hydrogen atom and a halogen atom includes -O-, -S-, -CO-, -COO-, -CONH-, -SO ₂ - and the like. Further, examples of the halogen-substituted alkylene group include groups in which some or all of the hydrogen atoms of an alkylene group have been substituted with halogen atoms. The number of carbon atoms in the alkylene group is preferably 1-10. From the viewpoint of heat resistance, a fluorine atom is preferred as the type of halogen atom to be substituted on the alkylene group. The number of carbon atoms in the aforementioned alkyl group is preferably 1-20, more preferably 1-8. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3-20, more preferably 3-12. The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocyclic ring containing at least one heteroatom selected from nitrogen, oxygen and sulfur atoms. Specific examples include furyl group, thienyl group, pyrrolyl group, oxazolyl group, pyridyl group, quinolinyl group, carbazolyl group and the like. As the aryl group, an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, is preferred, and a phenyl group and a naphthyl group are particularly preferred. Examples of substituents of the aryl group include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, halogen atoms and trifluoromethyl groups. The position and number of substituents are arbitrary, and when two or more substituents are present, these substituents may be the same or different.

From the viewpoint of heat resistance, Y ² in formula (AN-2) is a halogenated hydrocarbon group or a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom, a halogen-substituted alkylene group, an alkyl group, A group formed by combining a monovalent group selected from an alicyclic hydrocarbon group, a heteroaryl group and a substituted or unsubstituted aryl group is preferred, and is represented by the following formula (Y2-1) or (Y2-2) is more preferred, and a group represented by the following formula (Y2-1) is even more preferred.

In formula (Y2-1), R ^y1 is a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ^y20 COOR ^y21 - or R ^y22 COOR represents ^y23 CFH-,
R ^y20 and R ^y22 each independently represent an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group;
R ^y21 and R ^y23 each independently represent an alkylene group,
n represents an integer of 1 or more,
* represents a bond.

In formula (Y2-2), R ^y2 to R ^y6 each independently represent a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group, a fluorinated alkyl group or an alkoxy group, and * represents a bond. At least one of R ^y2 to R ^y6 is a fluorine atom or a fluorinated alkyl group.

Y ¹ in formula (AN-2) represents a group having a polymerizable group. The group having a polymerizable group represented by Y ¹ is preferably a group represented by formula (Y1-1).
Q ¹ -L ¹ -* (Y1-1)

In formula (Y1-1), L ¹ represents a single bond or a divalent linking group, Q ¹ represents a polymerizable group, and * represents a bond.

_The divalent linking group represented by L ^{1 includes} a divalent hydrocarbon group; and groups selected from -, -OCO-, -CONR ^a -, -NR ^a CO- and -S-. R ^a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of divalent hydrocarbon groups include alkylene groups and arylene groups. At least part of the hydrogen atoms in the divalent hydrocarbon group may be substituted with halogen atoms (preferably fluorine atoms).
The divalent linking group represented by L ¹ is an alkylene group having 1 to 10 carbon atoms; an arylene group having 6 to 20 carbon atoms; an arylene alkylene group having 7 to 20 carbon atoms; an alkylene group having 1 to 10 carbon atoms and a carbon number. A group formed by combining at least one selected from 6 to 20 arylene groups with at least one selected from -O-, -S-, -COO-, -CONR ^a - and -SO ₂ - is preferred.

The polymerizable group represented by Q ¹ includes an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include vinyl group, allyl group, methallyl group, (meth)acryloyl group and styrene group, preferably (meth)acryloyl group and styrene group, more preferably (meth)acryloyl group.

The group having a polymerizable group represented by Y ¹ of formula (AN-2) is preferably a group represented by formula (Y1-2) from the viewpoint of heat resistance.
Q ¹ -L ² -SO ₂ -* (Y1-2)

In formula (Y1-2), ^L2 represents a single bond or a divalent linking group, ^Q1 represents a polymerizable group, and * represents a bond.

Q ¹ in formula (Y1-2) has the same meaning as Q ¹ in formula (Y1-1), and the preferred range is also the same.

The divalent linking group represented by L ² includes a divalent hydrocarbon group; a divalent hydrocarbon group and -NR ^a -, -SO-, -SO ₂ -, -CO-, -O-, -COO and groups selected from -, -OCO-, -CONR ^a -, -NR ^a CO- and -S-. The divalent linking group represented by L ² is selected from an alkylene group having 1 to 10 carbon atoms; an arylene group having 6 to 20 carbon atoms; an alkylene group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms. A group formed by combining at least one and -O- is preferred.

Specific examples of the anion represented by the formula (AN-2) include anions having structures described in Examples described later, anions described in paragraph No. 0142 of JP-A-2017-066377, and the like.

[Resin having an anionic group in a side chain]
Examples of the resin having an anionic group in its side chain include resins having a repeating unit represented by the following formula (AN-10).
Formula (AN-10)

In formula (AN-10), R ¹⁰⁰ represents a hydrogen atom or an alkyl group. L ¹⁰ represents an alkylene group, an arylene group, -CONH-R ¹⁰¹ -, or -COO-R ¹⁰¹ -, and R ¹⁰¹ represents an alkylene group. ^P10 represents an anionic group.

The number of carbon atoms in the alkyl group represented by R ¹⁰⁰ is preferably 1-12, more preferably 1-8, even more preferably 1-4. The alkyl group is preferably a straight chain alkyl group. The alkyl group represented by R ¹⁰⁰ may have a substituent. A hydroxy group, an alkoxy group, etc. are mentioned as a substituent. R ¹⁰⁰ is preferably a hydrogen atom or a methyl group.

Examples of the anionic group represented by P ¹⁰ include -SO ₃ ^- and -COO ^- , with -SO ₃ ^- being preferred.

L ¹⁰ is preferably -CONH-R ¹⁰¹ -, -COO-R ¹⁰¹ -, more preferably -COO-R ¹⁰¹ -.

The resin having an anionic group in its side chain may contain other repeating units in addition to the repeating unit represented by formula (AN-10). Other repeating units include repeating units having a polymerizable group.

The weight average molecular weight of the resin having an anionic group in its side chain is preferably 1,000 to 500,000, more preferably 3,000 to 15,000. Details of the resin having an anionic group in its side chain are described in paragraphs 0101 to 0144 of JP-A-2015-232642, the contents of which are incorporated herein.

The coloring composition of the present invention preferably contains 1 to 50 parts by mass of magenta dye per 100 parts by mass of Pigment A. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. If the content of the magenta dye is within the above range, more excellent heat resistance can be easily obtained.

Also, the content of the magenta dye is preferably 0.4 to 30% by mass based on the total solid content of the coloring composition. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.

Further, the total content of the pigment A and the magenta color dye is preferably 30 to 85% by mass based on the total solid content of the coloring composition. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. The lower limit is preferably 35% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more.

<<Other colorants>>
The coloring composition of the present invention can contain coloring agents other than the diketopyrrolopyrrole pigment and the magenta dye (hereinafter also referred to as other coloring agents). Other colorants may be pigments or dyes. A pigment and a dye may be used in combination. Other colorants used in the present invention preferably contain pigments. Also, the pigment may be an organic pigment or an inorganic pigment. As the pigment, an inorganic pigment or a material obtained by partially replacing an organic-inorganic pigment with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.
The content of the pigment in the other colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. is particularly preferred. Also, the other coloring agent may be only a pigment.

The coloring composition of the present invention preferably contains a yellow coloring agent as another coloring agent, and more preferably contains a yellow pigment. According to this aspect, it is easy to form a cured film having spectral characteristics suitable for red pixels. Moreover, when a yellow pigment is used as another colorant, the dispersibility of the pigment A can be improved.

Examples of yellow colorants include azo compounds, quinophthalone compounds, isoindolinone compounds, isoindoline compounds and anthraquinone compounds. Preferred are isoindoline compounds, azo compounds and quinophthalone compounds, more preferred are isoindoline compounds and azo compounds. An isoindoline compound is particularly preferred because it facilitates the formation of a cured film having spectral characteristics more suitable for red.

Yellow colorants include Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232 (methine), 233 ( quinoline) and other yellow pigments.

