JP6450057B1 - Photosensitive colored resin composition and cured product thereof, color filter, and display device - Google Patents

Abstract

Provided is a photosensitive colored resin composition capable of forming a pattern with a desired line width while improving luminance after a high-temperature heating step. The color material includes a phthalocyanine pigment and a color material represented by the following general formula (1), and the content of the color material represented by the following general formula (1) is represented by the phthalocyanine pigment and the following general formula (1). It is a photosensitive coloring resin composition which is 20 mass% or more and 85 mass% or less with respect to the total content of the coloring material represented. (In general formula (1), each symbol is as described in the specification.)

Description

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

  In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (cell phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In terms of the performance of these image display devices, higher 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, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. As a light source at that time, 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 the organic light emitting display device, a color filter is used for color adjustment.

  As a recent trend, there is a demand for power saving of an image display device, and in order to improve the utilization efficiency of a backlight, a high brightness of a color filter is particularly demanded. This is a big problem especially for mobile displays (cell phones, smartphones, tablet PCs).

Here, the color filter is generally formed on the substrate to form the substrate, the colored layer including the colored patterns of the three primary colors of red, green, and blue, and the colored patterns. A light shielding portion.
As one method for forming such a colored layer, there is known a method in which a photosensitive colored resin composition containing a colorant and a photopolymerizable compound is applied onto a substrate and cured by irradiating ultraviolet rays or the like. It has been.

As the coloring material of the photosensitive colored resin composition, pigments and dyes are used. Although pigments are generally superior in heat resistance and light resistance as compared to dyes, they have a problem that the transmittance is low and the luminance is not sufficiently improved. Therefore, in recent years, photosensitive resin compositions for color filters using dyes with high transmittance have been studied from the viewpoint of further increasing the brightness of color filters, and the heat resistance and light resistance of dyes have been improved. In order to achieve this, the use of a rake color material in which a dye is insolubilized has been studied.
Patent Document 1 discloses a color filter using a specific color material containing a divalent or higher cation in which a plurality of dye skeletons are cross-linked by a cross-linking group and a divalent or higher anion. The color material is excellent in heat resistance, and a color filter using the color material is described as having high contrast, excellent solvent resistance and electrical reliability.

International Publication No. 2012/144521

  However, even if the specific color material of Patent Document 1 is used, since the heat resistance and light resistance are poor compared to the pigment, the chromaticity is likely to change after high-temperature heating (post-baking) in the color filter manufacturing process. Therefore, the brightness of the colored layer obtained is not yet sufficient, and further improvement is required.

In general, a colored layer for a color filter is patterned on a substrate. When forming a colored layer using the photosensitive colored resin composition, for example, after forming a coating film of the photosensitive colored resin composition on the substrate, it is exposed through a predetermined mask pattern, and then developed. Thus, a patterned colored layer can be obtained.
In recent years, in order to increase production efficiency, patterning with a smaller exposure amount has been required. However, when the present inventors try to form a blue colored layer using a phthalocyanine pigment, the colored layer as designed is formed. The knowledge that it may not be obtained was acquired.

  The present invention has been made based on the above knowledge, and is a photosensitive colored resin capable of forming a pattern with a desired line width while improving luminance after a high-temperature heating step (post-baking) in a color filter manufacturing step. It is an object of the present invention to provide a composition, a color filter with improved luminance formed using the photosensitive colored resin composition, and a display device excellent in display characteristics using the color filter.

The photosensitive colored resin composition according to the present invention is a photosensitive colored resin composition containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The color material includes a phthalocyanine pigment and a color material represented by the following general formula (1),
The content of the color material represented by the following general formula (1) is 20% by mass to 85% by mass with respect to the total content of the phthalocyanine pigment and the color material represented by the following general formula (1).

（一般式（１）中、各符号は後述のとおりである。）

(In the general formula (1), each symbol is as described later.)

The present invention provides a cured product of the photosensitive colored resin composition according to the present invention.
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 a cured product of the photosensitive colored resin composition according to the present invention. Provide a color filter.

  The present invention provides a display device having the color filter according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive coloring resin composition which can form a pattern with desired line width, improving the brightness | luminance after the high temperature heating process (post-baking) in a color filter manufacturing process, The said photosensitive coloring resin composition A color filter with improved luminance and a display device with excellent display characteristics using the color filter can be provided.

