JP7123660B2 - Photosensitive colored resin composition and cured product thereof, color filter, and display device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive colored resin composition and its cured product, a color filter, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. Recently, an organic light-emitting display device such as an organic EL display, which has high visibility due to self-luminescence, is also attracting attention as a next-generation image display device. As for the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility is desired.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image in a liquid crystal display device, the light that has passed through the color filter is colored into the color of each pixel that constitutes the color filter, and the light of these colors is combined to form a color image. As a light source in that case, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. In addition, the organic light emitting display device uses a color filter for color adjustment.

Therefore, in color filters, there is an increasing demand for higher brightness, higher contrast, and improved color reproducibility.
As a recent trend, there is a demand for power saving in image display devices, and there is a particular demand for higher brightness of color filters in order to improve the utilization efficiency of the backlight. In particular, mobile displays (mobile phones, smart phones, tablet PCs) are a big problem.

Here, the color filter generally includes a substrate, a colored layer formed on the substrate and including colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. and a light shielding part.
As one method for forming such a colored layer, a method is known in which a photosensitive colored resin composition containing a coloring material and a photopolymerizable compound is applied onto a substrate and cured by irradiation with ultraviolet rays or the like. It is

In Patent Document 1, even with a thin film and an appropriate colorant concentration, the Rec. ITU-R BT. As a colored curable resin composition capable of forming a color filter having a high coverage rate of the 2020 color gamut, the colorant is C.I. I. A colored curable resin composition is disclosed comprising Pigment Blue 16 and a red colorant and/or a violet colorant.

JP 2017-133009

However, even if the combination of coloring materials described in Patent Document 1 is used, the luminance of the finally obtained colored layer is not sufficient, and further improvement is desired. That is, when a pigment is used as the red colorant and/or the purple colorant, the brightness becomes low, and when a dye is used, the heat resistance and light resistance are poor. The chromaticity tends to change, and the brightness of the finally obtained colored layer is not sufficient, and further improvement is required.

Moreover, generally, the colored layer for the color filter is patterned on the substrate. When forming a colored layer using a photosensitive colored resin composition, for example, after forming a coating film of the photosensitive colored resin composition on a substrate, it is exposed through a predetermined mask pattern, and then developed. Thus, a patterned colored layer can be obtained.
In recent years, there has been a demand for patterning with a smaller amount of exposure in order to increase production efficiency. I. It has been found that when a phthalocyanine pigment containing Pigment Blue 16 is used to form a blue colored layer, the colored layer may not be formed as designed.

The present invention has been made based on the above findings, and suppresses the chromaticity change (ΔEab) and luminance decrease before and after the high-temperature heating process (post-baking) in the color filter manufacturing process, and the coloring obtained after the high-temperature heating process. While improving the brightness of the layer, a photosensitive colored resin composition capable of forming a pattern with a desired line width, a color filter having a good brightness formed using the photosensitive colored resin composition, and the color filter It is an object of the present invention to provide a display device having excellent display characteristics.

The photosensitive colored resin composition according to the present invention contains a coloring material, a binder component containing a photopolymerizable compound and a photoinitiator, and a solvent,
The colorant is C.I. I. Pigment Blue 16, and a lake colorant of a triarylmethane dye and a polyacid,
The photoinitiator is a photosensitive colored resin composition containing an oxime ester compound.

The present invention provides a cured product of the photosensitive colored resin composition according to the present invention.
The present invention provides a color filter comprising at least a substrate and colored layers provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to the present invention. , to provide color filters.
The present invention provides a display device having the color filter according to the present invention.

According to the present invention, the chromaticity change (ΔEab) before and after the high-temperature heating step (post-baking) in the color filter manufacturing process and the decrease in brightness are suppressed, and the brightness of the colored layer obtained after the high-temperature heating step is improved. A photosensitive colored resin composition capable of forming a pattern with a line width, a color filter having good brightness formed using the photosensitive colored resin composition, and a display device having excellent display characteristics using the color filter can be provided.

FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. FIG. 2 is a schematic diagram showing an example of the display device of the present invention. FIG. 3 is a schematic diagram showing another example of the display device of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive colored resin composition, the cured product thereof, the color filter, and the display device according to the present invention will be described in detail below.
In the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present invention, (meth)acryl represents each of acrylic and methacrylic, and (meth)acrylate represents each of acrylate and methacrylate.

I. Photosensitive colored resin composition The photosensitive colored resin composition according to the present invention contains a coloring material, a binder component containing a photopolymerizable compound and a photoinitiator, and a solvent,
The colorant is C.I. I. Pigment Blue 16, and a lake colorant of a triarylmethane dye and a polyacid,
The photoinitiator is characterized by containing an oxime ester compound.

The photosensitive colored resin composition of the present invention has a small chromaticity change (ΔEab) before and after high-temperature heating (post-baking) in the color filter manufacturing process, and a decrease in luminance is suppressed. It has the effect of being able to form a pattern with a desired line width while maintaining good brightness of the layer.
Since the post-baking process in the color filter manufacturing process involves heating at a high temperature of 230° C. or 240° C., conventionally, pigments have been used as the coloring material because the coloring material is less likely to fade during heating at the high temperature. Furthermore, in recent years, in order to increase production efficiency, patterning with a smaller amount of exposure has been demanded. was found to be not formed in some cases. This is because the blue phthalocyanine pigment absorbs around 300 nm, which is the absorption wavelength (radical generation wavelength) of the photoinitiator, so that the photopolymerization reaction does not proceed sufficiently, resulting in insufficient curing of the inside of the colored layer during exposure. presumed to be
In contrast, in the present invention, the phthalocyanine pigment C.I. I. By using a combination of a triarylmethane dye and a polyacid lake colorant for Pigment Blue 16, the lake colorant of the triarylmethane dye and polyacid hardly absorbs wavelengths around 300 nm. Even when a photosensitive colored resin composition for a blue colored layer is produced by combining a negative type photosensitive binder component, insufficient curing of the inside of the colored layer is unlikely to occur during exposure, making it easy to form a pattern with a desired line width. Furthermore, in the present invention, since the negative photosensitive binder component contains an oxime ester compound, insufficient curing of the inside of the colored layer is less likely to occur during exposure, making it easier to form a pattern with a desired line width.
Furthermore, a phthalocyanine pigment, C.I. I. By using Pigment Blue 16 in combination with a lake colorant of triarylmethane dyes and polyacids, which have improved heat resistance than dyes, the transmittance can be improved, and high temperature heating (post-baking) in the color filter manufacturing process It is presumed that the brightness of the colored layer finally obtained after high-temperature heating can be increased while suppressing the chromaticity change before and after and the decrease in brightness.
Moreover, C.I. I. By using Pigment Blue 16 in combination with a lake colorant of triarylmethane-based dyes and polyacids, which have improved heat resistance than dyes, even in a blue colored layer with a strong bluish color gamut, the final It is possible to form a pattern with a desired line width while the brightness of the colored layer obtained in 1 is good.

The photosensitive colored resin composition of the present invention contains at least a coloring material, a photopolymerizable compound, a photoinitiator, and a solvent, in a range that does not impair the effects of the present invention, further other components may contain.
Each component of the photosensitive colored resin composition of the present invention will be described in detail below.

[Color material]
In the present invention, the coloring material is C.I. I. Pigment Blue 16 and a lake colorant of triarylmethane-based dye and polyacid.

<C. I. Pigment Blue 16>
C. I. Pigment Blue 16 has a structure represented by the following chemical formula. C. I. Pigment Blue 16 is preferable from the viewpoint of widening the hue, particularly the color reproduction range. Also, C.I. I. When Pigment Blue 16 is used, since the coloring power is strong and the P/V ratio can be lowered, the plate-making property is improved, development chipping is easily suppressed, development residue is easily suppressed, and adhesion to the substrate is achieved. characteristics can be easily improved.

<Lake colorant of triarylmethane-based dye and polyacid>
In the present invention, a photosensitive colored resin composition capable of forming a pattern with a desired line width while suppressing chromaticity change and luminance reduction before and after the high temperature heating process and improving the luminance of the finally obtained colored layer. To achieve this, a lake colorant of a triarylmethane dye and a polyacid is included.
A lake colorant of a triarylmethane dye and a polyacid is a colorant obtained by turning a triarylmethane dye into a lake, and is therefore suitable for increasing brightness, like conventional triarylmethane dyes. Furthermore, since it is laked with a polyacid anion, it is superior in heat resistance and light resistance as compared with conventional triarylmethane dyes.
The lake colorant of the triarylmethane-based dye and polyacid has excellent heat resistance and achieves high brightness of the color filter. It is preferably one or more selected from the colorants represented by the general formula (2), and the colorant represented by the following general formula (1) forms a molecular association state, It is preferable in terms of exhibiting better heat resistance and light resistance and achieving higher brightness of the colored layer.

（一般式（１）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にＯ、Ｓ、Ｎが含まれていてもよい。Ｂ^ｃ－はｃ価のヘテロポリ酸アニオンを表す。Ｒ^ｉ～Ｒ^ｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ^ｉｉとＲ^ｉｉｉ、Ｒ^ｉｖとＲ^ｖが結合して環構造を形成してもよい。Ｒ^ｖｉ及びＲ^ｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、ハロゲン原子又はシアノ基を表す。Ａｒ^１は置換基を有していてもよい２価の芳香族基を表す。複数あるＲ^ｉ～Ｒ^ｖｉｉ及びＡｒ^１はそれぞれ同一であっても異なっていてもよい。
ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。複数あるｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）

(In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group has at least a saturated aliphatic carbonized Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may contain O, S, N. B ^c- is a c-valent heteropoly each of R ⁱ to R ^v independently represents a hydrogen atom, an ^optionally substituted alkyl group or an ^optionally substituted aryl group; ^iv and ^Rv may combine to form a ring structure, R ^vi and R ^vii are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen represents an atom or a cyano group, Ar ¹ represents an optionally substituted divalent aromatic group, and a plurality of R ⁱ to R ^vii and Ar ¹ may be the same or different. .
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. e is 0 or 1 and when e is 0 there is no bond. f and g represent integers of 0 or more and 4 or less, and f+e and g+e are 0 or more and 4 or less. Multiple e, f and g may be the same or different. )

（一般式（２）中、Ｒ^Ｉ、Ｒ^ＩＩ、Ｒ^ＩＩＩ、Ｒ^ＩＶ、Ｒ^Ｖ及びＲ^ＶＩは、それぞれ独立に、水素原子、炭素数１～３のアルキル基、又はフェニル基を表し、Ｘ^－は、（ＳｉＭｏＷ_１１Ｏ_４０）^４－／４及び（Ｐ_２Ｍｏ_ｙＷ_１８－ｙＯ_６２）^６－／６の少なくとも１つで表され、ｙ＝１、２または３の整数であるヘテロポリ酸アニオンを表す。）

(In general formula (2), R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and X ^- is represented by at least one of (SiMoW ₁₁ O ₄₀ ) ⁴⁻ /4 and (P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ /6, and y is an integer of 1, 2 or 3; represents an acid anion.)

Since the coloring material represented by the general formula (1) contains a divalent or higher valent anion and a divalent or higher cation, the aggregate of the coloring material has an anion and cation ratio of 1 molecule to 1 molecule. Because it is possible to form a molecular association in which multiple molecules associate through ionic bonds instead of ionic bonding, the apparent molecular weight is remarkably increased compared to the molecular weight of conventional lake pigments. It is presumed that the formation of such molecular associations increases the cohesive force in the solid state, reduces thermal motion, suppresses the dissociation of ion pairs and the decomposition of the cation part, and is less likely to fade than conventional lake pigments. be done.

A in the general formula (1) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is saturated at least at the terminal directly bonded to N Represents an aliphatic hydrocarbon group having an aliphatic hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, O (oxygen atom), S (sulfur atom), N (nitrogen atom) in the carbon chain It may be included. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic coloring site are not affected by the linking group A or other coloring sites, and the monomer and Similar colors can be retained.
In A, at least an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic, provided that the terminal carbon atom directly bonded to N does not have a π bond. may be any of, carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, the carbon chain contains O, S, N good too. For example, it may contain a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, etc., and a hydrogen atom may be further substituted with a halogen atom or the like.
In addition, the aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to at least N , may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of the robustness of the skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of the robustness of the skeleton. The term "bridged alicyclic hydrocarbon group" refers to a polycyclic aliphatic hydrocarbon group having a polycyclic structure having a bridged structure within an aliphatic ring, such as norbornane, bicyclo[2,2,2] octane, adamantane and the like. Among the bridged alicyclic hydrocarbon groups, norbornane is preferred. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, The group containing a benzene ring is especially preferable. For example, when A is a divalent organic group, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group substituted with two alkylene groups having 1 to 20 carbon atoms such as a xylylene group. etc.

The valence a in A is the number of color-forming cation sites constituting the cation, and a is an integer of 2 or more. In this lake colorant, since the valence a of the cation is 2 or more, the heat resistance is excellent. Among them, it is preferable that the valence a of the cation is 3 or more. Although the upper limit of a is not particularly limited, a is preferably 4 or less, more preferably 3 or less, from the viewpoint of ease of production.
The alkyl groups in R ⁱ to R ^v are not particularly limited. Examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, among which linear or branched alkyl groups having 1 to 8 carbon atoms are preferred, and linear alkyl groups having 1 to 5 carbon atoms are preferred. A chain or branched alkyl group is more preferable from the viewpoint of brightness and heat resistance. Among them, it is particularly preferable that the alkyl group in R ⁱ to R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group and the like. Examples of the substituted alkyl group include an aralkyl group such as a benzyl group. etc.
The aryl groups in R ⁱ to R ^v are not particularly limited. Examples include phenyl group and naphthyl group. Examples of substituents that the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, and the like.
Among them, from the viewpoint of chemical stability, R ⁱ to R ^v are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ or R ^iv and R ^v are bonded. preferably form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

Each of R ⁱ to R ^v can independently have the above structure. Among them, R ⁱ is preferably a hydrogen atom from the viewpoint of color purity ^. More preferably, all R ^v are the same.