Further, as a yellow colorant, compounds described in JP-A-2017-201003, compounds described in JP-A-2017-197719, paragraph numbers 0011 to 0062, 0137 of JP-A-2017-171912 Compounds described in ~ 0276, compounds described in paragraph numbers 0010 to 0062, 0138 to 0295 of JP-A-2017-171913, paragraph numbers 0011-0062, 0139-0190 of JP-A-2017-171914 Compounds described in JP 2017-171915, paragraphs 0010 to 0065, 0142 to 0222, compounds described in JP 2013-054339, paragraphs 0011 to 0034, quinophthalones Compounds, quinophthalone compounds described in paragraph numbers 0013 to 0058 of JP-A-2014-026228, isoindoline compounds described in JP-A-2018-062644, described in JP-A-2018-203798 A quinophthalone compound, a quinophthalone compound described in JP-A-2018-062578, a quinophthalone compound described in JP-A-6432077, a quinophthalone compound described in JP-A-2018-155881. A quinophthalone compound described in JP-A-2018-111757, a quinophthalone compound described in JP-A-2018-040835, and a quinophthalone compound described in JP-A-2017-197640. A quinophthalone compound, a quinophthalone compound described in JP-A-2016-145282, a quinophthalone compound described in JP-A-2014-085565, a quinophthalone compound described in JP-A-2014-021139, Quinophthalone compounds described in JP-A-2013-209614, quinophthalone compounds described in JP-A-2013-209435, quinophthalone compounds described in JP-A-2013-181015, JP-A-2013-061622 A quinophthalone compound described in JP-A-2013-054339, a quinophthalone compound described in JP-A-2013-032486, a quinophthalone compound described in JP-A-2012-226110. A quinophthalone compound described in JP-A-2008-074987, a quinophthalone compound described in JP-A-2008-081565, a quinophthalone compound described in JP-A-2008-074986, Quinophthalone compounds described in JP-A-2008-074985, quinophthalone compounds described in JP-A-2008-050420, quinophthalone compounds described in JP-A-2008-031281, JP-B-48-032765 A quinophthalone compound described in JP-A-2019-008014, a quinophthalone compound described in JP-A-2019-008014, and a compound represented by the following formula (QP1) can also be used.

In formula (QP1), X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom, and Z ¹ represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by formula (QP1) include compounds described in paragraph number 0016 of Japanese Patent No. 6443711 .

As a yellow colorant, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150 and C.I. I. Pigment Yellow 185, more preferably one or more selected from C.I. I. Pigment Yellow 139 and C.I. I. Pigment Yellow 150, more preferably one or more selected from C.I. I. Pigment Yellow 139 is particularly preferred.

Colorants other than the yellow colorant include the following.

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. ,
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc.,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane), 61 (xanthene), etc.
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 (monoazo), 88 (methine/polymethine system), etc.
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, 270, 279, 294 (Xanthene, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type) and the like.

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. can also be used. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green pigment, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, and the phthalocyanine compound described in JP 2019-008014. A phthalocyanine compound and a phthalocyanine compound described in JP-A-2018-180023 can be used.

Also, an aluminum phthalocyanine compound having a phosphorus atom can be used as the blue pigment. Specific examples include compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

Dyes other than the magenta dye are not particularly limited, and known dyes can be used. pyrazole azo compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, xanthene compounds, phthalocyanine compounds , benzopyran compounds, indigo compounds, and pyrromethene compounds.

Further, as other colorants, thiazole compounds described in JP-A-2012-158649, azo compounds described in JP-A-2011-184493, and azo compounds described in JP-A-2011-145540 can also be used. can.

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

The content of other colorants is preferably 40 parts by mass or less with respect to 100 parts by mass of Pigment A. The lower limit is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.
Also, the content of the yellow colorant is preferably 40 parts by mass or less with respect to 100 parts by mass of Pigment A. The lower limit is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.
Also, the content of the yellow coloring agent is preferably 100 parts by mass or less with respect to 100 parts by mass of the magenta dye. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. The upper limit is preferably 80 parts by mass or less, more preferably 60 parts by mass or less.
Also, the content of the yellow colorant is preferably 50 parts by mass or less with respect to the total of 100 parts by mass of the pigment A and the magenta dye. The lower limit is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
Further, the total content of pigment A, magenta color dye and other colorant is preferably 40 to 90% by mass based on the total solid content of the coloring composition. The lower limit is preferably 45% by mass or more, more preferably 50% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less.
Further, the total content of pigment A, magenta dye and yellow colorant is preferably 40 to 90% by mass based on the total solid content of the coloring composition. The lower limit is preferably 45% by mass or more, more preferably 50% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less.

<<Compound having a curable group>>
The coloring composition of the present invention contains a compound having a curable group. There is no particular limitation on the reaction mechanism when the compound having a curable group is cured. Radical polymerization reaction, cationic polymerization reaction, polycondensation reaction, nucleophilic addition reaction, cross-linking reaction by substitution reaction, and the like can be mentioned. The compound having a curable group is preferably a compound that cures by a radical polymerization reaction. Examples of curable groups include ethylenically unsaturated groups and epoxy groups. Examples of ethylenically unsaturated groups include vinyl groups, vinyloxy groups, allyl groups, methallyl groups, (meth)acryloyl groups, styrene groups, cinnamoyl groups and maleimide groups, and (meth)acryloyl groups, styrene groups and maleimide groups. A (meth)acryloyl group is preferred, and a (meth)acryloyl group is more preferred.

A compound having a curable group (hereinafter also referred to as a curable compound) may be a monomer or a resin such as a polymer. A monomer-type curable compound and a resin-type curable compound may be used in combination.

(Compound having an ethylenically unsaturated group)
In the present invention, the compound having an ethylenically unsaturated group used as the curable compound may be a monomer or a resin. It is preferable to contain a resin type compound for the reason that it is easy to form a cured film having excellent heat resistance. Hereinafter, a compound having an ethylenically unsaturated group is also referred to as a polymerizable compound. A monomer having an ethylenically unsaturated group is also called a polymerizable monomer. A resin having an ethylenically unsaturated group is also called a polymerizable resin.

The molecular weight of the polymerizable monomer is preferably less than 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and even more preferably 250 or more. The polymerizable monomer is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and 3 to 6 ethylenically unsaturated groups. more preferably a compound containing The polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of the polymerizable monomer include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph number 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, Compounds described in JP 2013-253224, paragraph numbers 0034 to 0038, JP 2012-208494, paragraph 0477, JP 2017-048367, JP 6057891, JP 6031807 , the contents of which are incorporated herein.

Polymerizable monomers include dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. ), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku ( Co., Ltd., NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which these (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (eg SR454, SR499, commercially available from Sartomer) are preferred. Further, NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used as polymerizable monomers. In addition, as polymerizable monomers, trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy-modified tri(meth)acrylate, trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, isocyanuric acid ethyleneoxy-modified tri(meth)acrylate. , pentaerythritol tri(meth)acrylate and the like are also preferably used. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) etc.

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

A compound having a caprolactone structure can also be used as the polymerizable monomer. Polymerizable monomers having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60 and DPCA-120.

A compound having an alkyleneoxy group can also be used as the polymerizable monomer. A polymerizable monomer having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and has 4 to 20 ethyleneoxy groups. Tri- to hexa-functional (meth)acrylate compounds are more preferred. Commercially available polymerizable monomers having an alkyleneoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having 4 ethyleneoxy groups and a trifunctional (meth)acrylate having 3 isobutyleneoxy groups, manufactured by Sartomer Co., Ltd. KAYARAD TPA-330, which is an acrylate, and the like.

As the polymerizable monomer, it is also preferable to use a compound that does not substantially contain environmental regulation substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable monomer, JP-B-48-041708, JP-B-51-037193, JP-B-02-032293, JP-B-02-016765 described urethane acrylates, JP-B-58- 049860, JP-B-56-017654, JP-B-62-039417, JP-B-62-039418 urethane compounds having an ethylene oxide skeleton, JP-A-63-277653, JP-A-63-277653, It is also preferable to use compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-260909 and JP-A-01-105238. Further, as the polymerizable monomer, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600 , T-600, AI-600, and LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

The weight average molecular weight of the polymerizable resin is preferably 3,000 or more, more preferably 5,000 or more, even more preferably 7,000 or more, and particularly preferably 10,000 or more. Moreover, the weight average molecular weight of the polymerizable resin is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less.

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

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

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

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

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

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

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

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

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

Preferably, the polymerizable resin further contains a repeating unit having a graft chain. When the polymerizable resin contains a repeating unit having a graft chain, aggregation of the pigment A can be more effectively suppressed due to steric hindrance caused by the graft chain. In addition, when the cured film is formed, the polymerizable resin can be polymerized in the vicinity of the pigment A to firmly hold the pigment A in the film, thereby more effectively suppressing the thermal diffusion of the pigment A due to heating. It is also possible to form a cured film having more excellent heat resistance. The polymerizable resin preferably contains 1.0 to 60 mol %, more preferably 1.5 to 50 mol %, of repeating units having a graft chain in the total repeating units of the polymerizable resin. A polymerizable resin containing a repeating unit having a graft chain is preferably used as a dispersant.