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

Hereinafter, the photosensitive colored resin composition, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In addition, C.I. I. Pigment Blue “PB”, C.I. I. Pigment violet is abbreviated as “PV” where appropriate.

I. Photosensitive colored resin composition The photosensitive colored resin composition according to the present invention is a photosensitive colored resin composition containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. There,
The color material includes a phthalocyanine pigment and a color material represented by the following general formula (1),
The content of the color material represented by the following general formula (1) is 20% by mass to 85% by mass with respect to the total content of the phthalocyanine pigment and the color material represented by the following general formula (1). It is characterized by.

（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 has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain, and B ^c- represents a c-valent anion. R ^{i to} R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁱⁱ , R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, and R ^vi and R ^vii each independently represents an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom, or .Ar ¹ represents cyano group represents a divalent aromatic group which may have a substituent Each plurality of ^R i ^{to R vii} and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. A plurality of e, f and g may be the same or different. )

The photosensitive colored resin composition of the present invention has an effect that a pattern can be formed with a desired line width while improving luminance after high-temperature heating (post-baking) in a color filter manufacturing process.
Since the post-baking process in the color filter manufacturing process is heated at a high temperature of 230 ° C. or 240 ° C., a pigment has been conventionally used as a coloring material because it is difficult to fade against the high temperature heating. Furthermore, in recent years, in order to increase production efficiency, patterning with a smaller amount of exposure is required. However, when the present inventors try to form a blue colored layer using a phthalocyanine pigment, the colored layer as designed is used. It was found that may not be formed. 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 and insufficient curing inside the colored layer occurs during exposure. It is estimated that
On the other hand, in the present invention, the phthalocyanine pigment is represented by the specific general formula (1) by using the color material represented by the specific general formula (1) in combination at a specific ratio. Since the coloring material hardly absorbs wavelengths of around 300 nm, the photosensitive coloring resin composition for the blue colored layer combined with the negative photosensitive binder component is unlikely to be insufficiently cured inside the colored layer during exposure. It becomes easy to form a pattern with a line width of.
Furthermore, the color material represented by the specific general formula (1) is used in combination with the phthalocyanine pigment at a specific ratio, thereby suppressing the fading caused by the color material represented by the specific general formula (1). However, it is estimated that the transmittance can be improved and the luminance of the colored layer finally obtained after high-temperature heating (post-baking) in the color filter manufacturing process can be improved.

The photosensitive colored resin composition of the present invention contains at least a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and in a range that does not impair the effects of the present invention. Further, other components may be contained.
Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail in order.

[Color material]
In the present invention, the coloring material includes a phthalocyanine pigment and the coloring material represented by the general formula (1), and the content of the coloring material represented by the following general formula (1) is the phthalocyanine pigment and the following general formula. It is 20 mass% or more and 85 mass% or less with respect to the total content of the color material represented by (1).

<Phthalocyanine pigment>
The phthalocyanine pigment is preferably a blue phthalocyanine pigment because it is used in combination with the colorant represented by the general formula (1), and a copper phthalocyanine pigment is preferable from the viewpoint of relatively high luminance. For example, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6. Among them, the phthalocyanine pigment is C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 15: 3, and C.I. I. It is preferably one or more selected from the group consisting of CI Pigment Blue 15: 4.

<Coloring material represented by general formula (1)>
On the other hand, since the color material represented by the general formula (1) contains a divalent or higher valent anion and a divalent or higher cation, in the aggregate of the color material, the anion and the cation are simply one molecule pair. The apparent molecular weight is significantly increased compared to the molecular weight of conventional lake pigments because it can form molecular aggregates in which multiple molecules are associated via ionic bonds, rather than being ionically bonded by one molecule. To do. The formation of such molecular aggregates increases cohesion in the solid state, reduces thermal motion, suppresses ion pair dissociation and cation decomposition, and is estimated to be less susceptible to fading than conventional lake pigments. Is done.

A in the general formula (1) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) has no π bond, and the organic group is saturated at least at the terminal directly bonded to N. An aliphatic hydrocarbon group having an aliphatic hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group is represented, and O (oxygen atom), S (sulfur atom), and N (nitrogen atom) are present 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 the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
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 terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is 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 2 alkylene groups having 1 to 20 carbon atoms such as a xylylene group Etc.

The valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. In this lake color material, since the cation valence a is 2 or more, it is excellent in heat resistance, and among them, the cation valence a is preferably 3 or more. The upper limit of a is not particularly limited, but a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.
The alkyl group in R ^{i to} R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms can be mentioned, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a straight chain having 1 to 5 carbon atoms. A chain or branched alkyl group is more preferable from the viewpoint of luminance and heat resistance. Among them, it is particularly preferred alkyl groups 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 substituted alkyl group includes an aralkyl group such as a benzyl group. Etc.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent that the aryl group may have include an alkyl group, a halogen atom, and an alkoxy group.
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. Thus, it is preferable to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R ^{i to} R ^v can each independently have the above structure, and among these, R ⁱ is preferably a hydrogen atom from the viewpoint of color purity, and from the viewpoint of ease of production and raw material procurement, R ⁱⁱ to R ^v More preferably, R ^v are all the same.

R ^vi and R ^vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. The alkyl group in 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 having 1 to 4 carbon atoms. More preferably, it is a group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which 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, and an alkoxy group.
Further, the alkoxy group in 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 has 1 to 4 carbon atoms. More preferably, it is an alkoxy group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, which may be linear or branched. The substituent that the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.
Examples of the halogen atom in R ^vi and R ^vii include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The number of substitutions of R ^vi and R ^vii , that is, f and g each independently represents an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, more preferably 0 or more and 1 or less. A plurality of f and g may be the same or different.
R ^vi and R ^vii may be substituted at any site of the aromatic ring having a resonance structure in the triarylmethane skeleton or the xanthene skeleton, and among them, —NR ⁱⁱ R ⁱⁱⁱ or —NR ^iv it is preferably substituted in the meta position relative to the substitution position of the amino group represented by R ^v.

The divalent aromatic group in Ar ¹ is not particularly limited. As the aromatic group for Ar ^1, the same aromatic groups as those described for the aromatic group for A can be used.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group containing a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ^{i to} R ^vii and Ar ¹ in one molecule may be the same or different. The 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), the anion part (B ^c− ) is a c-valent anion, which is a divalent or higher anion, and is not particularly limited. It may be an anion. Here, the organic anion represents an anion containing at least one carbon atom. Moreover, an inorganic anion represents the anion which does not contain a carbon atom. Specific examples of the organic anion and the inorganic anion include those described in International Publication No. 2012/144520 pamphlet.

Color material represented by the general formula (1) in the present invention include, among others, from the viewpoint of excellent heat resistance at a high luminance, it is preferable B ^c- is an inorganic anion.
Examples of the inorganic anion include an oxo acid anion (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ²⁻ ), molybdate ion (MoO ₄ ²⁻ ), etc.) and a plurality of oxo acids. And inorganic anions such as polyacid anions and mixtures thereof. Among these, a polyacid anion is preferable from the viewpoint of heat resistance.
The polyacid may be an isopolyacid anion (M _m O _n ) ^c- or a heteropoly acid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co.
Among these, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.

  In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent an integer of 1 or more. When b is 2 or more, a plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined. When d is 2 or more, the anion present in the molecular aggregate may be a single anion or a combination of two or more, and an organic anion and an inorganic anion may be used in combination. .

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. In the rake color material represented by the general formula (1) used in the present invention, those containing at least a triarylmethane skeleton are preferably used.
In addition, as a rake color material represented by General formula (1), it can prepare with reference to international publication 2012/144520 pamphlet, for example.

<Other colorants>
The color material in the photosensitive colored resin composition of the present invention includes the phthalocyanine pigment and the color material represented by the general formula (1) as essential components, but the color tone is within the range not impairing the effects of the present invention. In order to adjust the color, other color materials may be used in combination.
As other colorants, known pigments, dyes, lake colorants and the like can be used alone or in admixture of two or more.

Among other color materials, other blue color materials, purple color materials, and red color materials are preferably used, but are not limited thereto.
Other blue color materials include known organic blue pigments different from phthalocyanine pigments, triarylmethane-based lake color materials different from the color material represented by the general formula (1), and the like.
As a purple color material, C.I. I. Known organic purple pigments such as CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38.
Xanthene dyes and xanthene dye rake color materials as red to reddish purple color materials.