R ^vi and R ^vii each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano group. The alkyl group for R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms more preferably a group. The alkyl group having 1 to 4 carbon atoms includes methyl group, ethyl group, propyl group and butyl group, and may be linear or branched. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like.
The alkoxy group for R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and having 1 to 4 carbon atoms. is more preferably an alkoxy group of The alkoxy group having 1 to 4 carbon atoms includes methoxy, ethoxy, propoxy and butoxy groups, and may be linear or branched. The substituent that the alkoxy group may have is not particularly limited, but examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group and the like.
Halogen atoms in R ^vi and R ^vii include, for example, fluorine, chlorine, bromine and iodine atoms.
The substitution numbers of R ^vi and R ^vii , that is, f and g, each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1. A plurality of f and g may be the same or different.
In addition, R ^vi and R ^vii may be substituted at any site of a triarylmethane skeleton or an aromatic ring having a resonance structure within the xanthene skeleton, and among these, -NR ⁱⁱ R ⁱⁱⁱ or -NR ^iv It is preferably substituted at the meta position based on the substitution position of the amino group represented by ^Rv .

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group for Ar ¹ can be the same as those listed for the aromatic group for A.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group containing a condensed polycyclic carbocyclic ring having 10 to 14 carbon atoms. Among them, a phenylene group and a naphthylene group are more preferable because of their simple structure and inexpensive raw materials.

Plural R ⁱ to R ^vii and Ar ¹ in one molecule may be the same or different. A desired color can be adjusted by a combination of R ⁱ to R ^vii and Ar ¹ .

In the coloring material represented by the general formula (1) in the present invention, among others, B ^c- is a polyoxide anion because of its high brightness and excellent heat resistance.
The polyacid anion may be an isopolyacid anion (M _m O _n ) ^c- or a heteropolyacid anion (X ₁ M _m O _n ) ^c- . In the above ionic formula, M is a poly atom, X is a hetero atom, m is a composition ratio of poly atoms, and n is a composition ratio of oxygen atoms. Examples of polyatoms M include Mo, W, V, Ti, and Nb. Examples of the heteroatom X include Si, P, As, S, Fe, Co, and the like.
Among them, from the viewpoint of heat resistance, a polyoxide anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyoxide anion containing at least tungsten is more preferable.

In general formula (1), b indicates the number of cations, d indicates the number of anions in the molecular association, and b and d are integers of 1 or more. When b is 2 or more, a plurality of cations present in the molecular association may be of one type alone or in combination of two or more types. Further, when d is 2 or more, the plural anions present in the molecular association may be of one type alone or in combination of two or more types.

e in the general formula (1) is an integer of 0 or 1; e=0 represents a triarylmethane skeleton and e=1 represents a xanthene skeleton. A plurality of e may be the same or different. As the lake colorant represented by the general formula (1) used in the present invention, one containing at least a triarylmethane skeleton is preferably used.
In addition, as a lake colorant represented by general formula (1), for example, it can be prepared with reference to the pamphlet of International Publication No. 2012/144520.

On the other hand, in the colorant represented by the general formula (2), examples of the alkyl group having 1 to 3 carbon atoms in R ^I to R ^VI of the general formula (2) include a methyl group, an ethyl group, and n-propyl. groups, iso-propyl groups, and the like.

The structure of the cation moiety having a triarylmethane skeleton may be appropriately selected depending on the desired chromaticity and the like. Among them, from the viewpoint of easily achieving high brightness and high contrast, it is preferable to have the same structure as the cationic moiety of conventionally known triarylmethane dyes. As specific examples, for example, in the general formula (2), R ^I to R ^V are ethyl groups, R ^VI is a hydrogen atom Basic Blue 7, R ^I to R ^IV are methyl groups, R ^V is a phenyl group, Basic Blue 26 in which R ^VI is a hydrogen atom, Basic Blue 11 in which R ^I to R ^IV are a methyl group, R ^V is an ethyl group, and R ^VI is a hydrogen atom, R ^I to R ^V are a methyl group, and R ^VI is a phenyl Among them, it is preferable to have a cationic moiety structure similar to that of Basic Blue 7 from the viewpoint of easily achieving high brightness and high contrast.

X ⁻ in the general formula (2) is represented by at least one of (SiMoW ₁₁ O ₄₀ ) ⁴⁻ /4 and (P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ /6, y=1, A heteropolyacid anion that is an integer of 2 or 3. X ⁻ in the colorant represented by the general formula (2) is only one of (SiMoW ₁₁ O ₄₀ ) ⁴⁻ /4 or P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ /6. or (SiMoW ₁₁ O ₄₀ ) ⁴⁻ /4 and P ₂ Mo _y W _18-y O ₆₂ ) ⁶⁻ /6 may be mixed and used.

The lake colorant of the general formula (2) can be prepared, for example, with reference to International Publication No. 2012/039416 and International Publication No. 2012/039417.

In the photosensitive colored resin composition of the present invention, the lake colorant of triarylmethane dye and polyacid may be used singly or in combination of two or more.

<Other color materials>
The coloring material in the photosensitive colored resin composition of the present invention contains the C.I. I. Pigment Blue 16, and a triarylmethane-based dye and a polyacid lake colorant, but in order to adjust the color tone without impairing the effects of the present invention, may be used in combination with other colorants. good. For example, the colorant may further include a purple colorant different from the lake colorant of triarylmethane-based dye and polyacid.
As other coloring materials, known pigments, dyes, lake coloring materials and the like can be used singly or in combination of two or more.

Other blue colorants and purple colorants are preferably used as other colorants, but are not limited to these.
Other blue colorants include, for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 60 and the like, C.I. I. Known organic blue pigments different from Pigment Blue 16, and triarylmethane-based lake colorants different from the above-described lake colorants of triarylmethane-based dyes and polyacids.
In addition, as a blue color material, when a coating film of 2.5 μm is formed with P / V = 0.2 and the spectral transmittance spectrum is measured, the 440 nm transmittance is 60% or more and the 520 nm transmittance is 10% or more. In addition, a coloring material having a 580 nm transmittance of less than 10% is used.
In order to make a coating film of the blue colorant alone and measure the color, a coating solution is prepared by blending the blue colorant with an appropriate dispersant, a binder component and a solvent, coated on a transparent substrate and dried. and hardened if necessary. As the binder component, a non-curable thermoplastic resin composition may be used, or a photocurable (photosensitive) or thermosetting resin composition may be used as long as a transparent coating film capable of colorimetry can be formed. may be used. Further, in the colored resin composition of the present invention described later, by using a composition containing only a blue colorant as a colorant, a coating film containing only a blue colorant as a colorant may be formed and colorimetry may be performed. can. Specifically, for example, a solid content other than the coloring material used in the resin composition of Example 1 described later can be used as the binder component.
The spectral transmittance spectrum can be measured using a spectrophotometer (for example, Olympus Microspectrophotometer OSP-SP200).

As the purple colorant, known purple organic pigments, purple dyes, and purple lake colorants can be used, but in terms of heat resistance, it is selected from the group consisting of known purple organic pigments and purple lake colorants. At least one is preferred.
The purple colorant used in the present invention has a 440 nm transmittance of 40% or more and a 520 nm transmittance when a 2.5 μm coating film is formed at P / V = 0.2 and the spectral transmittance spectrum is measured. A colorant with a modulus of less than 10% and a 680 nm transmission of 40% or greater is used.
The purple colorant used in the present invention includes reddish purple colorants called red dyes.
The purple colorant alone can be formed into a coating film and colorimetrically measured in the same manner as the blue colorant described above.

Examples of the purple organic pigment include C.I. I. Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 and the like. Among them, Pigment Violet 23 is preferable because of its relatively excellent coloring power.

Examples of the purple dye include C.I. I. anthraquinone acid dyes such as Acid Violet 29, 31, 33, 34, 36, 36: 1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126; I. cyanine acid dyes such as Basic Red 12; triarylmethane acid dyes such as Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72; I. Acid Red 289, C.I. I. acid violet 9, C.I. I. Rhodamine-based acid dyes such as Acid Violet 30; also C.I. I. triarylmethane-based basic dyes such as Basic Violet 1, 3, 14, C.I. I. xanthene-based basic dyes such as Basic Violet 11, and the like.

Examples of the purple lake colorant include those obtained by turning the above purple dyes into lakes with a lake agent. The lake colorant of the dye may be a colorant in which the dye forms a salt with a counterion, for example, a lake colorant of an acid dye and a base, a lake colorant of a basic dye and an acid, and water It also includes organic pigments called lake pigments that are made insoluble by precipitating a soluble dye with a lake agent (precipitant).

As the purple dye and purple lake colorant, it is preferable that it is one or more selected from the group consisting of anthraquinone colorant, cyanine colorant, and xanthene colorant from the viewpoint of hue, especially xanthene color It is preferably one or more selected from the group consisting of materials.

A xanthene-based colorant is a colorant containing a compound having a xanthene skeleton.
A rhodamine-based colorant containing xanthene as a basic skeleton is preferable from the viewpoint of improving the brightness and contrast of the colored layer.
Among rhodamine colorants, the xanthene colorant preferably contains a compound represented by the following general formula (3).

（一般式（３）中、Ｒ^１～Ｒ^４は、それぞれ独立に、水素原子、置換基を有していても良い脂肪族炭化水素基、芳香族炭化水素基、又は芳香族複素環基であり、Ｒ^１とＲ^３、Ｒ^２とＲ^４がそれぞれ結合して環構造を形成してもよい。Ｒ^５は、水酸基、酸性基又はその塩、或いは、－Ｌ^１－Ｎ^－－Ｌ^２－Ｒ^６、ここで、Ｌ^１及びＬ^２は各々独立に、直接結合、―ＳＯ_２―、又は―ＣＯ―であり、Ｒ^６はハロゲン化脂肪族炭化水素基である。Ｘは、ハロゲン原子を表す。ｍは０～５の整数を表す。一般式（３）はアニオン性基を１個以上有するものであり、ｎは０以上の整数である。）

(In general formula (3), R ¹ to R ⁴ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic heterocyclic group; , R ¹ and R ³ , R ² and R ⁴ may combine to form a ring structure, and R ⁵ is a hydroxyl group, an acidic group or a salt thereof, or -L ¹ -N ^- -L ² —R ⁶ , wherein L ¹ and L ² are each independently a direct bond, —SO ₂ —, or —CO—, R ⁶ is a halogenated aliphatic hydrocarbon group, X is a halogen atom represents an integer of 0 to 5. General formula (3) has one or more anionic groups, and n is an integer of 0 or more.)

The aliphatic hydrocarbon group for R ¹ to R ⁴ may be linear, branched, or cyclic, and is not particularly limited. group hydrocarbon groups, or cyclic aliphatic hydrocarbon groups (alicyclic hydrocarbon groups) having 5 to 8 carbon atoms, and the like, and those having 10 or less carbon atoms are preferable from the viewpoint of heat resistance. The aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkyl group which is a saturated aliphatic hydrocarbon group.
The substituent that the aliphatic hydrocarbon group may have is not particularly limited, but for example, a halogen atom, an aromatic hydrocarbon group, a carbamoyl group, a monovalent group represented by —CO—OR ^a , a monovalent group represented by —O—CO—R ^a′ , a monovalent group represented by —SO ₂ —R ^a″ , a monovalent group represented by —R ^b —CO—O—R ^c , A monovalent group represented by —R ^b′ —O—CO—R ^c′ and a monovalent group represented by —R ^b″ —SO ₂ —R ^c″ are included.
Examples of the substituted aliphatic hydrocarbon group include benzyl group and the like, and may further have a halogen atom or an acidic group as a substituent.

The aromatic hydrocarbon group for R ¹ to R ⁴ is not particularly limited, but includes, for example, an optionally substituted aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms, especially a phenyl group. , a naphthyl group and the like are preferred.
The aromatic heterocyclic group for R ¹ to R ⁴ is not particularly limited, but includes an optionally substituted aromatic heterocyclic group having 5 or more and 20 or less carbon atoms. Those containing a nitrogen atom, an oxygen atom, or a sulfur atom are preferred. Further, specific examples of aromatic heterocyclic groups include furan, thiophene, pyrrole, pyridine and the like.
The substituent that the aromatic hydrocarbon group or aromatic heterocyclic group may have is not particularly limited, but examples include an aliphatic hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, a carbamoyl group, and —CO—O. monovalent group represented by -R ^a , monovalent group represented by -O-CO-R ^a' , monovalent group represented by -SO ₂ -R ^a '', -R ^b -CO-O- a monovalent group represented by R ^c , a monovalent group represented by —R ^b′ —O—CO—R ^c′ , a monovalent group represented by —R ^b″ —SO ₂ —R ^c″ , etc. The R ^a , R ^a′ , R ^a″ , R ^b , R ^b′ , R ^b″ , R ^c , R ^c′ and R ^c″ each represent an aliphatic hydrocarbon group. These substituents are preferably used because they do not adversely affect heat resistance and the like. By adjusting the electron-withdrawing and electron-donating properties of these substituents, it is possible to adjust the spectral characteristics. Also, the aliphatic hydrocarbon group here may be the same as the aliphatic hydrocarbon group for R ¹ to R ⁴ .

R ¹ and R ³ , R ² and R ⁴ respectively bonded to form a ring structure means that R ¹ and R ³ , R ² and R ⁴ respectively form a ring structure via a nitrogen atom It means that there is The ring structure is not particularly limited, but examples include 5- to 7-membered nitrogen-containing heterocycles, and specific examples include pyrrolidine ring, piperidine ring, morpholine ring and the like.