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

The graft chain preferably contains repeating units having at least one structure selected from polyester repeating units, polyether repeating units, poly(meth)acrylic repeating units, polyurethane repeating units, polyurea repeating units and polyamide repeating units. It more preferably contains repeating units having at least one structure selected from repeating units, polyether repeating units and poly(meth)acrylic repeating units, and more preferably contains polyester repeating units. Examples of polyester repeating units include repeating units having a structure represented by the following formula (G-1), formula (G-4), or formula (G-5). Further, the polyether repeating unit includes a repeating unit having a structure represented by the following formula (G-2). Examples of poly(meth)acrylic repeating units include repeating units having a structure represented by the following formula (G-3).

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

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

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

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

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

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

In formula (G-1a), R ^{1 G1} in each repeating unit when n1 is 2 or more may be the same or different. In addition, when ^RG1 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 formulas (G-2a) to (G-5a).

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

In formula (A-1-2), ^X2 represents the main chain of the repeating unit, ^L2 represents a single bond or a divalent linking group, and ^W1 represents a graft chain. The main chain of the repeating unit represented by X ² in formula (A-1-2) includes the structures described for X ¹ in formula (A-1-1), and the preferred range is also the same. The divalent linking group represented by L ² in formula (A-1-2) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, OCO—, —S—, and groups formed by combining two or more of these. The graft chain represented by W ¹ in formula (A-1-2) includes the above-described graft chains.

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

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

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

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

It is also preferred that the polymerizable resin further contains a repeating unit having an acid group. The dispersibility of the pigment A or the like can be further improved by including a repeating unit having an acid group in the polymerizable resin. Furthermore, developability can also be improved. Examples of acid groups include carboxyl groups, sulfo groups, and phosphoric acid groups.

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

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

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

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

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

When the polymerizable resin contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 80 mol% or less in the total repeating units of the polymerizable resin, and 10 to 80 mol%. more preferred.

The acid value of the polymerizable resin is preferably 20-150 mgKOH/g. More preferably, the upper limit is 100 mgKOH/g or less. The lower limit is preferably 30 mgKOH/g or more, more preferably 35 mgKOH/g or more. If the acid value of the polymerizable resin is within the above range, particularly excellent dispersibility is likely to be obtained. Furthermore, excellent developability is likely to be obtained.

In addition, the polymerizable resin may contain, as other repeating units, a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers"). ) can contain repeating units derived from monomer components.

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）で表される化合物の具体例としては、特開２０１０－１６８５３９号公報に記載された化合物が挙げられる。In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of the compound represented by formula (ED2) include compounds described in JP-A-2010-168539.

Specific examples of the ether dimer, for example, paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein. Only one kind of ether dimer may be used, or two or more kinds thereof may be used.

式中、Ｚ^１は、（ｍ＋ｎ）価の連結基を表し、
Ｙ^１およびＹ^２は、それぞれ独立して単結合または連結基を表し、
Ａ^１は顔料吸着部を含む基を表し、
Ｐ^１はポリマー鎖を表し、
ｎは１～２０を表し、ｍは１～２０を表し、ｍ＋ｎは３～２１であり、
ｎ個のＹ^１およびＡ^１はそれぞれ同一であってもよく、異なっていてもよく、
ｍ個のＹ^２およびＰ^１はそれぞれ同一であってもよく、異なっていてもよく、
Ｚ^１、Ａ^１およびＰ^１の少なくとも一つはエチレン性不飽和基を表す。
性基を含む。In the present invention, a compound represented by the following formula (SP-1) (hereinafter also referred to as compound (SP-1)) can also be used as the polymerizable resin. Compound (SP-1) can be preferably used as a dispersant.

In the formula, Z ¹ represents a (m+n)-valent linking group,
Y ¹ and Y ² each independently represent a single bond or a linking group;
A ¹ represents a group containing a pigment adsorption moiety,
P ¹ represents the polymer chain,
n represents 1 to 20, m represents 1 to 20, m+n is 3 to 21,
n Y ¹ and A ¹ may be the same or different,
m Y ² and P ¹ may be the same or different,
At least one of Z ¹ , A ¹ and P ¹ represents an ethylenically unsaturated group.
Contains sexual groups.

Ethylenically unsaturated groups contained in the compound (SP-1) include a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth)acryloyl group, a styrene group, a cinnamoyl group and a maleimide group. An acryloyl group, a styrene group and a maleimide group are preferred, a (meth)acryloyl group is more preferred, and an acryloyl group is particularly preferred.

In compound (SP-1), the ethylenically unsaturated group may be contained in any one of Z ¹ , A ¹ and P ¹ , but is preferably contained in P ¹ . Moreover, when P ¹ contains an ethylenically unsaturated group, P ¹ is preferably a polymer chain having a repeating unit containing an ethylenically unsaturated group in a side chain.

In formula (SP-1), A ¹ represents a group containing a pigment adsorption moiety. As the pigment adsorption part, an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxy A silyl group, an epoxy group, an isocyanate group and a hydroxy group, preferably a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a hydrocarbon group having 4 or more carbon atoms, and a hydroxy group. From the point of view, an acid group is more preferable. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, with the carboxyl group being preferred.

At least one pigment adsorption portion may be included in one ^A1 , and two or more may be included. A ¹ preferably contains 1 to 10 pigment-adsorbing moieties, more preferably 1 to 6 pigment-adsorbing moieties. In addition, the group containing a pigment adsorption moiety represented by A ¹ includes the aforementioned pigment adsorption moiety, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, and 1 to 400 and a group formed by bonding with a linking group consisting of 0 to 40 sulfur atoms. For example, one or more pigment adsorption sites via a chain saturated hydrocarbon group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms and a group formed by combining. The above chain saturated hydrocarbon group, cyclic saturated hydrocarbon group and aromatic hydrocarbon group may further have a substituent. Substituents include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, and an acyloxy group having 1 to 6 carbon atoms. , an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate ester group, a photocurable group, and the like. Further, when the pigment adsorption portion itself can constitute a monovalent group, the pigment adsorption portion itself may be ^A1 .

Further, the chemical formula weight of A ¹ is preferably 30-2000. The upper limit is preferably 1000 or less, more preferably 800 or less. The lower limit is preferably 50 or more, more preferably 100 or more. If the chemical formula weight of ^A1 is within the above range, the adsorptivity to the coloring material is good. The chemical formula weight of ^A1 is a value calculated from the structural formula.

In formula (SP-1), Z ¹ represents a (m+n)-valent linking group. (m+n)-valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. A group consisting of Examples of the (m+n)-valent linking group include the following structural units or groups (which may form a ring structure) formed by combining two or more of the following structural units.

The chemical formula weight of Z ¹ is preferably 20-3000. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 50 or more, more preferably 100 or more. The chemical formula weight of ^Z1 is a value calculated from the structural formula. Specific examples of the (m+n)-valent linking group can be referred to paragraphs 0043 to 0055 of JP-A-2014-177613, the contents of which are incorporated herein.

In Formula (SP-1), Y ¹ and Y ² each independently represent a single bond or a linking group. Linking groups include groups consisting of 1-100 carbon atoms, 0-10 nitrogen atoms, 0-50 oxygen atoms, 1-200 hydrogen atoms, and 0-20 sulfur atoms. be done. The groups described above may further have the substituents described above. Examples of the linking group represented by Y ¹ and Y ² include the following structural units or groups formed by combining two or more of the following structural units.

In formula (SP-1), P ¹ represents a polymer chain. The polymer chain represented by ^P1 has at least one selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units, polyamide repeating units, polyimide repeating units, polyimine repeating units and polyurethane repeating units in the main chain. A polymer chain having one type of repeating unit is preferred. Further, the polymer chain represented by ^P1 is preferably a polymer chain containing repeating units represented by the following formulas (P1-1) to (P1-5).

In the above formula, R ^G1 and R ^G2 each represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 is 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. The alkylene group may have a substituent. Substituents include aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated groups, and the like.
In the above formula, ^RG3 represents a hydrogen atom or a methyl group.
In the above formula, Q ^G1 represents -O- or -NH-, L ^G1 represents a single bond or an arylene group, and L ^G2 represents a single bond or a divalent linking group. Q ^G1 is preferably -O-. ^LG1 is preferably a single bond. The divalent linking group represented by L ^G2 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), —NH—, —SO—, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO-, -CONH-, and groups consisting of combinations of two or more thereof.
^RG4 represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkylthioether groups, arylthioether groups, heteroarylthioether groups, ethylenically unsaturated groups, acid groups, and the like. mentioned.