<Content ratio of coloring material>
In the photosensitive colored resin composition of the present invention, the content of the color material represented by the general formula (1) is based on the total content of the phthalocyanine pigment and the color material represented by the general formula (1). Although it is 20 mass% or more and 85 mass% or less, it is preferable that it is 30 mass% or more from the point of the easiness of the patterning with a brightness | luminance and desired line width, and also it is preferable that it is 40 mass% or more especially. On the other hand, from the viewpoint of heat resistance, it is preferably 80% by mass or less, and more preferably 75% by mass or less.

  Moreover, in the photosensitive coloring resin composition of this invention, in the range which does not impair the effect of this invention, in colors other than a phthalocyanine pigment and the color material represented by the said General formula (1), The total content of the phthalocyanine pigment and the color material represented by the general formula (1) may be 70% by mass or more and 100% by mass or less based on the total amount of the color material. Preferably, it is 80 mass% or more and 100 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less.

  The average primary particle size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle diameter of the color material is in the above range, a display device including a color filter manufactured using the color material dispersion of the present invention can be made with high contrast and high quality. .

Moreover, although the average dispersed particle diameter of the color material in the photosensitive colored resin composition varies depending on the type of the color material used, it is preferably within the range of 10 nm to 100 nm, and within the range of 15 nm to 60 nm. It is more preferable.
The average dispersed particle diameter of the color material in the photosensitive colored resin composition is a dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. Is. For particle size measurement with a laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted to a concentration that can be measured with a 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 meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is a 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, based on the total solid content of the photosensitive colored resin composition. . If it is more than the said lower limit, the colored layer at the time of apply | coating the photosensitive colored resin composition to predetermined | prescribed film thickness (usually 1.0 micrometer-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In the case of forming a colored layer having a particularly high color material concentration, the total content of the color material is 15% by mass or more and 65% by mass or less, more preferably 25%, based on the total solid content of the photosensitive colored resin composition. It is preferable to mix | blend in the ratio of the mass% or more and 60 mass% or less.

[Alkali-soluble resin]
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected 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 based on an acid value of 40 mgKOH / g or more.
The preferred 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, etc. Acrylic resin, carboxy group-containing epoxy (meth) acrylate resin, and the like.

Among these, particularly preferred are those having a carboxy group in the side chain and further having 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 curing step of the resin composition at the time of manufacturing the color filter, the alkali-soluble resins or the photopolymerizable compound such as the alkali-soluble resin and a polyfunctional monomer are cross-linked. Can be formed. The film strength of the cured film is further improved and the development resistance is improved, and the thermal contraction of the cured film is suppressed and the adhesiveness with the substrate is excellent.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxy group of the alkali-soluble resin Or by introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain. Etc.

Moreover, it is preferable that alkali-soluble resin has a hydrocarbon ring from the point which the adhesiveness of a colored layer is excellent. By having a hydrocarbon ring that is a bulky group in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is eased, and substrate adhesion is improved.
Examples of such hydrocarbon rings include aliphatic hydrocarbon rings that may have a substituent, aromatic hydrocarbon rings that may have a substituent, and combinations 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 a divalent or higher group.

Specific examples of the hydrocarbon ring include aliphatic groups 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, fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and cardo structures (9,9-diarylfluorene ); Groups in which some of these groups are substituted with substituents.
Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.

When an aliphatic hydrocarbon ring is included as the hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesion of the colored layer and improving the luminance of the obtained colored layer.
In addition, the inclusion of the cardo structure is particularly preferable from the viewpoint of improving the curability of the colored layer, suppressing fading of the coloring material, and improving solvent resistance (NMP swelling suppression).

An acrylic resin such as an acrylic copolymer having a constitutional unit having a carboxy group and a styrene-acrylic copolymer having a carboxy group includes, 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.
Examples of the carboxy group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. It is done. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints 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. Preferred are those containing a carboxy group such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. More preferably, it is a copolymer.

  Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl. (Meth) acrylate, styrene, etc. are mentioned. From the point that the cross-sectional shape of the colored layer after development has a large effect of being maintained in the heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( It is preferable to use at least one selected from (meth) acrylate, benzyl (meth) acrylate, and styrene.