R ³ and R ⁴ are preferably an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, and R ³ and R ⁴ are an aromatic hydrocarbon group or an aromatic heterocyclic group is preferably Among them, at least one of R ³ and R ⁴ is preferably an aromatic hydrocarbon group, and R ³ and R ⁴ are preferably aromatic hydrocarbon groups. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 or more and 10 or less carbon atoms, and a phenyl group suppresses the generation of foreign matter and forms a colored layer with improved brightness. It is preferable because it is possible.
In the case of an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, at least one is preferably substituted with an aliphatic hydrocarbon group.
As the aliphatic hydrocarbon group with which the hydrogen atom of the aromatic hydrocarbon group or the aromatic heterocyclic group is substituted, a linear aliphatic hydrocarbon group is particularly preferred. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 6 carbon atoms. Both R ³ and R ⁴ are an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, and are substituted with an aliphatic hydrocarbon group as described above. is preferred.
Further, at least one aromatic hydrocarbon group or aromatic heterocyclic group is substituted with two or more aliphatic hydrocarbon groups per one aromatic hydrocarbon group or aromatic heterocyclic group, This is preferable from the viewpoint of suppressing the generation of foreign matter and forming a colored layer with improved brightness.

Specific examples of the acidic group or a salt thereof include a carboxy group (--COOH), a carboxylate group ( ^--COO- ), a carboxylic acid group (--COOM, where M represents a metal atom.), a sulfonato group (--SO ₃ ⁻ ), sulfo group (—SO ₃ H), sulfonate group (—SO ₃ M, where M represents a metal atom), etc. Among them, sulfonato group (—SO ₃ ⁻ ), sulfo group (--SO ₃ H) or sulfonate group (--SO ₃ M). In addition, as a metal atom M, a sodium atom, a potassium atom, etc. are mentioned.

L ¹ and L ² in the -L ¹ -N ^- -L ² -R ⁶ group are each independently a direct bond, -SO ₂ -, or -CO-, especially -SO ₂ -, or - It is preferably CO—, and more preferably —SO ₂ — because generation of foreign matter is suppressed, heat resistance is excellent, and a colored layer with improved brightness can be formed.

R ⁶ in the -L ¹ -N ^- -L ² -R ⁶ group is a halogenated aliphatic hydrocarbon group, and examples of the halogen include a fluorine atom, a chlorine atom, an iodine atom, etc. Among them, a fluorine atom is preferably The halogenated aliphatic hydrocarbon group for R ⁶ is preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 to 8 carbon atoms, and a linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms. A branched halogenated aliphatic hydrocarbon group is more preferable, and a linear or branched halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms is even more preferable. Among them, the substitution rate of halogen atoms in the aliphatic hydrocarbon group (number of halogen atoms/total number of hydrogen atoms in the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more, Among them, 100% is preferable.
R ⁶ is preferably a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms.

Further, in the general formula (3), the substitution position of the -R ⁵ group of the benzene ring bonded to the xanthene skeleton is not particularly limited, but it is preferably ortho or para position with respect to the xanthene skeleton, It is preferable that the —R ⁵ group is substituted at the ortho position with respect to the xanthene skeleton from the viewpoint of various tolerances of the compound represented by the general formula (3). Although its mechanism of action is not clear, when the ^-R5 group is in the ortho position, it can form a ring structure by resonating with the carbon atom of the xanthene skeleton to which the benzene ring is attached, increasing the stability of the molecule, Therefore, it is presumed that various tolerances of the coloring material are improved.

The method for producing the compound represented by the general formula (3) is not particularly limited, and a known production method may be appropriately selected.

As the compound represented by the general formula (3), Acid Red 289, Acid Violet 9, Acid Violet 30, and the like are preferable from the viewpoint of increasing brightness.
From the viewpoint of heat resistance, a compound having a betaine structure in which m=1 and n=0 in general formula (3) is preferable.
Further, among them, m = 1 and n = 0, R ¹ and R ² are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and R ³ and R ⁴ are each independently an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, from the viewpoint of forming a colored layer excellent in brightness and light resistance.

The xanthene colorant is preferably a xanthene dye lake colorant (salt-forming compound).
As the xanthene-based dye lake colorant, a metal lake colorant is preferably used, and among them, a metal lake colorant containing the compound represented by the general formula (3) is preferably used. A metal lake colorant containing a metal atom is used as a lake agent. By using a laking agent containing metal atoms, the heat resistance of the coloring material is increased.
As the laking agent for the xanthene-based acid dye, a laking agent containing a metal atom that functions as a divalent or higher metal cation is preferable.

On the other hand, the counter anion of the xanthene-based basic dye may be an organic anion or an inorganic anion, but an inorganic anion is preferable from the viewpoint of various resistances.
Examples of inorganic anions include inorganic anions such as the aforementioned polyacid anions and mixtures thereof.

In addition, the counter ion (lake agent) of the dye in the rake colorant can be used singly or in combination of two or more.

<Content ratio of coloring material>
In the photosensitive colored resin composition of the present invention, the content of the lake colorant of the triarylmethane dye and the polyacid, while improving the brightness of the finally obtained colored layer, pattern with a desired line width From the point of obtaining a photosensitive colored resin composition capable of forming the, relative to the total content of all colorants, preferably 4% by mass or more, more preferably 6% by mass or more, 8% by mass The above is even more preferable. In addition, it is possible to form a pattern with a desired line width while improving the heat resistance of the coloring material, suppressing the chromaticity change and brightness reduction before and after the high temperature heating process, and improving the brightness of the finally obtained colored layer. From the viewpoint of obtaining a photosensitive colored resin composition, the content of the lake colorant of the triarylmethane dye and polyacid is preferably 32% by mass or less with respect to the total content of all colorants, It is more preferably 31% by mass or less, and even more preferably 29% by mass or less.

In the photosensitive colored resin composition of the present invention, C.I. I. The content of Pigment Blue 16 is the total content of all colorants from the viewpoint of obtaining a photosensitive colored resin composition capable of forming a pattern with a desired line width while improving the brightness of the finally obtained colored layer. is preferably 50% by mass or more, more preferably 55% by mass or more, even more preferably 60% by mass or more, and particularly preferably 68% by mass or more. In addition, it is possible to form a pattern with a desired line width while improving the heat resistance of the coloring material, suppressing the chromaticity change and luminance reduction before and after the high temperature heating process, and improving the luminance of the finally obtained colored layer. From the viewpoint of obtaining a photosensitive colored resin composition, C.I. I. The content of Pigment Blue 16 is preferably 96% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less with respect to the total content of all coloring materials. .

In the photosensitive colored resin composition of the present invention, C.I. I. Pigment Blue 16, the content ratio of the triarylmethane-based dye and the polyacid lake colorant, while improving the brightness of the finally obtained colored layer, the photosensitivity capable of forming a pattern with a desired line width From the viewpoint of obtaining a colored resin composition, C.I. I. Pigment Blue 16 is more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, of the triarylmethane-based dye and the polyacid lake colorant with respect to 100 parts by mass. In addition, it is possible to form a pattern with a desired line width while improving the heat resistance of the coloring material, suppressing the chromaticity change and luminance reduction before and after the high temperature heating process, and improving the luminance of the finally obtained colored layer. From the viewpoint of obtaining a photosensitive colored resin composition, C.I. I. Pigment Blue 16 is more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, with respect to 100 parts by mass of the triarylmethane-based dye and the polyacid lake colorant.

Moreover, in the photosensitive colored resin composition of the present invention, C.I. I. Pigment Blue 16, the triarylmethane-based dye, and polyacid may further contain other coloring materials other than the lake coloring materials, but C.I. I. The total content of Pigment Blue 16, the triarylmethane dye and the polyacid lake colorant is preferably 68% by mass or more, and 70% by mass or more, relative to the total content of all colorants. It is preferably 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less.

The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as the coloring layer of the color filter can develop a desired color, and varies depending on the type of coloring material used. is preferably in the range of 10 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less. The average primary particle size of the colorant is within the above range, so that the display device equipped with the color filter produced using the photosensitive colored resin composition of the present invention has high contrast and high quality. can be done.

Further, the average dispersed particle size of the colorant in the photosensitive colored resin composition varies depending on the type of colorant used, but is preferably in the range of 10 nm or more and 100 nm, and is in the range of 15 nm or more and 60 nm or less. is more preferable.
The average dispersed particle size of the colorant in the photosensitive colored resin composition is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is a thing. As for the measurement of the particle size by the laser light scattering particle size distribution meter, the solvent used in the colorant dispersion liquid is appropriately diluted to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times etc.), and can be measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is the volume average particle size.

The total content of the coloring material is preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, relative to the total solid content of the photosensitive colored resin composition. . If it is at least the above lower limit, the colored layer will have a sufficient color density when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm). Moreover, if it is below the said upper limit, while being excellent in storage stability, the coloring layer which has sufficient hardness and adhesiveness with a board|substrate can be obtained. Especially when forming a colored layer having a high colorant concentration, the total content of the colorant is 15% by mass or more and 65% by mass or less, more preferably 25% by mass, based on the total solid content of the photosensitive colored resin composition. It is preferable to mix at a ratio of 60% by mass or more and 60% by mass or more.

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator, and usually a compound having two or more ethylenically unsaturated double bonds is suitable. is preferably a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups.
Such a polyfunctional (meth)acrylate may be appropriately selected from among conventionally known ones and used. Specific examples include those described in JP-A-2013-029832.

One of these polyfunctional (meth)acrylates may be used alone, or two or more thereof may be used in combination. Further, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the photopolymerizable compound has three polymerizable double bonds (trifunctional) or more. Poly(meth)acrylates of trihydric or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferable. Specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth) ) acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate succinic acid-modified products, dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate and the like are preferred. When using a phosphorus atom-containing polyfunctional (meth) acrylate such as tri (2- (meth) acryloyloxyethyl) phosphate, the fading of the lake colorant is easily suppressed, and the brightness after post-baking is preferably increased in terms of ease. .

The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but the photopolymerizable compound is preferably 5 mass% or more with respect to the total solid content of the photosensitive colored resin composition. % by mass or less, more preferably 10% by mass or more and 40% by mass or less. If the content of the photopolymerizable compound is at least the above lower limit, photocuring will proceed sufficiently, and the exposed portion will be able to suppress elution during development. Alkali developability tends to be sufficient when an alkali-soluble resin is included.

[Photoinitiator]
The photoinitiator used in the photosensitive colored resin composition of the present invention includes an oxime ester compound.
In the photosensitive colored resin composition of the present invention, the phthalocyanine pigment C.I. I. By using a combination of a triarylmethane dye and a polyacid lake colorant for Pigment Blue 16, the lake colorant of the triarylmethane dye and polyacid hardly absorbs wavelengths around 300 nm. , C.I. I. Even an initiator having an absorption wavelength overlapping with that of Pigment Blue 16, that is, having an absorption wavelength around 300 nm can provide good curability and can be preferably used.
Therefore, in the present invention, the photoinitiator includes an oxime ester compound, which is an oxime ester photoinitiator having strong absorption around 300 nm, from the viewpoint of improving sensitivity. By using the oxime ester compound, when forming a fine line pattern, in-plane line width variations are easily suppressed. Furthermore, the use of an oxime ester compound tends to improve development resistance and enhance the effect of suppressing the occurrence of water stains. The term "water stain" means that when a component that enhances alkali developability is used, after alkali development and rinsing with pure water, water stain marks are produced. Such water stains disappear after post-baking, so there is no problem with the product. occur. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the visual inspection, the yield of the final color filter product will be lowered, which is a problem.
The oxime ester compound preferably has an aromatic ring, and more preferably has a condensed ring containing an aromatic ring, from the viewpoint of reducing contamination of the photosensitive colored resin composition and contamination of the device due to decomposition products. , a condensed ring containing a benzene ring and a heterocyclic ring.

Oxime ester compounds used as photoinitiators include 1,2-octadione-1-[4-(phenylthio)-, 2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP 2000-80068, JP 2001-233842, JP 2010-527339, JP 2010 -527338, can be appropriately selected from oxime ester photoinitiators described in JP-A-2013-041153 and the like. Commercially available products include Irgacure OXE-01 (manufactured by BASF) having a carbazole skeleton, Adeka Arkles NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Tenryu Denshi New Materials Co., Ltd.), and Adeka having a diphenyl sulfide skeleton. Arkles NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), TR-PBG-365 having a fluorene skeleton (Changzhou Strong Electronic New Materials Co., Ltd.) (manufactured by Sanyo), SPI-04 (manufactured by Samyang), etc. may also be used. In particular, it is preferable to use an oxime ester compound having a diphenylsulfide skeleton or a fluorene skeleton, and more preferably an oxime ester compound having a fluorene skeleton, from the viewpoint of improving brightness. Moreover, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.

If a highly sensitive photoinitiator is used for patterning with a small amount of exposure, the radicals will migrate to the unexposed area after radical generation. Therefore, when patterning the colored layer and forming desired micropores in the colored layer at the same time, the shape of the unexposed portion inside the exposed portion is maintained, and the peripheral portion of the unexposed portion is formed without rippling. was difficult. On the other hand, if an oxime ester compound having a fluorene skeleton is used in the combination of the coloring materials of the present invention, there is an advantage that desired micropores can be easily formed in the colored layer at the same time as the colored layer is patterned. Among them, the combined use of an oxime ester compound having a fluorene skeleton and an oxime ester compound having a diphenyl sulfide skeleton is preferable because the shape of micropores can be easily improved without significantly lowering the brightness and sensitivity. Note that the term "rippling" refers to the problem that straight or curved lines at pattern edges become non-uniform and dimensional accuracy deteriorates.

As for the photoinitiator, the oxime ester compound and a photoinitiator different from the oxime ester compound may be appropriately selected and used in combination as long as the effects of the present invention are not impaired.
As the photoinitiator different from the oxime ester compound, one or a combination of two or more of conventionally known various initiators can be used.
Examples of photoinitiators different from oxime ester compounds include α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and the like. Specifically, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (eg Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino) -1-(4-morpholinophenyl)-1-butanone (eg, Irgacure 369, manufactured by BASF), 4,4′-bis(diethylamino)benzophenone (eg, Hycure ABP, manufactured by Kawaguchi Yakuhin), diethylthioxanthone, and the like. be done.