The repeating number of the repeating unit in P ¹ is preferably 3-2000. The upper limit is preferably 1500 or less, more preferably 1000 or less. The lower limit is preferably 5 or more, more preferably 7 or more. Moreover, ^P1 is preferably a polymer chain having a repeating unit containing an ethylenically unsaturated group in its side chain. Further, the proportion of repeating units containing an ethylenically unsaturated group in a side chain in all repeating units constituting ^P1 is preferably 1 mol% or more, more preferably 2 mol% or more, It is more preferably 3 mol % or more. The upper limit can be 100 mol %. In addition, when P ¹ is a polymer chain having a repeating unit containing an ethylenically unsaturated group in its side chain, P ¹ may contain other repeating units in addition to the repeating unit containing an ethylenically unsaturated group in its side chain. It is also preferred to include Other repeating units include repeating units containing acid groups in side chains. In addition to the repeating unit containing an ethylenically unsaturated group in the side chain, P ¹ further contains a repeating unit containing an acid group in the side chain, so that when patterning is performed by a photolithography method, the generation of development residues is further reduced. can be effectively suppressed. When P ¹ contains a repeating unit containing an acid group in the side chain, the proportion of repeating units containing an acid group in the side chain in all repeating units constituting P ¹ is preferably 50 mol% or less, It is more preferably 2 to 48 mol %, even more preferably 4 to 46 mol %.

The weight average molecular weight of the polymer chain represented by P ¹ is preferably 1,000 or more, more preferably 1,000 to 10,000. The upper limit is preferably 9000 or less, more preferably 6000 or less, even more preferably 3000 or less. The lower limit is preferably 1200 or more, more preferably 1400 or more. The weight average molecular weight of ^P1 is a value calculated from the weight average molecular weight of the raw material used for introducing the polymer chain.

(Compound having an epoxy group)
In the present invention, as a compound having an epoxy group (hereinafter also referred to as an epoxy compound) used as a curable compound, a compound having two or more epoxy groups in one molecule is preferably used. The upper limit of the number of epoxy groups in the epoxy compound is preferably 100 or less, more preferably 10 or less, and even more preferably 5 or less.

The epoxy equivalent of the epoxy compound (=molecular weight of compound having epoxy group/number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 to 400 g/eq, and more preferably 100 to 300 g/eq. It is even more preferable to have

The epoxy compound may be a low-molecular compound (eg, molecular weight less than 1000) or a macromolecule (eg, molecular weight 1000 or more, weight-average molecular weight 1000 or more in the case of polymers). The molecular weight (weight average molecular weight in the case of a polymer) of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the molecular weight (weight average molecular weight in the case of polymers) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less.

As the epoxy compound, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408. Compounds can also be used. The contents of these are incorporated herein. Commercially available epoxy compounds include, for example, bisphenol A epoxy resins such as jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, and jER1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation) and the like, and bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007 and jER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (manufactured by DIC Corporation), LCE-21, RE-602S (manufactured by Nippon Kayaku Co., Ltd.) and the like. (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation) and the like. , EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (Nippon Kayaku Co., Ltd.) ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, EHPEAD PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) etc. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation) and the like.

The content of the curable compound is preferably 1 to 50 wt% of the total solid content of the coloring composition. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less.
Further, when a polymerizable monomer is used as the curable compound, the content of the polymerizable monomer is preferably 0.1 to 40% by mass based on the total solid content of the coloring composition. The lower limit is preferably 1% by mass or more, more preferably 2% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
Further, when a polymerizable resin is used as the curable compound, the content of the polymerizable resin is preferably 1 to 50% by mass based on the total solid content of the coloring composition. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less.
Further, the total content of the polymerizable monomer and the polymerizable resin is preferably 1 to 50 mass% of the total solid content of the coloring composition. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less. Moreover, the content of the polymerizable resin in the total amount of the polymerizable monomer and the polymerizable resin is preferably 70% by mass or more, more preferably 80% by mass or more.
Further, when an epoxy compound is used as the curable compound, the content of the epoxy compound is preferably 0.1 to 40% by mass based on the total solid content of the coloring composition. The lower limit is, for example, more preferably 1% by mass or more, and even more preferably 2% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and even more preferably 20% by mass or less. Epoxy compounds may be used singly or in combination of two or more. Further, when a polymerizable compound and a compound having an epoxy group are used in combination, the ratio (mass ratio) of the two is preferably the mass of the polymerizable compound: the mass of the compound having the epoxy group=100:1 to 100:400. , 100:1 to 100:100, more preferably 100:1 to 100:50.

A preferred embodiment of the coloring composition of the present invention includes the following.
The coloring composition comprises a monomer having an ethylenically unsaturated group (polymerizable monomer) and a resin,
M ¹ / B ¹ , which is the ratio of the mass M ¹ of the monomer (polymerizable monomer) having an ethylenically unsaturated group contained in the coloring composition and the mass B ¹ of the resin contained in the coloring composition, is 0.35 or less, preferably 0.25 or less, and more preferably 0.21 or less. According to the coloring composition of this aspect, it is possible to form a cured film having more excellent heat resistance. Furthermore, film shrinkage during the formation of a cured film can be suppressed. In particular, when a polymerizable resin is used as the resin, the above effect can be obtained more remarkably. The lower limit of the value of M ¹ /B ¹ is preferably 0.01 or more, more preferably 0.04 or more, and even more preferably 0.07 or more. The mass ^B1 of the resin is the total amount of the polymerizable resin described above and other resins described later. If the coloring composition does not contain other resins, the resin weight ^B1 is the weight of the polymerizable resin described above. Moreover, when the coloring composition does not contain a polymerizable resin, the mass ^B1 of the resin is the mass of the other resin.
Further, in the above aspect, the total content of the polymerizable monomer and the resin is preferably 1 to 50% by mass based on the total solid content of the coloring composition. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less.

<<other resins>>
The coloring composition of the present invention can further contain a resin that does not contain a curable group (hereinafter also referred to as other resin). Other resins are blended, for example, for dispersing particles such as pigments in the composition and for binder applications. A resin that is mainly used to disperse particles such as pigments is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

The weight average molecular weight (Mw) of other resins is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3000 or more, more preferably 5000 or more.

Other resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, and polyamides. Examples include imide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins. One of these resins may be used alone, or two or more may be mixed and used.

Other resins may have acid groups. The acid group includes, for example, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferred. Only one kind of these acid groups may be used, or two or more kinds thereof may be used. A resin having an acid group can also be used as an alkali-soluble resin.

As a resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and alkali-soluble polymers such as novolak resins. Phenolic resins, acidic cellulose derivatives having carboxyl groups in side chains, and resins obtained by adding acid anhydrides to polymers having hydroxyl groups can be mentioned. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, vinyl compounds, and the like. Alkyl (meth)acrylates and aryl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, etc. be done. Examples of vinyl compounds include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomers, polymethylmethacrylate macromonomers, and the like. Other monomers that can be used include N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenylmaleimide and N-cyclohexylmaleimide. In addition, these other monomers copolymerizable with (meth)acrylic acid may be of only one type, or may be of two or more types.

Acid group-containing resins include benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer, benzyl (meth) A multicomponent copolymer consisting of acrylate/(meth)acrylic acid/other monomers can be preferably used. Also, a copolymer of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer described in JP-A-07-140654, 2 -Hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene A macromonomer/benzyl methacrylate/methacrylic acid copolymer and the like can also be preferably used.

The acid group-containing resin is also preferably a polymer containing repeating units derived from the aforementioned monomer component containing the ether dimer.

式（Ｘ）において、Ｒ_１は、水素原子またはメチル基を表し、Ｒ_２は炭素数２～１０のアルキレン基を表し、Ｒ_３は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。The acid group-containing resin may contain a repeating unit derived from a compound represented by formula (X) below.

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

For the resin having an acid group, JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408 The descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein. Moreover, resin which has an acid group can also use a commercial item.

The acid value of the resin having acid groups is preferably 30-200 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less.

The coloring composition of the present invention can also contain a resin as a dispersant. Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably from 40 to 105 mgKOH/g, more preferably from 50 to 105 mgKOH/g, even more preferably from 60 to 105 mgKOH/g. Further, a basic dispersant (basic resin) represents a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol % when the total amount of acid groups and basic groups is 100 mol %. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, it is possible to further reduce the residue generated on the base of the pixels during pattern formation by photolithography.