  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. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photosensitive colored resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

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

  In addition, in the carboxy group-containing copolymer such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and ethylene The compound having an ionic double bond is preferably 10% by mass or more and 95% by mass or less, and 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.

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

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxy group, Epoxy (meth) obtained by making the reaction product of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones.
As the epoxy (meth) acrylate resin having a carboxy group, it is preferable that the hydrocarbon ring is included in the molecule, and among them, the one containing a cardo structure improves the curability of the colored layer and causes the colorant to fade. It is preferable from the standpoint of suppression and the remaining film ratio of the colored layer is increased.
The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

As the alkali-soluble resin, it is preferable to select and use an acid-soluble resin having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used for the developer. 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) with respect to an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that it is 80 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K 0070: 1992.

The ethylenically unsaturated bond equivalent in the case where 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 obtains the effect of excellent adhesion to the substrate. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes.
Here, the ethylenically unsaturated bond equivalent is a 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 the ethylenic double bond 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 in 1 g of alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992. It may be calculated.

  The alkali-soluble resin used in the photosensitive colored resin composition may be used singly or in combination of two or more, and the content is not particularly limited, but the photosensitive colored resin 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, based on the total solid content of the composition. When the content of the alkali-soluble resin is not less than the above lower limit value, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is not more than the above upper limit value, film roughness or lack of pattern can be caused during development. Can be suppressed.

[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 is usually a compound having two or more ethylenically unsaturated double bonds. In particular, a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in JP2013-029832A.

  These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the photosensitive colored resin composition of the present invention requires excellent photocurability (high sensitivity), the photopolymerizable compound has three (trifunctional) or more polymerizable double bonds. Preferred are poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid modified products. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, modified succinic acid of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaerythritol modified from succinic acid Hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate and the like are preferable. When a phosphorus atom-containing polyfunctional (meth) acrylate such as tri (2- (meth) acryloyloxyethyl) phosphate is used, fading of the rake color material is likely to be suppressed, and it is preferable from the viewpoint of easily improving luminance after post-baking. .

  The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but the photopolymerizable compound is preferably 5% by mass or more and 60% based on the total solid content of the photosensitive colored resin composition. It is in the range of 10% by mass or more and 40% by mass or less, more preferably 10% by mass or less. When the content of the photopolymerizable compound is not less than the above lower limit, photocuring sufficiently proceeds, the exposed portion can suppress elution during development, and the content of the photopolymerizable compound is not more than the above upper limit. Alkali developability is sufficient.

[Photoinitiator]
There is no restriction | limiting in particular as a photoinitiator used in the photosensitive coloring resin composition of this invention, From the conventionally known various initiators, it can be used 1 type or in combination of 2 or more types.
Examples of the photoinitiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and the like. be able to. Specific examples of the photoinitiator include benzophenone, 4,4′-bisdiethylaminobenzophenone, aromatic ketones such as 4-methoxy-4′-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and ethylbenzoin. Benzoin, biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, etc. Halomethyloxadiazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1 , 2-Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl]- Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-Benzoyl-4′-methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethyl Thioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1 [4- (4-Morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone , Α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1 -Propanone and the like.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- ( 4-Morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (for example, High Cure ABP, manufactured by Kawaguchi Chemical), and diethylthioxanthone are preferably used. Further, an α-aminoacetophenone photoinitiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and a thioxanthone photoinitiator such as diethylthioxanthone are combined. Is preferable from the viewpoint of adjusting sensitivity, suppressing water stain and improving development resistance.