For example, in the photoinitiator, it is preferable to use an oxime ester compound in combination with an α-aminoacetophenone photoinitiator from the viewpoint of suppressing water staining and improving sensitivity. A photoinitiator having a tertiary amine structure such as α-aminoacetophenone has a tertiary amine structure, which is an oxygen quencher, in its molecule. can be improved.
Further, in the photoinitiator, it is preferable to combine an oxime ester compound with a thioxanthone photoinitiator from the viewpoint of adjusting sensitivity, suppressing water staining, and improving development resistance. Combining a photoinitiator is preferable because the brightness and development resistance are improved, the sensitivity is easily adjusted, the effect of suppressing the occurrence of water staining is high, and the development resistance is improved.

The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, relative to the total solid content of the photosensitive colored resin composition, It is preferably in the range of 0.1 mass % or more and 12.0 mass % or less, more preferably 1.0 mass % or more and 8.0 mass % or less. When the content is at least the above lower limit, photocuring proceeds sufficiently to suppress the elution of the exposed portion during development. can be suppressed.
In addition, the solid content is everything other than the solvent, and liquid photopolymerizable compounds and the like are also included.

Further, in the photosensitive colored resin composition of the present invention, when the photoinitiator contains another photoinitiator different from the oxime ester compound, the total content of the oxime ester compound is the same as the photoinitiator used in the present invention. It is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 70 parts by mass or more in the total 100 parts by mass of the above.
On the other hand, from the viewpoint of sufficiently exhibiting the combined effect with the other photoinitiator, the total content of the oxime ester compound is 95 parts by mass or less in 100 parts by mass of the total photoinitiator used in the present invention. is preferably 85 parts by mass or less.

[solvent]
The solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive colored resin composition and is capable of dissolving or dispersing them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such as ethyl lactate and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 -glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA) and carbitol acetate; Diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether , dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; tetrahydrofuran and the like. Cyclic ether solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; aromatic hydrocarbons such as toluene and xylene organic solvents such as Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of solubility of other components. Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, and ethyl ethoxypropionate. , ethyl lactate, and 3-methoxybutyl acetate are preferably one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.

In the photosensitive colored resin composition according to the present invention, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. With respect to the total amount of the photosensitive colored resin composition containing the solvent, it is usually preferably in the range of 55% by mass or more and 95% by mass or less, and among them, it is in the range of 65% by mass or more and 88% by mass or less. is more preferable. When the content of the solvent is within the above range, excellent applicability can be obtained.

[Dispersant]
In the photosensitive colored resin composition of the present invention, the coloring material is preferably dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersing agent, for example, a cationic, anionic, nonionic, amphoteric, silicone or fluorine surfactant can be used. Among surfactants, polymer dispersants are preferred because they can be uniformly and finely dispersed.

Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co)polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides obtained by reacting poly(lower alkyleneimine) with free carboxy group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and free carboxy (a reaction product obtained by reacting one or more compounds selected from three compounds: polyesters, polyamides, or cocondensates of esters and amides (polyesteramides) having groups), and the like.

As the polymer dispersant, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value is preferable because it can suitably disperse the coloring material and has good dispersion stability. Among them, a polymeric dispersant containing a polymer containing a structural unit having a tertiary amine is preferable from the viewpoint of good dispersibility, no deposition of foreign matter during coating film formation, and improved brightness and contrast.
A structural unit having a tertiary amine is a site having affinity with the coloring material. A polymer containing a structural unit having a tertiary amine usually contains a structural unit that serves as a site having affinity with a solvent. As a polymer containing a structural unit having a tertiary amine, among others, a block portion containing a structural unit having a tertiary amine (hereinafter sometimes referred to as A block) and a block portion having solvent affinity ( Hereinafter, it may be referred to as B block.) is preferable in terms of excellent heat resistance and ability to form a coating film with high brightness.

The structural unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may constitute the main chain.
Among them, a structural unit having a tertiary amine in the side chain is preferable. Among them, a structural unit represented by the following general formula (I) is preferable because the main chain skeleton is difficult to thermally decompose and has high heat resistance. is more preferable.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ｑは、２価の連結基、Ｒ^２は、炭素数１～８のアルキレン基、－［ＣＨ（Ｒ^５）－ＣＨ（Ｒ^６）－Ｏ］_ｘ－ＣＨ（Ｒ^５）－ＣＨ（Ｒ^６）－又は－［（ＣＨ_２）_ｙ－Ｏ］_ｚ－（ＣＨ_２）_ｙ－で示される２価の有機基、Ｒ^３及びＲ^４は、それぞれ独立に、置換されていてもよい鎖状又は環状の炭化水素基を表すか、Ｒ^３及びＲ^４が互いに結合して環状構造を形成する。Ｒ^５及びＲ^６は、それぞれ独立に水素原子又はメチル基である。
ｘは１～１８の整数、ｙは１～５の整数、ｚは１～１８の整数を示す。）

(In general formula (I), R ¹ is a hydrogen atom or a methyl group, Q is a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, —[CH(R ⁵ )—CH( R ⁶ )—O] _x —CH(R ⁵ )—CH(R ⁶ )— or a divalent organic group represented by —[(CH ₂ ) _y —O] _z —(CH ₂ ) _y —, R ³ and R ⁴ each independently represent an optionally substituted chain or cyclic hydrocarbon group, or R ³ and R ⁴ combine to form a cyclic structure, R ⁵ and R ⁶ are Each independently represents a hydrogen atom or a methyl group.
x is an integer of 1-18, y is an integer of 1-5, and z is an integer of 1-18. )

The divalent linking group Q in the general formula (I) includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, an ether group having 1 to 10 carbon atoms (- R'--OR''-: R' and R'' are each independently an alkylene group), combinations thereof, and the like. Among them, Q is a -COO- group or -CONH- in view of the heat resistance of the obtained polymer, the solubility in propylene glycol monomethyl ether acetate (PGMEA) which is suitably used as a solvent, and the fact that it is a relatively inexpensive material. It is preferably a group.

The divalent organic group R ² in the general formula (I) is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH(R ⁶ )-O] _x -CH(R ⁵ )-CH. (R ⁶ )— or —[(CH ₂ ) _y —O] _z —(CH ₂ ) _y —. The alkylene group having 1 to 8 carbon atoms may be linear or branched.
^R5 and ^R6 are each independently a hydrogen atom or a methyl group.
From the standpoint of dispersibility, R ² is preferably an alkylene group having 1 to 8 carbon atoms. Among them, R ² is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. groups are more preferred.

Examples of the cyclic structure formed by combining R ³ and R ⁴ in the general formula (I) include a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensing two of these. be done. The nitrogen-containing heterocyclic ring is preferably non-aromatic, more preferably saturated.

Examples of structural units represented by the general formula (I) include alkyl group-substituted amino groups such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate and diethylaminopropyl (meth)acrylate. Examples include group-containing (meth)acrylates and alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.

Moreover, as will be described later, at least part of the amino groups of the constituent units having the tertiary amine may be salt-formed with a salt-forming agent.

As the structural unit contained in the solvent affinity block portion, a conventionally known structural unit copolymerizable with the general formula (I) can be appropriately selected and used.
Also, for example, the B block may be similar to the B block of WO2016/104493.

In addition, among others, the B block contains at least one selected from a structural unit represented by the following general formula (B1) and a structural unit represented by the following general formula (B2). It is preferable from the viewpoint that a decrease can be suppressed, a colored layer with high brightness can be formed, and cracks in the ITO film formed adjacent to the colored layer can be suppressed.

（一般式（Ｂ１）中、Ａ^１は２価の連結基、Ｒ^１１は酸素原子を含んでいても良い２、３若しくは４価の脂肪族炭化水素基又は炭素原子、Ｒ^１０及びＲ^１２はそれぞれ独立に水素原子又はメチル基を表す。ｎは１、２又は３である。）

(In the general formula (B1), A ¹ is a divalent linking group, R ¹¹ is a divalent, trivalent or tetravalent aliphatic hydrocarbon group optionally containing an oxygen atom or a carbon atom, R ¹⁰ and R ¹² are Each independently represents a hydrogen atom or a methyl group, and n is 1, 2 or 3.)

（一般式（Ｂ２）中、Ａ^２は２価の連結基、Ａ^３及びＡ^４はそれぞれ独立に、２、３又は４価の連結基、Ｒ^１３は酸素原子及び窒素原子から選ばれる少なくとも一種を含んでいても良い２価の炭化水素基、Ｒ^１４、Ｒ^１６、Ｒ^１８及びＲ^１９はそれぞれ独立に、酸素原子を含んでいても良い２価の脂肪族炭化水素基、Ｒ^１０、Ｒ^１５及びＲ^１７はそれぞれ独立に、水素原子又はメチル基を表す。ｎ^１は０、１、２又は３、ｎ^２は０又は１、ｎ^３は０、１又は２を表し、ｎ^１＋ｎ^２は１、２又は３であり、ｎ^１＋ｎ^２＋ｎ^３は１、２又は３である。ｍ^１は１、２又は３、ｍ^２は０、１又は２を表し、ｍ^１＋ｍ^２は１、２又は３である。）

(In the general formula (B2), A ² is a divalent linking group, A ³ and A ⁴ are each independently a divalent, trivalent or tetravalent linking group, and R ¹³ is at least one selected from an oxygen atom and a nitrogen atom. R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a divalent aliphatic hydrocarbon group which may contain an oxygen atom, R ¹⁰ , R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, n ¹ represents 0, 1, 2 or 3, n ² represents 0 or 1, n ³ represents 0, 1 or 2, n ¹ + n ² is 1, 2 or 3, n ¹ +n ² +n ³ is 1, 2 or 3, m ¹ is 1, 2 or 3, m ² is 0, 1 or 2, m ¹ +m ² is 1 , 2 or 3.)

As A ¹ in the general formula (B1), the divalent linking group in A ² , A ³ and A ⁴ in the general formula (B2), and the trivalent or tetravalent linking group in A ³ and A ⁴ , For example, an aliphatic hydrocarbon group, an aromatic group, a -CONH- group, a -COO- group, and a combination thereof, in the carbon chain O (oxygen atom), S (sulfur atom), N (nitrogen atom) may be included and may have a substituent. The tetravalent linking group may be a carbon atom.
The aliphatic hydrocarbon group for A ¹ , A ² , A ³ and A ⁴ may be linear, branched or cyclic and may be saturated or unsaturated, may have a substituent, and may have a carbon chain A heteroatom such as O, S, N may be contained therein. For example, the carbon chain may contain an ether group, a thioether group, a carbonyl group, an oxycarbonyl group, an amide group, or the like. Moreover, a halogen atom, an alkoxy group, a phenoxy group, etc. are mentioned as said substituent.
The aromatic group for A ¹ , A ² , A ³ and A ⁴ includes a monocyclic or polycyclic aromatic group, optionally having a substituent, and a heterocyclic ring containing O, S, N There may be. Examples of aromatic groups include groups containing a benzene ring and naphthalene ring, and among these, groups containing a benzene ring are preferred. Substituents are the same as those mentioned above.
The combination of the aliphatic hydrocarbon group and the aromatic group in A ¹ , A ² , A ³ and A ⁴ includes a structure in which the aliphatic hydrocarbon group and the aromatic group are directly bonded, and the aliphatic hydrocarbon A structure in which the group and the aromatic group are linked by a linking group containing a hetero atom such as the ether group is mentioned.
As the divalent linking group for A ¹ in the general formula (B1) and A ² in the general formula (B2), among others, a divalent group containing a —COO— group and an alkylene group having 1 to 10 carbon atoms is preferred, and a divalent linking group that is a combination of a —COO— group and an alkylene group having 1 to 10 carbon atoms is more preferred. Among them, an alkylene group having 1 to 10 carbon atoms is preferable as the divalent linking group for A ³ and A ⁴ in the general formula (B2). The alkylene group in A ¹ in the general formula (B1) and A ² , A ³ and A ⁴ in the general formula (B2) may be linear, branched or cyclic. shape is preferred. In addition, the alkylene group may have a substituent, and may contain a heteroatom such as O, S, N, etc. in the carbon chain.
As the trivalent linking group for A ³ and A ⁴ in the general formula (B2), among them, an atomic group remaining after removing 3 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 10 carbon atoms is preferable, More preferred are atomic groups remaining after 3 hydrogen atoms are removed from an aliphatic saturated hydrocarbon having 1 to 5 carbon atoms. These aliphatic saturated hydrocarbon groups may have a substituent, and may contain a heteroatom such as O, S or N in the carbon chain.
The tetravalent linking group for A ³ and A ⁴ in the general formula (B2) includes, among others, an atomic group or a carbon atom remaining after removing 4 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 10 carbon atoms. is preferred, and the remaining atomic groups or carbon atoms obtained by removing 4 hydrogen atoms from an aliphatic saturated hydrocarbon having 1 to 5 carbon atoms are more preferred. These aliphatic saturated hydrocarbon groups may have a substituent, and may contain a heteroatom such as O, S or N in the carbon chain.

The divalent hydrocarbon group which may contain at least one selected from an oxygen atom and a nitrogen atom in R ¹³ of the general formula (B2) is either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. may include, for example, linear, branched or cyclic alkylene and alkenylene groups, arylene groups, and combinations thereof, which may contain at least one selected from oxygen atoms and nitrogen atoms, and in the carbon chain , -CONH- group, -COO- group, ether group and the like may be included.

Examples of divalent aliphatic hydrocarbon groups which may contain an oxygen atom in R ¹¹ in general formula (B1) and R ¹⁴ , R ¹⁶ , R ¹⁸ and R ¹⁹ in general formula (B2) include , linear, branched or cyclic alkylene groups and alkenylene groups, and the carbon chain may contain an ether group or the like. Among them, an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom is preferable, and an alkylene group having 2 to 10 carbon atoms which may contain an oxygen atom is more preferable.
In addition, when there are a plurality of R ¹⁴ , R ¹⁶ , R ¹⁸ or R ¹⁹ in the general formula (B2), the plurality of R ¹⁴ , the plurality of R ¹⁶ , the plurality of R ¹⁸ and the plurality of R ¹⁹ are each They may be the same or different.
Further, the trivalent or tetravalent aliphatic hydrocarbon group which may contain an oxygen atom in R ¹¹ of the general formula (B1) includes, for example, linear, branched or cyclic aliphatic saturated hydrocarbons or aliphatic Examples include aliphatic hydrocarbon groups or carbon atoms remaining after 3 or 4 hydrogen atoms are removed from a group unsaturated hydrocarbon, and an ether group or the like may be included in the carbon chain. Among them, the remaining aliphatic saturated hydrocarbon group or carbon after removing 3 or 4 hydrogen atoms from a linear, branched or cyclic saturated aliphatic hydrocarbon having 1 to 10 carbon atoms which may contain an oxygen atom Atoms are preferred.