It is also preferable that the resin used as the dispersant is a graft resin. Examples of the graft resin include a resin having a repeating unit represented by the formula (A-1-2) described in the section of the polymerizable resin described above. Details of the graft resin can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

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

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

Dispersants are also available as commercial products, and specific examples thereof include BYK Chemie's DISPERBYK series (e.g., DISPERBYK-111, 161, etc.), Nippon Lubrizol Co., Ltd.'s Solsperse series ( For example, Solsperse 76500, etc.). Also, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can be used, the contents of which are incorporated herein. In addition, the resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.

When the coloring composition of the present invention contains other resins, the content of the other resin is preferably 30% by mass or less in the total solid content of the coloring composition of the present invention, be 20% by mass or less is more preferable, and 10% by mass or less is even more preferable.
Further, the total content of the curable compound and other resins described above is preferably 1 to 50% by mass based on the total solid content of the coloring composition of the present invention. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less.

<<Photoinitiator>>
The coloring composition of the present invention preferably contains a photopolymerization initiator. In particular, when a compound having an ethylenically unsaturated group is used as the curable compound, the colored composition of the present invention preferably further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet range to the visible range are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, thio compounds. , ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazoles. dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, α-hydroxyketone compounds , α-aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and Japanese Patent No. 6301489, the contents of which are incorporated herein.

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

Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2000-080068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, Patent No. Compounds described in WO 2015/152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, WO 2017/164127 Compounds described in paragraph numbers 0025 to 0038 of No. 2013, compounds described in International Publication No. 2013/167515, and the like. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.), and Adeka Optomer N-1919. (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A-2012-014052). As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

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

As a photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO2013/083505.

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

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

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

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

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As the photopolymerization initiator, a bifunctional or trifunctional or higher functional radical photopolymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is reduced, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the colored composition can be improved. . Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Paragraph numbers 0407 to 0412, dimers of oxime compounds described in paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compounds described in JP-A-2013-522445 ( G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiators described in paragraph number 0007 of JP 2017-523465, JP 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP-A-2017-151342, and the like.

The content of the photopolymerization initiator in the total solid content of the coloring composition of the present invention is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% 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.

<<Pigment derivative>>
The coloring composition of the present invention can contain pigment derivatives. Pigment derivatives include compounds having a structure in which a portion of a pigment is substituted with an acid group or a basic group. As pigment derivatives, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03 -153780, JP 03-045662, JP 04-285669, JP 06-145546, JP 06-212088, JP 06-240158, JP 10-030063 No., JP-A-10-195326, paragraph numbers 0086 to 0098 of WO 2011/024896, paragraph numbers 0063 to 0094 of WO 2012/102399, paragraph number 0082 of WO 2017/038252 , Compounds described in paragraph number 0171 of JP 2015-151530, etc., compounds described in JP 2015-172732, compounds described in JP 2014-199308, JP 2014-085562 The compound described, the compound described in JP-A-2014-035351, and the compound described in JP-A-2008-081565 can be used, the contents of which are incorporated herein.

The content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. If the content of the pigment derivative is within the above range, the dispersibility of the pigment can be enhanced and aggregation of the pigment can be efficiently suppressed. Only one kind of pigment derivative may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.

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

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

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

In the present invention, it is preferable to use a solvent with a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a ppt (parts per trillion) level solvent may be used, and such a high-purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

Methods for removing impurities such as metals from the solvent include, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.

The content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.

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

In addition, it is preferable that the colored composition of the present invention does not substantially contain any environmentally regulated substances from the viewpoint of environmental regulations. In the present invention, "substantially free of environmentally regulated substances" means that the content of environmentally regulated substances in the colored composition is 50 ppm by mass or less, preferably 30 ppm by mass or less. , is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmental controlled substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) law, VOC (Volatile Organic Compounds) regulations, etc. methods are strictly regulated. These compounds may be used as a solvent when producing each component used in the coloring composition of the present invention, and may be mixed into the coloring composition as a residual solvent. From the viewpoint of safety to humans and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the amount of environmentally regulated substances, there is a method in which the system is heated or decompressed to raise the temperature to the boiling point of the environmentally regulated substances or higher, and the environmentally regulated substances are distilled off from the system. In the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase the efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like is added and distilled off under reduced pressure in order to suppress the radical polymerization reaction from progressing during the vacuum distillation and the intermolecular cross-linking. may These distillation methods include the stage of raw materials, the stage of products obtained by reacting raw materials (for example, resin solutions and polyfunctional monomer solutions after polymerization), or the stages of colored compositions prepared by mixing these compounds. is possible at any stage.

<<polymerization inhibitor>>
The coloring composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.

<<Surfactant>>
The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Surfactants include those described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.

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

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

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

Fluorine-based surfactants also include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.

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

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

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

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

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa Kojunyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) ) and the like.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd. ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie).

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

<<Ultraviolet absorber>>
The coloring composition of the present invention can contain an ultraviolet absorber. A conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used as the ultraviolet absorber. Such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, paragraph numbers 0317-0334 of JP-A-2013-068814, Examples include compounds described in paragraphs 0061-0080 of JP2016-162946, the contents of which are incorporated herein. Examples of commercially available UV absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Benzotriazole compounds include the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016). Compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used as ultraviolet absorbers.

The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Antioxidant>>
The coloring composition of the present invention can contain an antioxidant. Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like. In addition, antioxidants include compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, and compounds described in WO 2017/164024. can also be 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 kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Other Ingredients>>
The coloring composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. In addition, the coloring composition of the present invention may contain a latent antioxidant, if desired. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing the protective group by the reaction is exemplified. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.). Further, as described in JP-A-2018-155881, C.I. I. Pigment Yellow 129 may be added for the purpose of improving weatherability.

The coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of metal oxides include TiO ₂ , ZrO ₂ , Al ₂ O ₃ and SiO ₂ . The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm. Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.

The coloring composition of the present invention may contain a light resistance improver. As the light resistance improver, compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475, compounds described in paragraph numbers 0018-0021 of JP-A-2012-103475, in particular Compounds described in paragraphs 0015 to 0018 of JP 2011-257591, compounds described in paragraphs 0017 to 0021 of JP 2011-191483, described in paragraphs 0108 to 0116 of JP 2011-145668 and compounds described in paragraph numbers 0103 to 0153 of JP-A-2011-253174.

In the coloring composition of the present invention, the content of free metals not bound or coordinated with pigments is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less. , is particularly preferably substantially free. According to this aspect, stabilization of pigment dispersibility (prevention of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuations due to elution of metal atoms and metal ions, display Effects such as improved characteristics can be expected. In addition, JP-A-2012-153796, JP-A-2000-345085, JP-A-2005-200560, JP-A-08-043620, JP-A-2004-145078, JP-A-2014-119487, Described in JP 2010-083997, JP 2017-090930, JP 2018-025612, JP 2018-025797, JP 2017-155228, JP 2018-036521, etc. You can also get the effect of Examples of the free metal types include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Ni, Cd, Pb, Bi and the like are included. Further, in the coloring composition of the present invention, the content of free halogen that is not bonded or coordinated with the pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, and 10 ppm or less. It is more preferable, and it is particularly preferable that it does not contain substantially. Halogens include F, Cl, Br, I and their anions. Methods for reducing free metals and halogens in the colored composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

It is also preferred that the coloring composition of the present invention is substantially free of terephthalate.

<Container>
The container for the coloring composition of the present invention is not particularly limited, and known containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resins and a bottle with a 7-layer structure of 6 types of resins for the purpose of suppressing contamination of raw materials and coloring compositions. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351. In addition, the inner wall of the coloring composition is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, improving the storage stability of the composition, and suppressing deterioration of components. Storage conditions for the coloring composition of the present invention are not particularly limited, and conventionally known methods can be used. Alternatively, the method described in JP-A-2016-180058 can also be used.

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

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

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

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

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

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

<Cured film>
The cured film of the present invention is a cured film obtained from the coloring composition of the present invention described above. The cured film of the present invention can be used for color filters and the like. Specifically, it can be preferably used as a colored layer (pixel) of a color filter, and more specifically, it can be preferably used as a red colored layer (red pixel) of a color filter. The film thickness of the cured film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

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

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

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

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

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

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

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

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

The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.