In the present invention, the photoinitiator preferably includes an oxime ester photoinitiator from the viewpoint of improving sensitivity. By using an oxime ester photoinitiator, in-plane line width variations are easily suppressed when forming a fine line pattern. Furthermore, by using an oxime ester photoinitiator, the development resistance is improved, and the effect of suppressing the occurrence of water stain tends to be increased. In addition, water stain means that, when a component that enhances alkali developability is used, a trace of water stain is generated after rinsing with pure water after alkali development. Such water stain disappears after post-baking, so there is no problem as a product, but it is detected as unevenness in the appearance inspection of the patterning surface after development, and there is a problem that it is impossible to distinguish between normal products and abnormal products. Arise. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.
As the oxime ester photoinitiator, those having an aromatic ring are preferable, and those having a condensed ring including an aromatic ring are preferable from the viewpoint of reducing contamination of the photosensitive colored resin composition by decomposition products and contamination of the apparatus. Is more preferable, and it is more preferable to have a condensed ring including a benzene ring and a hetero ring.
As the oxime ester photoinitiator, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, Special Table 2010-527339, Special Table 2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP2013-041153A and the like. As commercial products, Irgacure OXE-01 (manufactured by BASF) having a carbazole skeleton, Adeka Arcles NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials), ADEKA having a diphenyl sulfide skeleton ARCULS NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Power Electronics New Materials), TR-PBG-365 (Changzhou Power Electronics New Materials, Inc.) having a fluorene skeleton Product), SPI-04 (manufactured by Sanyo) or the like may be used. In particular, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of improving luminance. Further, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
In addition, when two or more oxime ester photoinitiators are used in combination, two or more oxime ester compounds having different sensitivities are appropriately selected and combined to maintain a good sensitivity while maintaining the line width during pattern formation. Further, it is preferable in that the development resistance and luminance are easily improved and the effect of suppressing the occurrence of water stain is high. In particular, the combined use of two types of oxime ester photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton increases heat resistance. From the viewpoint that the luminance is easily improved.

  In addition, when using a highly sensitive photoinitiator in order to pattern with a small exposure amount, a radical will move to an unexposed part after radical generation. Therefore, when patterning the colored layer, simultaneously forming the desired micropores in the colored layer, the shape of the unexposed part inside the exposed part is maintained and the peripheral part of the unexposed part is formed without any wrinkles. It was difficult. On the other hand, when an oxime ester photoinitiator having a fluorene skeleton is used for 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 when the colored layer is patterned. is there. Among these, when an oxime ester photoinitiator having a fluorene skeleton and an oxime ester photoinitiator having a phenyl sulfide skeleton are used in combination, the shape of the micropores can be easily improved without greatly reducing the brightness and sensitivity. To preferred. When it is easy to form desired micropores in the colored layer, the photosensitive colored resin composition of the present invention forms, for example, a colored layer on the TFT substrate in order to form a reflective color filter. It is also suitable for applications in which through holes for conduction are formed in the colored layer. Note that “billing” refers to a problem in which dimensional accuracy is deteriorated due to non-uniformity of straight lines or curves at the pattern end.

Moreover, it is preferable to use the α-aminoacetophenone photoinitiator in combination with the oxime ester photoinitiator from the viewpoint of suppressing water stain and improving sensitivity. A photoinitiator having a tertiary amine structure such as an α-aminoacetophenone series has a tertiary amine structure that is an oxygen quencher in the molecule, so that radicals generated from the initiator are hardly deactivated by oxygen, and the sensitivity It is because it can improve.
Further, it is preferable to combine a thioxanthone photoinitiator with an oxime ester photoinitiator in terms of sensitivity adjustment, water stain suppression and development resistance improvement, and two or more oxime ester photoinitiators and thioxanthone A combination of a photoinitiator is preferable in that the brightness and development resistance are improved, the sensitivity is easily adjusted, the effect of suppressing the occurrence of water stain 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 effects of the present invention are not impaired, but with respect to the total solid content of the photosensitive colored resin composition, Preferably it is 0.1 mass% or more and 12.0 mass% or less, More preferably, it exists in the range of 1.0 mass% or more and 8.0 mass% or less. When this content is not less than the above lower limit, photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development. On the other hand, if it is not more than the above upper limit, the yellowing of the resulting colored layer becomes strong and the luminance Can be suppressed.
In addition, solid content is all except a solvent, and a liquid photopolymerizable compound etc. are also contained.

[solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive colored resin composition and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent 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; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Tone solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate, butyl carbitol acetate (BCA), carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol mono Glycol ether solvents such as chill ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactone solvents such as butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Examples thereof include organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), carbitol acetate, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate It is preferable that it is 1 or more types selected from the group which consists of ethyl lactate and 3-methoxybutyl acetate from the point of the solubility of another component, and the applicability | paintability.

  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. Usually, it is preferably in the range of 55% by mass to 95% by mass with respect to the total amount of the photosensitive colored resin composition containing the solvent, and more preferably in the range of 65% by mass to 88% by mass. It is more preferable. When the content of the solvent is within the above range, the coating property can be excellent.