R ¹⁰ and R ¹² in the general formula (B1), and R ¹⁰ , R ¹⁵ and R ¹⁷ in the general formula (B2) are, among others, highly reactive, improve the film strength, and improve the brightness and brightness of the colored layer. A hydrogen atom is preferable from the viewpoint of improving the crack resistance of the ITO film.
In addition, when there are multiple R ¹² in the general formula (B1), and when there are multiple R ¹⁵ or R ¹⁷ in the general formula (B2), multiple R ¹² , multiple R ¹⁵ and multiple Each R ¹⁷ may be the same or different.

In the general formula (B2), n ¹ + n ² >n from the viewpoints of the hydroxyl value of the dispersant being likely to be appropriate, the solvent re-solubility and development adhesion, and the brightness and crack resistance of the ITO film. ³ is preferred and m ¹ >m ² is preferred.

The number of (meth)acryloyl groups in the side chain of at least one selected from the structural units represented by the general formula (B1) and the structural units represented by the general formula (B2) is not particularly limited. , from the viewpoint of improving the crack resistance of the ITO film, it is preferably 2 or more, while from the viewpoint of dispersion stability, it is preferably 6 or less, and more preferably 3 or less. , one or two.

At least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) is, for example, a monomer that induces the structural unit represented by the general formula (I) and an unsaturated double bond that can be copolymerized with a monomer having a hydroxyl group (hereinafter referred to as a "hydroxyl group-containing monomer") to introduce a structural unit having a hydroxyl group, and an isocyanate group and a (meth) acryloyl group. The isocyanate group of the compound (hereinafter referred to as "isocyanate group-containing (meth)acrylate") can be introduced by reacting the hydroxyl group in the structural unit.
Further, the structural unit represented by the general formula (B2) is, for example, a hydroxyl group-containing monomer is used to introduce a structural unit having a hydroxyl group, and one isocyanate group of the diisocyanate compound reacts with the hydroxyl group in the structural unit. and reacting the other isocyanate group of the diisocyanate compound with the hydroxyl group of the compound having a hydroxyl group and a (meth)acryloyl group.
In addition, the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.
Since the hydroxyl group and the isocyanate group are highly reactive, the reaction temperature can be lowered to about 70 to 90° C., and there is no need to use an amine catalyst, the structure represented by the general formula (B1) is obtained by the above method. By introducing at least one selected from units and structural units represented by the general formula (B2), yellowing due to heating and catalysts during the reaction can be suppressed, so yellowing of the colored layer is also suppressed. and the brightness of the colored layer can be improved. Moreover, since the hydroxyl value can be easily adjusted in the above introduction method, solvent re-solubility and the like can be improved by adjusting the hydroxyl value to an appropriate value.

The hydroxyl group-containing monomer is not particularly limited as long as it is a monomer having an unsaturated double bond copolymerizable with the monomer from which the structural unit represented by the general formula (I) is derived, and at least one hydroxyl group. , For example, 2-hydroxyethyl (meth) acrylate, 2 (or 3)-hydroxypropyl (meth) acrylate, 2 (or 3 or 4)-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, etc. Hydroxyalkyl (meth)acrylates, alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, hydroxyaryloxyalkyl (meth)acrylates such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, hydroxyalkoxyalkyls (meth)acrylate monomers having a hydroxyl group such as (meth)acrylate, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, ε-caprolactone 1 mol adduct of 2-hydroxyethyl(meth)acrylate; N-(hydroxyalkyl)(meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide (Meth)acrylamide-based monomers having a hydroxyl group such as; vinyl ether-based monomer having a hydroxyl group; hydroxyalkyl allyl ether such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, 2- (or 3- or 4-) hydroxybutyl allyl ether, etc. Among them, a (meth)acrylate monomer having a hydroxyl group is preferable, and from the viewpoint of improving developability, it has a primary hydroxyl group. It is preferable to having a hydroxyl group. In addition, the primary hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the secondary hydroxyl group is a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a secondary carbon atom. In addition, from the viewpoint of improving the development adhesion, it is preferable to use a hydroxyl group-containing monomer in which the glass transition temperature (Tgi) of the homopolymer of each monomer is 0° C. or higher, and further 10° C. or higher. It is preferred to use hydroxyl group-containing monomers.
The (meth)acrylate-based monomer having a hydroxyl group is at least one selected from hydroxyalkyl (meth)acrylates, hydroxyarylalkyl (meth)acrylates, hydroxyalkoxyalkyl (meth)acrylates and hydroxyaryloxyalkyl (meth)acrylates. more preferably at least one selected from hydroxyalkyl (meth)acrylates and hydroxyaryloxyalkyl (meth)acrylates, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and 2 -hydroxy-3-phenoxypropyl (meth)acrylate is particularly preferred.

Examples of the isocyanate group-containing (meth)acrylate used when introducing the structural unit represented by the general formula (B1) include 2-isocyanatoethyl (meth)acrylate and 3-isocyanatopropyl (meth) Acrylates, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, (meth)acrylic acid 2-(2- isocyanatoethoxy)ethyl, 1,1-(bisacryloyloxymethyl)ethyl isocyanate and derivatives thereof. Examples of such derivatives include compounds having isocyanate groups masked with a blocking agent and at least one (meth)acryloyl group, such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate. , 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl methacrylate, and the like.
Examples of these commercially available products include Karenz AOI (registered trademark), Karenz MOI (registered trademark), AOI-VM (registered trademark), Karenz MOI-EG (registered trademark), Karenz BEI (registered trademark), and Karenz MOI-BP. (registered trademark), Karenz MOI-BM (registered trademark) (manufactured by Showa Denko KK), and the like.

As the isocyanate group-containing (meth)acrylate used when introducing the structural unit represented by the general formula (B2), for example, a hydroxyl group-containing (meth)acrylate and a diisocyanate compound having a molar ratio of about 1:1 reaction products.
The hydroxyl-containing (meth)acrylate in the reaction product includes, for example, a (meth)acrylate-based monomer having a hydroxyl group that can be used as the hydroxyl-containing monomer, and a hydroxyl-containing polyfunctional (meth)acrylate. can be done. A hydroxyl group-containing polyfunctional (meth)acrylate is a compound having at least one hydroxyl group and two or more (meth)acryloyl groups, and is not particularly limited. Those having 2 to 5 groups are preferred. Specific examples of hydroxyl group-containing polyfunctional (meth)acrylates include, for example, trimethylolpropane di(meth)acrylate, di- or tri-(meth)acrylate of pentaerythritol, di-, tri-, tetra- or penta(meth)-acrylate of dipentaerythritol. acrylates and the like.
Examples of diisocyanate compounds include hexamethylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate, m- or p-xylylene diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, lysine diisocyanate, pyridinediyl isocyanate and the like.

The isocyanate group-containing (meth)acrylate preferably contains 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more and 0.1 equivalent of isocyanate group with respect to 1 equivalent of hydroxyl group of the hydroxyl group-containing monomer. It is preferable to use it so that it is 8 equivalents or less from the viewpoint of easily adjusting the hydroxyl value to an appropriate value, development adhesion, resolubility in a solvent, and adhesion of the colored resin composition.

In addition, the isocyanate group-containing (meth)acrylate has a (meth)acryloyl group of preferably 0.1 equivalent or more and 3.0 equivalent or less, more preferably 0.15 equivalent, relative to 1 equivalent of hydroxyl group of the hydroxyl group-containing monomer. From the viewpoint of brightness and crack resistance of the ITO film, it is preferable to use the equivalent of 2.5 equivalents or less.

Further, the structural unit represented by the general formula (B2) is reacted with one isocyanate group of the diisocyanate compound with the hydroxyl group of the structural unit derived from the hydroxyl group-containing monomer, and the other isocyanate group of the diisocyanate compound is further In the case of a structural unit introduced by reacting a hydroxyl-containing (meth)acrylate, the hydroxyl-containing (meth)acrylate here is a reaction of the hydroxyl-containing (meth)acrylate and a diisocyanate compound at a molar ratio of about 1:1. The same ones as described for the product can be used. In this case, one isocyanate group of the diisocyanate compound is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more and 0.1 equivalent or more, relative to 1 equivalent of hydroxyl group of the structural unit derived from the hydroxyl group-containing monomer. It is preferable to use a diisocyanate compound with an equivalent weight of 8 or less in terms of easily adjusting the hydroxyl value to an appropriate value, development adhesion, solvent re-solubility, and adhesion of the colored resin composition.
Further, the hydroxyl group of the hydroxyl group-containing (meth)acrylate is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more and 0.8 equivalent with respect to 1 equivalent of the other isocyanate group of the diisocyanate compound. It is preferable to use a hydroxyl group-containing (meth)acrylate so as to satisfy the following.

In the block copolymer, the content of at least one selected from the structural units represented by the general formula (B1) and the structural units represented by the general formula (B2) is not particularly limited. , and from the viewpoint of the effect of suppressing cracks in the ITO film formed adjacent to the colored layer, it is preferably 1% by mass or more with respect to the total mass of all structural units of the block copolymer. It is more preferably 4% by mass or more, and more preferably 4% by mass or more. On the other hand, from the viewpoint of improving plate-making properties, it is preferably 35% by mass or less, and 30% by mass or less. More preferably, it may be 20% by mass or less.
At least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) may consist of one type or two or more types of structural units. May contain units.

In addition, the (meth)acryloyl group equivalent in the side chain of the block copolymer before salt formation is preferably in the range of 100 to 6,000, more preferably in the range of 250 to 4,500. If the (meth)acryloyl group equivalent is at least the above lower limit, the brightness of the colored layer and the crack resistance of the ITO film are further improved, and if it is at most the above upper limit, alkali developability, coloring material dispersibility, and plate-making properties improves.
Here, the (meth)acryloyl group equivalent is the weight average molecular weight per mole of (meth)acryloyl groups in the block copolymer before salt formation, and is represented by the following formula (1).

Formula (1)
(Meth) acryloyl group equivalent (g / mol) = W' (g) / M' (mol)
(In formula (1), W ' represents the mass (g) of the block copolymer before salt formation, and M ' is contained in the block copolymer W ' (g) before salt formation (meta) represents the number of moles (mol) of acryloyl groups.)

The (meth)acryloyl group equivalent is, for example, the number of (meth)acryloyl groups contained per 1 g of the block copolymer before salt formation, in accordance with the iodine value test method described in JIS K 0070: 1992. may be calculated by measuring

In addition, in the synthesis of the block copolymer used in the present invention, by appropriately adjusting the charge amount of each structural unit, the block copolymer has a desired content ratio of the structural units and a copolymer having desired performance. can be combined. Among them, using the hydroxyl group-containing monomer and the isocyanate group-containing (meth)acrylate, at least selected from the structural units represented by the general formula (B1) and the structural units represented by the general formula (B2) When one type is introduced, in the synthesis of the block copolymer, the charging amount of the hydroxyl group-containing monomer is 5% by mass or more with respect to the total amount of the monomer, which improves the brightness of the colored layer and the crack resistance of the ITO film. and more preferably 10% by mass or more. From the viewpoint of solvent resolubility, the amount of the hydroxyl group-containing monomer charged is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of the monomers. In addition, the amount of the isocyanate group-containing (meth)acrylate to be charged is 10% by mass with respect to the amount of the hydroxyl group-containing monomer to improve the brightness of the colored layer and the crack resistance of the ITO film and the adhesion. It is preferably 15% by mass or more, and preferably 120% by mass or less, preferably 90% by mass, from the viewpoint of solvent re-solubility, development adhesion, brightness, and crack resistance of the ITO film. % or less, and even more preferably 85 mass % or less.

In the present invention, the dispersant is a polymer having a structure represented by the general formula (I) and an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less. It is preferable from the viewpoint of preventing precipitation and improving the brightness and contrast.
When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and alkali developability and solvent re-solubility are also excellent. Amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of sample, and can be measured by the method defined in JIS-K7237: 1995. . When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so the block copolymer itself used as the dispersant can be measured.

The acid value of the dispersant used in the present invention is preferably 0 mgKOH/g from the viewpoints of further improving solvent re-solubility and development adhesion, substrate adhesion and dispersion stability. It is believed that the lower the acid value, the less susceptible to erosion by a basic developer, and the better the development adhesion. On the other hand, from the viewpoint of the effect of suppressing development residue, it is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. Further, the acid value of the dispersant used in the present invention is preferably 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesion and solvent re-solubility. Above all, the acid value of the dispersant is more preferably 12 mgKOH/g or less, and even more preferably 8 mgKOH/g or less, from the viewpoint of good development adhesion and solvent re-solubility.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is 0 mgKOH from the viewpoint of further improving solvent resolubility and development adhesion, and from the viewpoint of substrate adhesion and dispersion stability. /g is preferred. On the other hand, from the viewpoint of the effect of suppressing development residue, it is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. In addition, the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less, from the viewpoint of good development adhesion and solvent re-solubility. Preferably, it is even more preferably 8 mgKOH/g or less.