<Manufacturing method of color filter>
Next, a method for manufacturing the color filter of the present invention will be described. The color filter of the present invention comprises the steps of forming a colored composition layer on a support using the colored composition of the present invention described above, and forming a pattern on the colored composition layer by a photolithography method or a dry etching method. It can be manufactured through the process of

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

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

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

The coloring composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process. When pre-baking is performed, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher. The pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

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

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

Further, the exposure may be performed by continuously irradiating the light, or by pulsing the light (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles. In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more. The frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, and even more preferably 4 kHz or higher. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. The maximum instantaneous illuminance is preferably 50000000 W/ ^m2 or more, more preferably 100000000 W/ ^m2 or more, and even more preferably 200000000 W/ ^m2 or more. The upper limit of the maximum instantaneous illuminance is preferably 1000000000 W/m ² or less, more preferably 800000000 W/m ² or less, and even more preferably 500000000 W/m ² or less. It should be noted that the pulse width is the time during which the light is applied in the pulse period. Also, the frequency is the number of pulse cycles per second. Further, the maximum instantaneous illuminance is the average illuminance within the time during which the light is irradiated in the pulse period. Further, the pulse cycle is a cycle in which light irradiation and rest in pulse exposure are set as one cycle.

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

Next, the unexposed portion of the colored composition layer is removed by development to form a pattern (pixels). The development and removal of the unexposed portion of the colored composition layer can be performed using a developer. As a result, the unexposed portion of the colored composition layer in the exposure step is eluted into the developer, leaving only the photocured portion. The temperature of the developer is preferably 20 to 30° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

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

After development, it is preferable to carry out additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure processing and post-baking are post-development curing treatments for complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. . When the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Also, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

(Dry etching method)
Next, the case of forming a pattern by dry etching to manufacture a color filter will be described. Pattern formation by a dry etching method is a step of forming a colored composition layer on a support using the colored composition of the present invention, and curing the entire colored composition layer to form a cured product layer; a step of forming a photoresist layer on the cured layer; a step of patternwise exposing the photoresist layer and then developing it to form a resist pattern; and etching the cured layer using the resist pattern as a mask. and dry etching using a gas. In forming the photoresist layer, it is preferable to further perform a pre-baking process. In particular, as the formation process of the photoresist layer, a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable. Regarding pattern formation by a dry etching method, descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.

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

A plurality of photodiodes and transfer electrodes made of polysilicon or the like are provided on the substrate, forming the light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal-oxide semiconductor) image sensor, etc.). and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. and a color filter on the device protective film. Furthermore, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) on the device protective film and below the color filter (on the side close to the substrate), or a configuration having a condensing means on the color filter, etc. There may be. Moreover, the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure are described in JP-A-2012-227478, JP-A-2014-179577, International Publication No. 2018/043654, and US Patent Application Publication No. 2018/0040656. device. An imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, etc.), but also for vehicle-mounted cameras and monitoring cameras.

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

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

<Method for measuring weight average molecular weight (Mw) and number average molecular weight (Mn)>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin and macromonomer were calculated by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI detector)
Pre-column TSKGUARDCOLUMN MP (XL) 6 mm × 40 mm (manufactured by Tosoh Corporation)
Sample side column: Directly connect the following 4 columns (all manufactured by Tosoh Corporation)
TSK-GEL Multipore-HXL-M 7.8mm x 300mm
Reference side column: Same as sample side column Thermostatic bath temperature: 40°C
Mobile phase: Tetrahydrofuran Sample side mobile phase flow rate: 1.0 mL/min Reference side mobile phase flow rate: 0.3 mL/min Sample concentration: 0.1% by mass
Sample injection volume: 100 μL
Data acquisition time: 16 to 46 minutes after sample injection Sampling pitch: 300 ms (milliseconds)

<Method for measuring acid value>
The acid value of the resin was determined by neutralization titration using an aqueous sodium hydroxide solution. Specifically, a solution obtained by dissolving the resin in a solvent is titrated with an aqueous sodium hydroxide solution using a potentiometric method, the number of millimoles of the acid contained in 1 g of the solid content of the resin is calculated, and then the value was determined by multiplying the molecular weight of potassium hydroxide (KOH), 56.1.

<Method for measuring C=C value (ethylenically unsaturated group value)>
The C=C value of the resin was measured by the following method.
The low-molecular-weight component (a) of the ethylenically unsaturated group site is removed from the resin by alkali treatment, the content thereof is measured by high performance liquid chromatography (HPLC), and the C=C value is calculated from the following formula based on the measured value. Calculated.
Specifically, 0.1 g of the resin was dissolved in a tetrahydrofuran/methanol mixture (50 mL/15 mL), 10 mL of a 4 mol/L sodium hydroxide aqueous solution was added, and the mixture was reacted at 40° C. for 2 hours. The reaction solution was neutralized with 10.2 mL of a 4 mol/L methanesulfonic acid aqueous solution, then a mixture of 5 mL of ion-exchanged water and 2 mL of methanol was transferred to a 100 mL volumetric flask, and the volume was increased with methanol for HPLC measurement. A sample is prepared and measured under the following conditions. The content of the low-molecular-weight component (a) was calculated from a separately prepared calibration curve for the low-molecular-weight component (a), and the C=C value was calculated from the following formula.

C value of resin = C value [mmol/g] = (content of low-molecular-weight component (a) [ppm]/molecular weight of low-molecular-weight component (a) [g/mol])/(weight of resin [g] x (Solid concentration of resin liquid [mass%]/100) x 10)

- HPLC measurement conditions -
Measuring instrument: Agilent-1200 (manufactured by Agilent Technologies Inc.)
Column: Phenomenex Synergi 4u Polar-RP 80A, 250 mm × 4.60 mm (inner diameter) + guard column Column temperature: 40 ° C.
Analysis time: 15 minutes Flow rate: 1.0 mL/min (maximum liquid transfer pressure: 182 bar (18.2 MPa))
Injection volume: 5 μl
Detection wavelength: 210 nm
Eluent: tetrahydrofuran (for HPLC without stabilizer)/buffer solution (ion-exchange aqueous solution containing 0.2% by volume of phosphoric acid and 0.2% by volume of triethylamine) = 55/45 (% by volume)
In addition, in this specification, volume % is a value in 25 degreeC.

<Method for measuring amine value>
Accurately weigh about 0.5 g of resin, add 50 mL of acetic acid (100% by mass) to dissolve, and perform electrotitration with 0.1 mol / L perchloric acid (potentiometric titration) potentiometric automatic titrator (AT-710M; Kyoto Electronics Kogyo Co., Ltd.) was used for titration. In addition, a blank test was performed in the same manner for correction.
Amine value = a x 5.611/c
a: 0.1 mol/L Perchloric acid consumption (mL)
c: amount of resin (g)

<Preparation of Pigment Dispersions RD1 to RD7, CRD1 to CRD4, and YD1 to YD4>
A mixed liquid was obtained by mixing raw materials shown in the table below. The resulting mixture was subjected to dispersion treatment using an Ultra Apex Mill (trade name) manufactured by Kotobuki Kogyo Co., Ltd. as a circulating dispersing device (bead mill) to prepare each pigment dispersion. Among the components shown in the table below, the numerical values shown in the parts by mass column of dispersant 1 and dispersant 2 are solid content values.

<Preparation of magenta colorant solutions MD1 to MD33>
Magenta colorant solutions MD1 to MD33 were obtained by mixing the raw materials shown in the table below.

<Preparation of magenta colorant solutions CMD1 to CMD2>
A mixed liquid was obtained by mixing raw materials shown in the table below. The resulting mixture was subjected to dispersion treatment using Ultra Apex Mill (trade name) manufactured by Kotobuki Kogyo Co., Ltd. as a circulating dispersing device (bead mill) to prepare magenta colorant solutions CMD1 and CMD2. Among the components shown in the table below, the numerical value shown in the column of parts by mass of the dispersant is the value of the solid content.

顔料ＣＲ１～ＣＲ４：下記構造の化合物。

顔料Ｙ１：Ｃ．Ｉ．ピグメントイエロー１３８
顔料Ｙ２：Ｃ．Ｉ．ピグメントイエロー１３９
顔料Ｙ３：Ｃ．Ｉ．ピグメントイエロー１５０
顔料Ｙ４：Ｃ．Ｉ．ピグメントイエロー１８５The materials listed in the above table are as follows.
(pigment)
Pigments R1 to R5: Compounds having the following structures. Pigment R1 is C.I. I. Pigment Red 272.

Pigments CR1 to CR4: Compounds having the following structures.