Moreover, in the present invention, the glass transition temperature of the dispersant is preferably 30° C. or higher from the viewpoint of improving adhesion to development. That is, the glass transition temperature of the dispersant is preferably 30° C. or higher, regardless of whether the dispersant is a pre-salt block copolymer or a salt-type block copolymer. If the glass transition temperature of the dispersant is low, it will be close to the temperature of the developing solution (usually about 23° C.), and there is a risk that the development adhesion will be reduced. It is presumed that this is because when the glass transition temperature approaches the developer temperature, the movement of the dispersant increases during development, and as a result, the development adhesion deteriorates. When the glass transition temperature is 30° C. or higher, the molecular movement of the dispersant during development is suppressed, so it is presumed that the decrease in development adhesion is suppressed.
The glass transition temperature of the dispersant is preferably 32° C. or higher, more preferably 35° C. or higher, from the viewpoint of development adhesion. On the other hand, the temperature is preferably 200° C. or less from the viewpoint of operability during use, such as facilitating accurate weighing.
The glass transition temperature of the dispersant in the present invention can be obtained by measuring by differential scanning calorimetry (DSC) according to JIS K7121.
Also, the glass transition temperature (Tg) of the block part and the block copolymer can be calculated by the following formula.
1/Tg=Σ(Xi/Tgi)
Here, it is assumed that the block part is copolymerized with n monomer components from i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ takes the sum from i=1 to n. As the homopolymer glass transition temperature value (Tgi) of each monomer, the value in Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.

Further, the glass transition temperature of the dispersant used in the present invention is set to a specific value or higher, and the development adhesiveness is improved, so the glass transition temperature value (Tgi) of the homopolymer of the monomer is 10 ° C. or higher. is preferably 75% by mass or more, more preferably 85% by mass or more, in the B block in total.

In the block copolymer, the ratio m/n between the number m of the constituent units of the A block and the number n of the constituent units of the B block is in the range of 0.05 to 1.5. and more preferably in the range of 0.1 to 1.0 from the viewpoint of dispersibility and dispersion stability of the colorant.

The weight-average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, more preferably 2000 to 15000, from the viewpoint of improving the dispersibility and dispersion stability of the colorant. It is more preferably 3,000 to 12,000.
Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) as a standard polystyrene conversion value. Note that macromonomers, salt-type block copolymers, and graft copolymers, which are raw materials for block copolymers, are also processed under the above conditions.

In the present invention, from the viewpoint of the dispersibility and dispersion stability of the coloring material, at least part of the amino groups in the polymer containing the structural unit having the tertiary amine, an organic acid compound or a halogenated hydrocarbon It is also preferable to use, as a dispersant, a salt formed by a salt-forming agent such as a salt-forming agent (such a polymer may be hereinafter referred to as a salt-type polymer).
Among them, the polymer containing a structural unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. and excellent dispersion stability. Specific examples of the organic acid compound used in such a dispersant include, for example, organic acid compounds described in JP-A-2012-236882 and the like as suitable ones.
The halogenated hydrocarbon is preferably at least one selected from allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

The content when using a dispersant is not particularly limited as long as it can uniformly disperse the coloring material. It can be used at a mass % or more and 40 mass % or less. Further, it is preferably blended in an amount of 2% by mass or more and 30% by mass or less, particularly preferably 3% by mass or more and 25% by mass or less, based on the total solid content of the photosensitive colored resin composition. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable.

[Alkali-soluble resin]
In the photosensitive colored resin composition of the present invention, it is preferable to use an alkali-soluble resin from the viewpoint of imparting developability. The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
A preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. Specifically, for example, an acrylic copolymer having a carboxy group, a styrene-acrylic copolymer having a carboxy group, and the like. acrylic resins, epoxy (meth)acrylate resins having a carboxy group, and the like.

Among these, particularly preferred are those having a carboxy group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. In the case of containing a photopolymerizable functional group, in the step of curing the resin composition during the production of the color filter, the alkali-soluble resins are cross-linked, or the alkali-soluble resin and the photopolymerizable compound such as a polyfunctional monomer are crosslinked. can form The film strength of the cured film is further improved, the development resistance is improved, and the heat shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.
A method for introducing an ethylenic double bond into an alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of the alkali-soluble resin to introduce an ethylenic double bond into the side chain. Alternatively, a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and an ethylenic double bond is introduced into the side chain. etc.

Moreover, the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and substrate adhesion is improved.
Examples of such a hydrocarbon ring include an optionally substituted aliphatic hydrocarbon ring, an optionally substituted aromatic hydrocarbon ring, and a combination thereof. may have a substituent such as an alkyl group, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, or a halogen atom.
The hydrocarbon ring may be contained as a monovalent group or may be contained as a divalent or higher group.

Specific examples of hydrocarbon rings include aliphatic rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane. Hydrocarbon rings; Aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; Chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene, and cardo structures (9,9-diarylfluorene ); a group in which a part of these groups is substituted with a substituent, and the like.
Examples of the substituents include alkyl groups, cycloalkyl groups, alkylcycloalkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and halogen atoms.

When an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is also preferably improved.
Further, when the cardo structure is contained, the curability of the colored layer is improved, the fading of the coloring material is suppressed, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable.

Acrylic resins such as acrylic copolymers having a structural unit having a carboxy group and styrene-acrylic copolymers having a carboxy group are, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co)polymer obtained by (co)polymerizing other polymerizable monomers by a known method.
Carboxy group-containing ethylenically unsaturated monomers include, for example, (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. be done. Also, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. Anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as precursors of the carboxy group. Among them, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin in the present invention is a carboxy group-containing copolymer such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring. Is preferably, a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond acrylic copolymer and styrene - carboxy group-containing such as acrylic copolymer A copolymer is more preferred.

Ethylenically unsaturated monomers having a hydrocarbon ring include, for example, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (Meth)acrylates, styrene, etc., and from the point that the effect of maintaining the cross-sectional shape of the colored layer after development is large even in heat treatment, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl ( At least one selected from meth)acrylate, benzyl (meth)acrylate, and styrene is preferably used.

The carboxy group-containing copolymer may further contain other structural units such as a structural unit having an ester group such as methyl (meth)acrylate and ethyl (meth)acrylate. A structural unit having an ester group functions not only as a component that suppresses the alkali solubility of the photosensitive colored resin composition, but also as a component that improves the solubility in a solvent and the solvent re-solubility.

The carboxy group-containing copolymer can be made into an alkali-soluble resin having desired performance by appropriately adjusting the amount of each structural unit charged.
The amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the monomers in order to obtain a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, and 40% by mass or less relative to the total amount of the monomer. It is more preferable to have

Further, in a carboxyl group-containing copolymer such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having an ethylenic double bond, which is more preferably used as an alkali-soluble resin, the epoxy group and ethylene The amount of the compound having a double bond is preferably 10% by mass or more and 95% by mass or less, preferably 15% by mass or more and 90% by mass or less, based on the charged amount of the carboxy group-containing ethylenically unsaturated monomer. more preferred.

A preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When it is 1,000 or more, the binder function after curing is improved, and when it is 50,000 or less, pattern formation becomes good during development with an alkaline developer.
The weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

The epoxy (meth)acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth)acrylate obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used.
As the epoxy (meth)acrylate resin having a carboxyl group, it is preferable to have the above-mentioned hydrocarbon ring in the molecule. Among them, those containing a cardo structure improve the curability of the colored layer and prevent the colorant from fading. It is preferable from the viewpoint of suppressing it and increasing the residual film rate of the colored layer.
Epoxy (meth)acrylate resins having a carboxy group may be used alone or in combination of two or more.

From the standpoint of developability (solubility) in an alkaline aqueous solution used as a developer, it is preferable to select and use an alkali-soluble resin having an acid value of 50 mgKOH/g or more. The alkali-soluble resin preferably has an acid value of 70 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of developability (solubility) in an alkaline aqueous solution used as a developer and adhesion to a substrate. It is preferably 80 mgKOH/g or more and 280 mgKOH/g or less.
In addition, in the present invention, the acid value can be measured according to JIS K 0070:1992.

The ethylenically unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and provides the effect of excellent adhesion to the substrate. From the point of view, it is preferably in the range of 100 to 2000, more preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Also, if it is 100 or more, the ratio of other structural units such as structural units having a carboxy group and structural units having a hydrocarbon ring can be relatively increased, so that excellent developability and heat resistance can be obtained. there is
Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Formula (1)
Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenic double bonds contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent is determined, for example, by measuring the number of ethylenic double bonds contained per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992. can be calculated.

Alkali-soluble resin used in the photosensitive colored resin composition may be used alone, may be used in combination of two or more, the content is not particularly limited, photosensitive colored resin The content of the alkali-soluble resin is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less, relative to the total solid content of the composition. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.

[Antioxidant]
It is preferable that the photosensitive colored resin composition according to the present invention further contains an antioxidant from the viewpoint of improving the heat resistance, suppressing the fading of the coloring material, and improving the luminance. The photosensitive colored resin composition according to the present invention contains an antioxidant in combination with an oxime ester compound, so that excessive radical chains in the micropores do not impair the curability when forming the micropores in the cured film. Since the reaction can be controlled, micropores having a desired shape can be formed more easily.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the points and the shape of the micropores. It may be a latent antioxidant as described in WO2014/021023.

Hindered phenol antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF), 1,3 ,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5- Di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical) ), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate ( trade name: Irgamod 195, manufactured by BASF) and the like. Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance.

The content of the antioxidant is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, based on 100 parts by mass of the total solid content in the colored resin composition. More preferably, the amount is not less than 5.0 parts by mass and not more than 5.0 parts by mass. If it is at least the above lower limit value, it is excellent in heat resistance and light resistance. On the other hand, if it is the above upper limit or less, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

When an antioxidant is used in combination with the oxime ester compound, the content of the antioxidant is 1 part by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the total amount of the oxime ester compound. is preferably 3 parts by mass or more and 80 parts by mass or less, and even more preferably 5 parts by mass or more and 45 parts by mass or less. Within the above range, the effect of the above combination is excellent.

[Optional additional ingredients]
The photosensitive colored resin composition of the present invention may optionally contain various additives. Additives include, for example, mercapto compounds, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
Specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.

In the photosensitive colored resin composition of the present invention, the P / V ratio ((colorant component mass in the composition) / (solid content mass other than the colorant component in the composition) ratio) is the blue colored resin composition When used as a product, the P/V ratio is preferably 0.20 or more, more preferably 0.28 or more, and still more preferably 0.35 or more from the viewpoint of desired color development. preferable. On the other hand, it is preferably 0.65 or less from the viewpoint of excellent solvent re-solubility, development residue, development adhesion, development resistance, suppression effect of development chipping and unevenness, contrast, suppression of micropore blistering, etc. It is more preferably 0.50 or less, and even more preferably 0.45 or less.

[Method for producing a photosensitive colored resin composition]
The method for producing a photosensitive colored resin composition of the present invention comprises a colorant, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, an alkali-soluble resin, an antioxidant, and optionally It is preferable from the viewpoint of improving the contrast that the various additive components used are contained and the coloring material can be uniformly dispersed in the solvent by a dispersant. can do.
As a method for preparing the resin composition, for example, (1) first, a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and an alkali-soluble resin and a light are added to the dispersion. A method of mixing a polymerizable compound, a photoinitiator, and optionally various additive components; (3) A dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and, if desired, a dispersant in a solvent. A method of adding and mixing various additive components, and then adding and dispersing a coloring material; (4) adding a coloring material, a dispersant, and an alkali-soluble resin to a solvent to prepare a coloring material dispersion; Then, to the dispersion, an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and optionally various additive components are added and mixed; and a method of simultaneously adding and mixing the material, the photopolymerizable compound, the photoinitiator, and various additive components that are optionally used.
In the above example, the method of using the coloring material by dispersing it is mentioned, but when using a coloring material with high solvent solubility among the coloring materials, the coloring material may be dissolved in a solvent and used. , the coloring material may be added to the solvent together with other components and mixed.
Also, C.I. I. Pigment Blue 16 and a lake colorant of triarylmethane dye and polyacid may be used by co-dispersing two or more of the colorants, or a colorant dispersion in which each colorant is dispersed or dissolved may be prepared and mixed for use.
Among these methods, the above methods (1) and (4) are preferable because they can effectively prevent the aggregation of the colorant and uniformly disperse the colorant.

Examples of dispersing machines for dispersing treatment include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills. As preferable dispersing conditions for the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

The photosensitive colored resin composition of the present invention suppresses the chromaticity change and luminance decrease before and after repeating the high temperature heating process, while improving the luminance of the finally obtained colored layer, the pattern with the desired line width. Since it can be formed, it is suitably used for color filters.

<Cured film of colored resin composition for color filter>
The colored resin composition for a color filter has a chromaticity coordinate of x=0.110 or more and 0.146 or less and y=0.108 or more and 0.108 or more in the XYZ color system of JIS Z8701 measured using a C light source. It is preferable that a cured film in the range of 173 or less can be formed.
Among them, from the viewpoint of improving color reproducibility, the chromaticity coordinates in the XYZ color system of JIS Z8701 measured using the C light source are x = 0.112 or more and 0.141 or less, and y = 0.110 or more. It is preferable to be able to form a cured film in the range of 0.153 or less, and it is possible to form a cured film in the range of x = 0.114 to 0.136 and y = 0.112 to 0.143 More preferably, it is possible to form a cured film in the range of x=0.116 or more and 0.131 or less and y=0.114 or more and 0.133 or less.
The film thickness of the cured film here is the film after coating, drying, and curing the polyfunctional monomer by exposing the colored resin composition for a color filter, and then post-baking in a clean oven at 230° C. for 30 minutes. thickness.

II. Cured Product The cured product according to the present invention is a cured product of the photosensitive colored resin composition according to the present invention.
The cured product according to the present invention, for example, by forming a coating film of the photosensitive colored resin composition according to the present invention, drying the coating film, exposing, and, if necessary, developing can be done. The method of forming, exposing, and developing the coating film may be, for example, the same method as that used in the formation of the colored layer provided in the color filter according to the present invention, which will be described later.
In addition, the cured product according to the present invention has good brightness even after the high-temperature heating step, has a pattern formed with a desired line width, and is suitably used as a colored layer of a color filter.

III. Color filter The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin composition according to the present invention. It is a hardened material.

Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light shielding portion 2 and a colored layer 3. As shown in FIG.

[Colored layer]
At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition according to the present invention, that is, a colored layer formed by curing the colored resin composition.
The colored layer is usually formed in the opening of the light shielding part on the substrate, which will be described later, and is usually composed of colored patterns of three or more colors.
The arrangement of the colored layers is not particularly limited, and may be a general arrangement such as a stripe type, mosaic type, triangle type, four-pixel arrangement type, or the like. Moreover, the width, area, etc. of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the photosensitive colored resin composition, and is preferably in the range of 1 μm or more and 5 μm or less.

The colored layer can be formed, for example, by the following method.
First, the photosensitive colored resin composition of the present invention described above is applied onto a substrate described later using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. to form a wet coating. Among them, the spin coating method and the die coating method can be preferably used.
Then, after drying the wet coating film using a hot plate or an oven, it is exposed through a mask of a predetermined pattern, and a photopolymerizable compound such as an alkali-soluble resin and a polyfunctional monomer is exposed to light. A cured coating film is formed by a polymerization reaction. Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like. The exposure amount is, for example, 30 mJ to 80 mJ, and in the case of a small exposure amount, for example, about 30 mJ.
Moreover, in order to accelerate the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected according to the mixing ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as the developing method.
After the development processing, the developer is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after development processing. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

[Light shielding part]
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate, which will be described later, and can be the same as those used as light-shielding portions in general color filters.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like are available. be.

The film thickness of the light-shielding portion is set to about 0.2 μm or more and 0.4 μm or less in the case of a metal thin film, and about 0.5 μm or more and 2 μm or less in the case of a black pigment dispersed or dissolved in a binder resin. is set by

[substrate]
As the substrate, a transparent substrate or a silicon substrate, which will be described later, or a substrate obtained by forming a thin film of aluminum, silver, silver/copper/palladium alloy, or the like on the substrate is used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
Although the thickness of the transparent substrate is not particularly limited, a thickness of about 100 μm or more and 1 mm or less can be used depending on the application of the color filter of the present invention.
The color filter of the present invention includes, in addition to the above-described substrate, light shielding portion and colored layer, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like. good too.

IV. Display Device A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device. In the present invention, even in a horizontal electric field type liquid crystal display device, various display defects such as alignment disorder of liquid crystal due to the electrical characteristics of green pixels and burn-in phenomenon due to switching threshold shift are suppressed. Apparatus is preferably selected.

[Liquid crystal display device]
A liquid crystal display device of the present invention includes the above-described color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram showing an example of the display device of the present invention, and is a schematic diagram showing an example of a liquid crystal display device. As illustrated in FIG. 2, a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention.
Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

[Organic Light Emitting Display Device]
An organic light-emitting display device according to the present invention is characterized by having the above-described color filter according to the present invention and an organic light-emitting material.
The organic light-emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing another example of the display device of the present invention, and is a schematic diagram showing an example of an organic light-emitting display device. As illustrated in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. As shown in FIG. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80 .

As a lamination method of the organic light emitter 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. method, and a method of bonding the organic light emitter 80 formed on another substrate onto the inorganic oxide film 60, and the like. As for the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light emitter 80, known structures can be appropriately used. The organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
The organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the invention.
The acid value of the block copolymer before salt formation was obtained by a method according to the method described in JIS K 0070:1992.
The amine value of the block copolymer before salt formation was determined according to the method described in JIS K 7237:1995.
The weight average molecular weight (Mw) was measured by Shodex GPC System-21H using polystyrene as a standard and THF as an eluent. Moreover, the method for measuring the acid value was based on JIS K 0070.
The glass transition temperature (Tg) of the block copolymer before and after salt formation was measured by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology) according to the method described in JIS K7121. was measured using

(Synthesis Example 1: Synthesis of alkali-soluble resin A)
A polymerization tank was charged with 150 parts by mass of PGMEA, heated to 100° C. under a nitrogen atmosphere, and then 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA) and Perbutyl O (manufactured by NOF Corporation) ) and 2 parts by mass of a chain transfer agent (n-dodecylmercaptan) were continuously added dropwise over 1.5 hours. After that, the reaction was continued while maintaining the temperature at 100° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization two hours after the completion of the dropping of the mixture for forming the main chain.
Next, while blowing in air, 14 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, and the temperature was raised to 110°C. Then, 0.8 parts by mass of triethylamine was added and the mixture was heated to 110°C for 15 hours. An addition reaction was carried out to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) of 9,000, acid value of 90 mgKOH/g, solid content of 40% by mass).

(Synthesis Example 2: Synthesis of Block Copolymer 1)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was sufficiently purged with nitrogen. rice field. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. B-block monomers 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by mass, 2-(trimethylsilyloxy)ethyl methacrylate (TMSMA) 29.1 parts by mass, and 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass Part, n-butyl methacrylate (BMA) 13.7 parts by mass, benzyl methacrylate (BzMA) 9.5 parts by mass, methyl methacrylate (MMA) 17.5 parts by mass, using an addition funnel for 60 minutes dripped. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, purified by vacuum drying, and diluted with PGMEA to obtain a solid content 30% by mass solution. Add 32.5 parts by mass of water, raise the temperature to 100 ° C. and react for 7 hours, deprotect the structural unit derived from EEMA to make it a structural unit derived from methacrylic acid (MAA), and deprotect the structural unit derived from TMSMA. A structural unit derived from 2-hydroxyethyl methacrylate (HEMA) was used. The resulting block copolymer PGMEA solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain block copolymer 1 (amine value: 95 mg KOH/ g, acid value 8 mgKOH/g, Tg 38°C). The weight average molecular weight Mw was 7,730.

(Synthesis Example 3: Synthesis of salt-type block copolymer 2)
250 parts by mass of THF and 0.75 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was sufficiently purged with nitrogen. rice field. After cooling the reaction flask to −60° C., 6.1 parts by mass of butyllithium (15% by mass hexane solution), 1.4 parts by mass of diisopropylamine, and 1.2 parts by mass of methyl isobutyrate were injected using a syringe. B-block monomers 2-ethylhexyl methacrylate (EHMA) 9 parts by weight, n-butyl methacrylate (BMA) 13.4 parts by weight, benzyl methacrylate (BzMA) 7.5 parts by weight, methyl methacrylate (MMA) 47 parts by weight 0.5 parts by mass was added dropwise over 60 minutes using an addition funnel. After 30 minutes, 22.6 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. It was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain a block copolymer 2 containing the structural unit represented by the general formula (I). (Amine value: 95 mgKOH/g, acid value: 0 mgKOH/g) Weight average molecular weight Mw was 7,600.
50 parts by mass of the obtained block copolymer 2 was dissolved in 213 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto and reacted at 90° C. for 12 hours to obtain a PGMEA solution of salt-type block copolymer 2 (solid content: 20%).

(Synthesis Example 4: Synthesis of salt-type block copolymer 3)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was sufficiently purged with nitrogen. rice field. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. B block monomers 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by mass, 2-ethylhexyl methacrylate (EHMA) 12.1 parts by mass, n-butyl methacrylate (BMA) 12.9 parts by mass, methacrylic acid 9.0 parts by mass of benzyl (BzMA), 16.6 parts by mass of methyl methacrylate (MMA), and 17.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA) were added dropwise over 60 minutes using an addition funnel. After 30 minutes, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, purified by vacuum drying, and diluted with PGMEA to obtain a solid content 30% by mass solution. 32.5 parts by mass of water was added, the temperature was raised to 100° C., and the mixture was reacted for 7 hours to deprotect the structural units derived from EEMA to obtain structural units derived from methacrylic acid (MAA). The resulting PGMEA solution of block copolymer 3 was reprecipitated in hexane, filtered and vacuum dried for purification. The purified block copolymer 3 is dissolved again in 400 parts by mass of PGMEA, and 5.3 parts by mass of isocyanate A (2-isocyanatoethyl methacrylate, trade name: Karenz MOI, manufactured by Showa Denko), dibutyl tin (trade name: Neostan U- 100, Nitto Kasei Co., Ltd.) 0.008 parts by mass was added and the temperature was raised to 80 ° C., followed by reaction for 2 hours, A block containing a structural unit represented by general formula (I), and general formula A block copolymer 3 solution (solid content: 20% by mass) having a B block containing a structural unit represented by (B1) and a structural unit derived from a carboxy group-containing monomer was obtained.

50 parts by mass of the obtained block copolymer 3 solution was placed in a 100 mL round bottom flask, and 1.27 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry Co., Ltd.) (PPA is , 0.5 mol) and stirred at a reaction temperature of 30° C. for 20 hours to obtain a solution of salt type block copolymer 3 having a solid content of 20% by mass. The acid value of the salt-type block copolymer 3 after salt formation was the same as that of the block copolymer 3 before salt formation, but the amine value after salt formation was specifically calculated as follows.
9 parts by mass of salt-type block copolymer 3 (solid matter after reprecipitation) and 1 g of a mixed solution of 91 parts by mass of chloroform-D1 NMR are placed in an NMR sample tube, and the 13C-NMR spectrum is measured by a nuclear magnetic resonance apparatus ( FT NMR, JNM-AL400 manufactured by JEOL Ltd.) was used, and measurement was performed at room temperature under the conditions of 10,000 times of integration. Among the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salted nitrogen atom and the carbon atom peak adjacent to the salted nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of salt-formed amino groups to the total number of amino groups is calculated, and it is not different from the theoretical salt-forming ratio (all phenylphosphonic acid forms a salt with the terminal nitrogen site of DMMA of block copolymer 3). I confirmed that

(Synthesis Example 5: Synthesis of lake colorant with triarylmethane dye and polyacid)
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate 3 and Intermediate 4 described in WO 2012/144521, 15.9 g of Intermediate 1 represented by the following chemical formula (a) (yield rate of 70%) was obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
・MS (ESI) (m / z): 511 (+), divalent ・Elemental analysis value: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of lake colorant with triarylmethane dye and polyacid 5.00 g (4.58 mmol) of intermediate 1 was added to 300 ml of water and dissolved at 90° C. to obtain an intermediate 2 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid/n-hydrate H ₃ [PW ₁₂ O ₄₀ ]/nH ₂ O (n=30) manufactured by Nippon Inorganic Chemical Industry was added to 100 mL of water and stirred at 90°C. to prepare a phosphotungstic acid aqueous solution. An aqueous solution of phosphotungstic acid was mixed with the previous intermediate 2 solution at 90° C., and the resulting precipitate was collected by filtration and washed with water. The resulting cake was dried to obtain 13.25 g (yield 98%) of a coloring material B represented by the following chemical formula (b), which is a lake coloring material of a triarylmethane dye and a polyacid. .
The obtained compound was confirmed to be the target compound from the following analysis results. (molar ratio W/Mo=100/0)
・MS (ESI) (m / z): 510 (+), divalent ・Elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) , 5.17%, 4.11%)
Also, it was confirmed by ³¹ P-NMR that the polyacid structure of phosphotungstic acid was maintained even after the coloring material B was formed.

(Synthesis Example 6: Synthesis of xanthene-based lake colorant)
5.0 g of Acid Red 289 was added to 500 ml of water and dissolved at 80° C. to prepare a dye solution. 3.85 g of polyaluminum chloride (“trade name: Takibain #1500” manufactured by Taki Kagaku Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5% by mass, alumina content 23.5% by mass) to 200 ml of water and stirred at 80° C. to prepare an aqueous polyaluminum chloride solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the dye solution at 80° C. over 15 minutes, and the mixture was further stirred at 80° C. for 1 hour. The precipitate formed was collected by filtration and washed with water. The resulting cake was dried to obtain 6.30 g (yield 96.2%) of Colorant C, which is a xanthene (rhodamine acid dye) lake colorant.

(Production Example 1: Preparation of colorant dispersion liquid A)
In a 225 mL mayonnaise bottle, 57.8 parts by mass of PGMEA, 16.3 parts by mass of the alkali-soluble resin A solution (solid content: 40 mass%) of Synthesis Example 1, and the salt-type block copolymer 2 solution of Synthesis Example 3 (solid content: 20 mass%). mass%) 13.0 parts by mass was added and stirred.
there C. I. Pigment Blue 16 (PB16, trade name: Heliogen Blue D7490, manufactured by BASF) 13.0 parts by mass and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are added, and pre-crushed for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.). After shaking, the mixture was changed to 200 parts of zirconia beads having a particle size of 0.1 mm, and dispersed for 4 hours with a paint shaker as main pulverization to obtain a colorant dispersion liquid A.

(Production Example 2: Preparation of Colorant Dispersion B)
In a 225 mL mayonnaise bottle, 63.3 parts by mass of PGMEA, 13.0 parts by mass of the alkali-soluble resin A solution of Synthesis Example 1 (solid content 40% by mass), block copolymer 1 solution of Synthesis Example 2 (amine value 95 mg KOH / g , acid value 8 mgKOH/g, solid content 45% by mass) were added and stirred. 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.6 molar equivalent with respect to the tertiary amino group of the block copolymer) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
13.0 parts by mass of coloring material B, which is a lake coloring material of triarylmethane-based dye and polyacid in Synthesis Example 5, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added, and a paint shaker (Asada (manufactured by Iron Works Co., Ltd.) for 1 hour, then changed to 200 parts of zirconia beads having a particle size of 0.1 mm, and dispersed for 4 hours with a paint shaker as main pulverization to obtain a coloring material dispersion liquid B.

(Production Example 3: Preparation of colorant dispersion liquid C)
In a 225 mL mayonnaise bottle, 61.3 parts by mass of PGMEA, 11.3 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) of Synthesis Example 1, and the salt-type block copolymer 2 solution of Synthesis Example 3 (solid content: 20 22.5 parts by mass) were added and stirred.
5.0 parts by mass of the coloring material C, which is the xanthene-based lake coloring material of Synthesis Example 6, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are added thereto, and pre-crushed for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.). After shaking for a period of time, 200 parts of zirconia beads having a particle diameter of 0.1 mm were used, and dispersion was carried out for 6 hours using a paint shaker as main pulverization to obtain a coloring material dispersion liquid C.