Pigment Y1: C.I. I. pigment yellow 138
Pigment Y2: C.I. I. pigment yellow 139
Pigment Y3: C.I. I. pigment yellow 150
Pigment Y4: C.I. I. pigment yellow 185

(magenta dye)
Magenta dyes M1 to M32: Salts of cationic cyanine chromophores and anions listed in the table below. Each of magenta dyes M1 to M32 has a solubility of 1 g or more in 100 g of water at 23° C. or a solubility in 100 g of propylene glycol monomethyl ether acetate at 23° C.

[Cationic cyanine chromophore]
In the structural formulas below, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Hex represents a hexyl group.

[Counter anion]

Counter anions AJ-1 to AJ-4: resins (AJ-1) to (AJ-4) having anionic groups produced by the following methods

AJ-1: A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts by mass of methyl ethyl ketone and heated to 75° C. under a nitrogen stream. Separately, 20.0 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 12.5 parts by weight of methyl methacrylate, 20.0 parts by weight of n-butyl methacrylate, 20.0 parts by weight of 2-ethylhexyl methacrylate, 3.5 parts by weight of methacrylic acid. 0 parts by mass, 16.5 parts by mass of 2-hydroxyethyl methacrylate, 6.5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile), and 25.1 parts by mass of methyl ethyl ketone were homogenized and then added dropwise. It was charged into a funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 3390, and the mixture was cooled to 50°C. 3.2 parts by mass of methyl chloride and 22.0 parts by mass of ethanol were added thereto and reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour and further reacted for 2 hours. Thus, a resin (AJ-1) having an anionic group content of 47% by mass was obtained.

AJ-2 to AJ-4: Resins (AJ-2) to (AJ-4) were obtained in the same manner as resin (AJ-1), except that the material compositions were changed to those shown in the table below.

Magenta dye M33: A compound (xanthene compound) having the following structure. The magenta dye M33 has a solubility of 1 g or more in 100 g of water at 23°C or a solubility in 100 g of propylene glycol monomethyl ether acetate at 23°C.

(magenta color pigment)
Magenta color pigment CM1: C.I. I. pigment red 122
Magenta color pigment CM2: C.I. I. pigment red 177
Both the magenta color pigment CM1 and the magenta color pigment CM2 have a solubility in 100 g of water at 23°C and a solubility in 100 g of propylene glycol monomethyl ether acetate at 23°C of less than 0.1 g.

(pigment derivative)
Pigment derivative Sy1: a compound having the following structure

(dispersant)
Dispersant D1: resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw: 20000, C=C value: 0.0 mmol/g, Acid value: 75 mgKOH/g, amine value: 0.0 mmol/g)

Dispersant D2: Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw: 20000, C=C value: 0.0 mol/g, Acid value: 50 mgKOH/g, amine value: 0.0 mmol/g)

Dispersant D3: Resin PA-1 produced by the following method
In a three-necked flask, 60.78 g of a macromonomer B-1 solution having a concentration (solid content) of 50% by mass (PGMEA: 30.39 g, macromonomer B-1 (30.39 g)), ω-carboxy-poly 50.99 g of caprolactone monoacrylate (Aronix M-5300, manufactured by Toagosei Co., Ltd.) and 159.5 g of PGMEA (propylene glycol 1-monomethyl ether 2-acetate) were introduced to obtain a mixture.
The mixture was stirred while blowing with nitrogen. The mixture was then heated to 75° C. while flowing nitrogen through the flask. Next, 0.82 g of dodecyl mercaptan and then 0.43 g of 2,2′-azobis(methyl 2-methylpropionate) (hereinafter also referred to as “V-601”) are added to the mixture, and polymerized. The reaction started.
After the mixture was heated at 75° C. for 2 hours, an additional 0.43 g of V-601 was added to the mixture. After 2 hours, an additional 0.43 g of V-601 was added to the mixture.
After reacting for an additional 2 hours, the mixture was heated to 90° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, 9.6 g of dimethyldodecylamine as an amine compound and 0.3 g of 2,2,6,6-tetramethylpiperidine 1-oxyl as a polymerization inhibitor were added under air, and then 9.01 g of 4-hydroxybutyl acrylate glycidyl ether was added dropwise.
After completion of the dropwise addition, the reaction was continued for 24 hours at 90° C. in air, and the completion of the reaction was confirmed by measuring the acid value. Resin PA-1 was obtained by adding PGMEA to the obtained mixture so as to obtain a 30% by mass solution.
The resulting resin PA-1 had a weight average molecular weight (Mw) of 17200, an acid value of 70 mgKOH/mg, a C=C value of 0.45 mmol/g, and an amine value of 0.45 mmol/g.
Macromonomer B-1: compound having the following structure (Mw: 3000)

Dispersant D4: Resin PA-2 produced by the following method
In a three-necked flask, 82.76 g of a macromonomer B-1 solution having a concentration (solid content) of 50% by mass (PGMEA: 41.38 g, macromonomer B-1 (41.38 g)), ω-carboxy-poly 44.14 g of caprolactone monoacrylate (Aronix M-5300, manufactured by Toagosei Co., Ltd.) and 159.5 g of PGMEA were introduced to obtain a mixture.
The mixture was stirred while blowing with nitrogen. The mixture was then heated to 75° C. while flowing nitrogen through the flask. Next, 0.82 g of dodecyl mercaptan and then 0.43 g of V-601 were added to the mixture to initiate the polymerization reaction.
After the mixture was heated at 75° C. for 2 hours, an additional 0.43 g of V-601 was added to the mixture. After 2 hours, an additional 0.43 g of V-601 was added to the mixture.
After reacting for an additional 2 hours, the mixture was heated to 90° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, 6.43 g of dimethyldodecylamine as an amine compound and 0.3 g of 4-hydroxy-2,2,6,6,-tetramethylpiperidine 2-oxyl as a polymerization inhibitor were added under air. 8.05 g) of 4-hydroxybutyl acrylate glycidyl ether was added dropwise as a reactive compound.
After completion of the dropwise addition, the reaction was continued for 24 hours at 90° C. in air, and the completion of the reaction was confirmed by measuring the acid value. Resin PA-2 was obtained by adding PGMEA to the obtained mixture so as to obtain a 30% by mass solution.
The resulting resin PA-2 has a weight average molecular weight (Mw) of 23300, an acid value of 60 mgKOH/mg,
The C=C value was 0.4 mmol/g, and the amine value was 0.3 mmol/g.
Met.

(solvent)
Solvent S1: propylene glycol monomethyl ether acetate (PGMEA)

<Preparation of coloring composition>
Coloring compositions of Examples and Comparative Examples were prepared by mixing the raw materials shown in the table below.

樹脂Ｂ２：下記構造の樹脂（主鎖に付記した数値はモル比である。Ｍｗ：１１０００）

樹脂Ｂ３：下記構造の樹脂（主鎖に付記した数値はモル比である。Ｍｗ：１００００）

The raw materials listed in the above table are as follows.
(resin)
Resin B1: Resin having the following structure (numerical values attached to the main chain are molar ratios, Mw: 30000)

Resin B2: Resin having the following structure (numerical values attached to the main chain are molar ratios; Mw: 11000)

Resin B3: Resin having the following structure (numerical values attached to the main chain are molar ratios, Mw: 10000)

光重合開始剤Ｉ５：下記構造の化合物

(Polymerizable monomer)
Polymerizable monomer E1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable monomer E2: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerizable monomer E3: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polymerizable monomer E4: succinic acid-modified dipentaerythritol pentaacrylate Polymerizable monomer E5: Dipentaerythritol hexaacrylate Polymerizable monomer E6: Dipentaerythritol pentaacrylate (photopolymerization initiator)
Photoinitiator I1: IRGACURE 369 (manufactured by BASF)
Photoinitiator I2: IRGACURE OXE01 (manufactured by BASF)
Photoinitiator I3: IRGACURE OXE02 (manufactured by BASF)
Photoinitiator I4: a compound having the following structure

Photoinitiator I5: a compound having the following structure

(Surfactant)
Surfactant F1: A compound having the following structure (in the following formula, % indicating the ratio of repeating units is mol %, Mw: 14000).