(Production Examples 4 to 7: Preparation of Colorant Dispersions D to G)
In Production Example 1, C.I. I. Pigment Blue 16 can be replaced with C.I. I. Pigment Violet 23 (trade name Hostaperm Violet RL-NF manufactured by Clariant), C.I. I. Pigment Blue 15:6 (trade name FASTOGEN BLUE A510 manufactured by DIC Corporation), C.I. I. Pigment Blue 15:3 (trade name: Chromophine Blue A-220JC, manufactured by Dainichiseika Kogyo Co., Ltd.), or C.I. I. Colorant dispersions D, E, F, and G were obtained in the same manner as in Production Example 1, except that Pigment Green 59 (PG59, trade name: FASTOGEN GREEN C100, manufactured by DIC Corporation) was used.

(Production Example 8: Preparation of colorant dispersion H)
In a 225 mL mayonnaise bottle, 57.8 parts by mass of PGMEA, 16.3 parts by mass of the alkali-soluble resin A solution of Synthesis Example 1 (solid content: 40 mass%), 3 solutions of the salt-type block copolymer of Synthesis Example 4 (solid content: 20 13.0 parts by mass) were added and stirred.
there C. I. Pigment Blue 16 (PB16, trade name: Heliogen Blue D7490, manufactured by BASF) 13.0 parts by mass and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are added, and pre-crushed for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.). After shaking, the mixture was changed to 200 parts of zirconia beads having a particle size of 0.1 mm, and dispersed with a paint shaker for 4 hours as main pulverization to obtain a coloring material dispersion liquid H.

(Preparation Example 1: Preparation of photosensitive binder component CR-1)
Dipentaerythritol hexaacrylate (DPHA) (Aronix M402 (manufactured by Toa Gosei Co., Ltd.)) is added as a photopolymerizable compound to 36.5 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Synthesis Example 1. 21.9 parts by mass, 2.7 parts by mass of an oxime ester compound having a carbazole skeleton as an initiator (trade name: Adeka Arcles NCI-831, manufactured by ADEKA), antioxidant IRGANOX1010 (manufactured by BASF) 0.8 parts by mass , and 38.1 parts by mass of PGMEA were added to obtain a photosensitive binder component CR-1.

(Preparation Example 2: Preparation of photosensitive binder component CR-2)
Preparation Example 1 except that the oxime ester compound having a carbazole skeleton in Preparation Example 1 was replaced with an oxime ester compound having a diphenyl sulfide skeleton (trade name: TR-PBG-3057, manufactured by Changzhou Tenryu Denshi New Materials Co., Ltd.). A photosensitive binder component CR-2 was obtained in the same manner as in Example 1.

(Preparation Example 3: Preparation of photosensitive binder component CR-3)
Photosensitivity was obtained in the same manner as in Preparation Example 1, except that the oxime ester compound having a carbazole skeleton in Preparation Example 1 was changed to an oxime ester compound having a fluorene skeleton (trade name: SPI-03, manufactured by Sanyang). A binder component CR-3 was obtained.

(Preparation Example 4: Preparation of photosensitive binder component CR-4)
Photosensitization in the same manner as in Preparation Example 1, except that the oxime ester compound having a carbazole skeleton in Preparation Example 1 was changed to an α-aminoketone photoinitiator (trade name: Irgacure 369 (Irg369), manufactured by BASF). A binder component CR-4 was obtained.

(Preparation Example 5: Preparation of photosensitive binder component CR-5)
In Preparation Example 1, instead of 2.7 parts by mass of the oxime ester compound having a carbazole skeleton, α-aminoketone photoinitiator (trade name: Irgacure 907 (Irg907), manufactured by BASF) 1.35 parts by mass and thioxanthone-based light A photosensitive binder component CR-5 was obtained in the same manner as in Preparation Example 1, except that the initiator (trade name: DOUBLECURE DETX, manufactured by Double Bond Chemical) was changed to 1.35 parts by mass.

(Example 1: Preparation of photosensitive colored resin composition)
Colorant dispersion liquid A 18.3 parts by mass, colorant dispersion liquid B 7.1 parts by mass, photosensitive binder component CR-1 of Preparation Example 1 26.0 parts by mass, surfactant Megafac R08MH (manufactured by DIC) 0 02 parts by mass and 48.6 parts by mass of PGMEA were mixed to obtain a photosensitive colored resin composition of Example 1.

(Examples 2-3: Preparation of photosensitive colored resin composition)
In Example 1, in the same manner as in Example 1, except that the photosensitive binder component CR-1 of Preparation Example 1 was replaced with the photosensitive binder component CR-2 or CR-3 of Preparation Example 2 or 3. , to obtain a photosensitive colored resin composition of Example 2 or 3.

(Examples 4 to 8: Preparation of photosensitive colored resin composition)
Photosensitive colored resin compositions of Examples 4 to 8 in the same manner as in Example 1 except that the colorant dispersion used was changed so that the colorant ratio (solid content mass ratio) shown in Table 1 was obtained. got stuff

(Examples 9 to 13: Preparation of photosensitive colored resin composition)
Photosensitive colored resin compositions of Examples 9 to 13 in the same manner as in Example 3 except that the colorant dispersion used was changed so that the colorant ratio (solid content mass ratio) shown in Table 1 was obtained. got stuff

(Example 14: Preparation of photosensitive colored resin composition)
Example 14 was prepared in the same manner as in Example 3 except that the colorant dispersion A used was changed to the colorant dispersion H so that the colorant ratio (solid content mass ratio) shown in Table 1 was obtained. A photosensitive colored resin composition was obtained.

(Comparative Examples 1, 2, 4, 5: Preparation of comparative photosensitive colored resin composition)
Comparative Examples 1, 2, 4, and 5 were compared in the same manner as in Example 1, except that the colorant dispersion liquid used was changed so that the colorant ratio (solid content mass ratio) shown in Table 2 was obtained. A photosensitive colored resin composition was obtained.

(Comparative Example 3: Preparation of comparative photosensitive colored resin composition)
In Comparative Example 2, in the same manner as in Comparative Example 2, except that the photosensitive binder component CR-5 of Preparation Example 5 was used instead of the photosensitive binder component CR-1 of Preparation Example 1. Thus, a colored resin composition was obtained.

(Comparative Example 6: Preparation of comparative photosensitive colored resin composition)
Comparative photosensitive colored resin composition of Comparative Example 6 in the same manner as in Comparative Example 3 except that the colorant dispersion used was changed so that the colorant ratio (solid content mass ratio) shown in Table 2 was obtained. got

(Comparative Examples 7-8: Preparation of comparative photosensitive colored resin composition)
In Example 1, in the same manner as in Example 1, except that the photosensitive binder component CR-4 or CR-5 of Preparation Example 4 or 5 was used instead of the photosensitive binder component CR-1 of Preparation Example 1. , a comparative photosensitive colored resin composition of Comparative Example 7 or 8 was obtained.

(Comparative Example 9: Preparation of comparative photosensitive colored resin composition)
Comparative photosensitive coloring of Comparative Example 9 in the same manner as in Comparative Example 3 except that the coloring material and coloring material dispersion used were changed so that the coloring material ratio (solid content mass ratio) shown in Table 2 was obtained. A resin composition was obtained.
The xanthene dye AR52 (Acid Red 52, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added as a solid content during the preparation of the photosensitive colored resin composition and dissolved in PGMEA.

[Evaluation method]
<Brightness evaluation, heat resistance evaluation>
Each of the photosensitive colored resin compositions of Examples and Comparative Examples was placed on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") having a thickness of 0.7 mm, and the chromaticity after post-baking was y = 0.120. It was applied using a spin coater so that the After that, it was dried by heating on a hot plate at 80° C. for 3 minutes. A cured film (blue colored film) was obtained by irradiating ultraviolet rays of 60 mJ/cm ² using an ultra-high pressure mercury lamp without passing through a photomask. The resulting film was post-baked in a clean oven at 230° C. for 25 minutes, and the luminance was measured using a “spectroscopic microscopic measuring device OSP-SP200” manufactured by Olympus Corporation. In addition, in the cured films using the photosensitive colored resin compositions of Comparative Examples 4 to 6, even if the film thickness was changed, it was not possible to achieve a color with a chromaticity of y = 0.120 after post-baking. rice field.
After that, the resulting film was further post-baked in a clean oven at 240°C for 25 minutes, the chromaticity (L ₀ , a ₀ , b ₀ ) of this colored film was measured, and then further in a clean oven at 240°C. After post-baking for 50 minutes, the chromaticity (L ₁ , a ₁ , b ₁ ) of the obtained colored film was measured again, and the luminance was also measured.
The table shows the brightness after thermal testing (230° C. for 25 minutes + 240° C. for 25 minutes + 240° C. for 50 minutes post-bake).
Also, the change in chromaticity of the colored film was evaluated from 25 minutes to 75 minutes at 240° C. according to the following formula. The results are shown in the table.
ΔEab={(L ₁ −L ₀ ) ² +(a ₁ −a ₀ ) ² +(b ₁ −b ₀ ) ² } ^1/2
The smaller the value of ΔEab, the more excellent the heat resistance is evaluated. If ΔEab is 3.0 or less, it is judged that there is no practical problem.

<Evaluation of line width shift>
The photosensitive colored resin compositions of Examples and Comparative Examples were each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater so that the film thickness was 3 μm. was applied to Then, after drying by heating on a hot plate at 80 ° C. for 3 minutes, 30 mJ using an ultra-high pressure mercury lamp through a photomask pattern having a fine line pattern (line width shift evaluation pattern) with an opening width of 90 μm. /cm ² of ultraviolet rays. After that, the glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and post-baked in a clean oven at 230° C. for 30 minutes. Of the independent thin lines of the colored layer thin line pattern formed on the glass substrate, the width (line width) of the actually measured independent thin lines when the opening width of the photomask was 90 μm and the design line width was 90 μm was measured.
It is evaluated that a pattern can be formed with a desired line width as the deviation from the design line width is smaller.
When the line width shift value (μm), which is the deviation from the designed line width, is calculated by the following formula, it is judged that there is no practical problem if it is −5 μm or more and 2 μm or less.
Line width shift value (μm) = measured line width (μm) - 90 (μm)

[Summary of results]
From the results in the table, it can be seen that the colorant is C.I. I. Pigment Blue 16, and the photosensitive colored resin compositions of Examples 1 to 14 in which the lake colorant of triarylmethane dye and polyacid are combined, the chromaticity change and luminance decrease of the colored film before and after the high temperature heating process. It is clear that the brightness after the heat resistance test (230° C. for 25 minutes + 240° C. for 25 minutes + 240° C. for 50 minutes after post-baking) is high, and it is possible to form a pattern with a desired line width. was done.
On the other hand, as in the prior art, C.I. I. In Comparative Example 1, in which Pigment Blue 16 was combined with a violet pigment, although it was possible to exhibit a strong bluish blue color similar to that of Examples, the brightness was low, and the shift value from the design line width was large, which was the desired value. It was difficult to obtain a pattern with a line width. C. I. In Comparative Example 9, in which Pigment Blue 16 was combined with a xanthene-based acid dye (Acid Red 52), although it was possible to exhibit a blue with a strong bluish tinge similar to that of Examples, the luminance was low, and furthermore, the design line width was low. The shift value of is large, and it is difficult to obtain a pattern with a desired line width.
Comparative Example 4 using only a triarylmethane-based dye and a polyacid lake coloring material as the coloring material, C.I. I. Comparative Example 5 using only C.I. Pigment Blue 16 and C.I. I. In Comparative Example 6, in which Pigment Blue 15:6 and a lake colorant of triarylmethane-based dye and polyacid were combined, a strong bluish blue color (y = 0.120) similar to that of Examples could not be exhibited. rice field.
C.I. I. Pigment Blue 16 and a lake colorant of triarylmethane dye and polyacid were used in combination, but in Comparative Examples 7 and 8 in which no oxime ester compound was used as a photoinitiator, the shift value from the designed line width was It was difficult to obtain a pattern with a large desired line width, and the luminance was inferior to those of Examples 1 to 3 having the same coloring material content.

Among the examples, when comparing Examples 1 to 3, when the oxime ester compound contains an oxime ester compound having a fluorene skeleton, the finally obtained brightness after the heat resistance test is improved, and the line width is It was found that patterns can be formed.
Further, when comparing Examples 3 and 14, the A block containing a structural unit having a tertiary amine, the structural unit represented by the general formula (B1), and the structural unit represented by the general formula (B2) By using a block copolymer dispersing agent containing a B block containing at least one selected from, the chromaticity change and luminance decrease of the colored film before and after the high temperature heating process are suppressed, and the luminance after the heat resistance test was found to be improved.

REFERENCE SIGNS LIST 1 substrate 2 light shielding part 3 colored layer 10 color filter 20 counter substrate 30 liquid crystal layer 40 liquid crystal display device 50 organic protective layer 60 inorganic oxide film 71 transparent anode 72 hole injection layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 Cathode 80 Organic Light Emitting Body 100 Organic Light Emitting Display

Claims (6)

Containing a coloring material, a binder component containing a photopolymerizable compound and a photoinitiator, and a solvent,
The colorant is C.I. I. Pigment Blue 16, and a lake colorant of a triarylmethane dye and a polyacid,
The content of the lake colorant of the triarylmethane dye and polyacid is 4% by mass or more and 32% by mass or less with respect to the total content of all colorants,
The above C.I. I. Pigment Blue 16, and the total content of the lake colorant of the triarylmethane dye and polyacid is 68% by mass or more with respect to the total content of all colorants,
The photosensitive colored resin composition, wherein the photoinitiator contains an oxime ester compound. 2. The photosensitive colored resin composition according to claim 1, wherein the colorant further comprises a purple colorant different from the lake colorant of triarylmethane dye and polyacid. The photosensitive colored resin composition according to claim 1 or 2, wherein the oxime ester compound contains an oxime ester compound having a fluorene skeleton. A cured product of the photosensitive colored resin composition according to any one of claims 1 to 3 . A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured photosensitive colored resin composition according to any one of claims 1 to 3 . A color filter that is a thing. A display device comprising the color filter according to claim 5 .

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