(Polymerization inhibitor)
Polymerization inhibitor H1: p-methoxyphenol

(solvent)
Solvent S1: propylene glycol monomethyl ether acetate (PGMEA)

<Heat resistance evaluation>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied on a glass substrate by spin coating so that the film thickness was 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. A stratum was formed. Each coloring composition was applied onto the glass substrate with the underlayer by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to obtain a coating film. The obtained coating film was exposed to light with a wavelength of 365 nm at an exposure amount of 500 mJ/cm ² . Then, it was heated at 220° C. for 5 minutes using a hot plate to obtain a cured film having a thickness of 0.5 μm. The obtained cured film was measured for light transmittance (transmittance) in the range of 400 to 700 nm using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.
Next, the cured film prepared above was heated at 265° C. for 5 minutes. The transmittance of the cured film after heating was measured, the maximum value of the change in transmittance was determined, and the heat resistance was evaluated according to the following criteria.
The transmittance was measured 5 times for each sample, and the average value of the 3 times results excluding the maximum and minimum values was adopted. Further, the maximum value of the change in transmittance means the change in the wavelength at which the change in transmittance of the cured film before and after heating is the largest in the wavelength range of 400 to 700 nm.
(Evaluation criteria)
5: The maximum value of change in transmittance is 1% or less.
4: The maximum value of change in transmittance exceeds 1% and is 1.5% or less.
3: The maximum value of change in transmittance exceeds 1.5% and is 2.0% or less.
2: The maximum value of change in transmittance exceeds 2.0% and is 2.5% or less.
1: The maximum value of change in transmittance exceeds 2.5%.

As shown in the above table, cured films having excellent heat resistance could be produced by using the colored compositions of the examples. In addition, the cured films obtained from the coloring compositions of Examples had favorable spectral characteristics as a red colored layer.

In each example, even if two types of pigment A specified in claim 1 are used in combination, the same effects as in each example can be obtained.

(Example 63)
10.64 parts by mass of pigment R1, 1.33 parts by mass of pigment derivative Sy1, 1.99 parts by mass of dispersant D1, 1.99 parts by mass of dispersant D2, and 2.0 parts by mass of magenta dye M1. 02 parts by mass of solvent S1 and 82.03 parts by mass of solvent S1 were mixed to obtain a mixture. The resulting mixture was subjected to dispersion treatment using Ultra Apex Mill (trade name) manufactured by Kotobuki Kogyo Co., Ltd. as a circulating dispersing device (bead mill) to prepare dispersion MRD1. In the coloring composition of Example 1, in the same manner as the coloring composition of Example 1, except that 60.91 parts by mass of the dispersion MRD1 was added instead of the pigment dispersion 1 and the magenta colorant solution. A coloring composition of Example 63 was prepared. Using this coloring composition, the heat resistance was evaluated by the same method as above, and the evaluation was "2".

(Example 1001)
A green composition was applied onto a silicon wafer by spin coating so that the film thickness after post-baking was 1.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), light with a wavelength of 365 nm was irradiated (exposed) at an exposure amount of 1000 mJ/cm ² through a 2 μm square dot pattern mask. Then, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, the green composition was patterned by heating (post-baking) at 200° C. for 5 minutes using a hot plate. Similarly, the Red composition and the Blue composition were sequentially patterned to form green, red and blue colored patterns (Bayer patterns).
As the red composition, the coloring composition of Example 3 was used. The Green composition and Blue composition will be described later. Note that the Bayer pattern includes one red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. 2 is a repeating pattern of a 2×2 array of color filter elements having a color filter element. The obtained color filter was incorporated into a solid-state imaging device according to a known method. This solid-state imaging device had a favorable image recognition ability.

- Green composition -
[Preparation of Green Pigment Dispersion]
C. I. Pigment Green 36, 6.4 parts by mass, C.I. I. Pigment Yellow 150 of 5.3 parts by mass, a dispersing agent (Disperbyk-161, manufactured by BYK Chemie) of 5.2 parts by mass, and PGMEA of 83.1 parts by mass. A pigment dispersion was prepared by mixing and dispersing for 3 hours. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under a pressure of 2,000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to prepare a green pigment dispersion.

[Preparation of Green Composition]
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a green composition.
Green pigment dispersion: 73.7 parts by mass 40% by mass PGMEA solution of resin B2: 0.3 parts by mass Polymerizable monomer E1: 1.2 parts by mass Photopolymerization initiator I2: 0.6 parts by mass Surfactant F1 1% by mass PGMEA solution: 4.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.): 0.5 parts by mass PGMEA: 19.5 parts by mass

-Blue composition-
[Preparation of Blue Pigment Dispersion]
C. I. Pigment Blue 15:6, 9.7 parts by mass, C.I. I. A mixture of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was prepared in a bead mill (zirconia beads with a diameter of 0.3 mm). A pigment dispersion was prepared by mixing and dispersing for 3 hours. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under a pressure of 2,000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to prepare a blue pigment dispersion.

光重合開始剤Ｉ２：０．８質量部
界面活性剤Ｆ１の１質量％ＰＧＭＥＡ溶液：４．２質量部
ＰＧＭＥＡ：４５．８質量部[Preparation of Blue composition]
After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.
Blue pigment dispersion: 44.9 parts by mass 40% by mass PGMEA solution of resin B2: 2.1 parts by mass Polymerizable monomer E1: 1.5 parts by mass Polymerizable monomer having the following structure: 0.7 parts by mass

Photopolymerization initiator I2: 0.8 parts by mass Surfactant F1 1% by mass PGMEA solution: 4.2 parts by mass PGMEA: 45.8 parts by mass

Claims (17)

A diketopyrrolopyrrole pigment, a magenta dye, a compound having a curable group, and a photopolymerization initiator,
The diketopyrrolopyrrole pigment contains a pigment A which is a compound represented by the following formula (1) , and the proportion of the pigment A in the total mass of the diketopyrrolopyrrole pigment contained in the coloring composition is 99. % by mass or more,
The magenta dye contains at least one selected from the group consisting of xanthene compounds and cyanine compounds,
The compound having a curable group includes a compound having an ethylenically unsaturated group,
The content of the pigment A in the total solid content of the coloring composition is 35% by mass or more,
A coloring composition containing 5 to 50 parts by mass of the magenta dye with respect to 100 parts by mass of the pigment A ;

wherein R ¹¹ and R ¹² each independently represent a substituent,
R ²¹ and R ²² each independently represent an electron donating group, the electron donating group being a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an amino group;
n11 and n12 each independently represents an integer of 0 to 4; The coloring composition according to claim 1, wherein the pigment A is a compound represented by the following formula (2);

wherein R ¹¹ and R ¹² each independently represent a substituent,
R ²¹ and R ²² each independently represent an electron donating group, the electron donating group being a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group or an amino group;
n11 and n12 each independently represents an integer of 0 to 4; 3. The coloring composition according to claim 1, wherein said electron-donating group possessed by said pigment A is a hydroxy group, an alkyl group or an alkoxy group. 3. The coloring composition according to claim 1 , wherein said electron-donating group possessed by said pigment A is an alkyl group having 1 to 3 carbon atoms. The coloring composition according to any one of claims 1 to 4 , wherein the pigment A is a red pigment. The coloring composition according to any one of claims 1 to 5 , wherein the magenta dye comprises a salt of a cationic cyanine chromophore and an imide anion. The imide anion is an imide anion represented by formula (AN-2), the coloring composition according to claim 6;

In formula (AN-2), Y ¹ represents a group having a polymerizable group,
Y. ² represents a group represented by formula (Y2-1) or formula (Y2-2);

In formula (Y2-1), R ^y1 is a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ^y20 COOR ^y21 - or R ^y22 COOR ^y23 represents CFH-, and R ^y20 and R ^y22 each independently represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group; ^y21 and R ^y23 each independently represents an alkylene group, n represents an integer of 1 or more, * represents a bond;
In formula (Y2-2), R ^y2 ～R ^y6 each independently represents a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group, a fluorinated alkyl group or an alkoxy group; * represents a bond; ^y2 ～R ^y6 at least one of is a fluorine atom or a fluorinated alkyl group. A colored composition according to any one of claims 1 to 7 , further comprising a yellow colorant. The coloring composition according to any one of claims 1 to 8 , wherein the content of the pigment A in the total solid content of the coloring composition is 40% by mass or more. The coloring composition according to any one of claims 1 to 9 , wherein the diketopyrrolopyrrole pigment contains two or more of the pigments A. The coloring composition according to any one of claims 1 to 10 , which is for a solid-state imaging device. The coloring composition according to any one of claims 1 to 11 , which is for color filters. A cured film obtained from the colored composition according to any one of claims 1 to 12 . A step of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 12 , and patterning the colored composition layer by a photolithography method or a dry etching method. and forming a pattern. A color filter comprising the cured film according to claim 13 . A solid-state imaging device comprising the cured film according to claim 13 . An image display device comprising the cured film according to claim 13 .