[Dispersant]
In the photosensitive colored resin composition of the present invention, the colorant is preferably used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer dispersant is preferable because it can be uniformly and finely dispersed.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid 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 their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethyleneimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxy group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxy) Polyester, polyamide or ester-amide co-condensate having a group ( Li esteramide) reaction products obtained by reacting one or more compound selected from among the three compounds of the), and the like.

As the polymer dispersant, among them, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value is preferable from the viewpoint that the colorant can be suitably dispersed and the dispersion stability is good. Among these, a polymer dispersant containing a polymer containing a structural unit having a tertiary amine is preferable from the viewpoint of good dispersibility, no precipitation of foreign matters when forming a coating film, and improvement of luminance and contrast.
The structural unit having a tertiary amine is a site having an affinity for the colorant. A polymer containing a structural unit having a tertiary amine usually contains a structural unit that becomes a site having an affinity for a solvent. As a polymer containing a structural unit having a tertiary amine, among them, a block part containing a structural unit having a tertiary amine (hereinafter sometimes referred to as A block) and a block part having solvent affinity ( In the following, it is preferable that a block copolymer having a B block) is excellent in heat resistance and capable of forming a coating film having high luminance.

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, and among them, the structural unit represented by the following general formula (I) is preferable because the main chain skeleton is hardly thermally decomposed and has high heat resistance. It 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 _{- [(CH 2) y -O} ] z - (CH 2) y - 2 monovalent organic group represented by, ^{R 3} And R ⁴ each independently represents an optionally substituted chain or cyclic hydrocarbon group, or R ³ and R ⁴ are bonded to each other to form a cyclic structure, and R ⁵ and R ⁶ are Each independently represents a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

  Examples of the divalent linking group Q in the general formula (I) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (- R′—OR ″ —: R ′ and R ″ each independently represents an alkylene group) and combinations thereof. Among these, Q is a —COO— group or —CONH— from the viewpoint of heat resistance of the polymer obtained, solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and 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.
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.
R ² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. 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 monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.

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

  Further, as will be described later, at least a part of the amino group of the structural unit having the tertiary amine may be salted with a salt-forming agent.

As the structural unit contained in the solvent affinity block part, a structural unit copolymerizable with the conventionally known general formula (I) can be appropriately selected and used.
For example, the B block may be the same as the B block of International Publication No. 2016/104493.

Further, among them, in the present invention, the dispersant is a polymer having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less that includes the structure represented by the general formula (I), and has good dispersibility. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
When the amine value is within the above range, it is excellent in viscosity stability over time and heat resistance, and also in alkali developability and solvent resolubility. The 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 a sample, and can be measured by the method defined in JIS-K7237: 1995. . When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is itself The amine value of can be measured.

The acid value of the dispersant used in the present invention is preferably 0 mgKOH / g from the viewpoint of further improving the solvent re-solubility and development adhesion, and from the viewpoint of substrate adhesion and dispersion stability. The smaller the acid value, the less likely it is to be eroded by the basic developer, which is considered to improve the development adhesion. On the other hand, from the viewpoint of the effect of suppressing the development residue, it is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more. Moreover, it is preferable that the acid value of the dispersing agent used for this invention is 18 mgKOH / g or less from the point which can prevent the deterioration of image development adhesiveness and the solvent resolubility. Among these, 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 that the development adhesion and the solvent re-solubility are improved.
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 the solvent resolubility and development adhesion, and from the standpoint of substrate adhesion and dispersion stability. / G is preferable. On the other hand, from the viewpoint of the effect of suppressing the development residue, it is preferably 1 mgKOH / g or more, and 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 improving development adhesion and solvent resolubility. Preferably, it is still more preferably 8 mgKOH / g or less.

Moreover, in this invention, it is preferable that the glass transition temperature of a dispersing agent is 30 degreeC or more from the point which image development adhesiveness improves. That is, whether the dispersant is a block copolymer before salt formation or a salt block copolymer, the glass transition temperature is preferably 30 ° C. or higher. When the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and the development adhesion may be lowered. This is presumably because when the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, resulting in poor development adhesion. When the glass transition temperature is 30 ° C. or higher, the molecular motion of the dispersant during development is suppressed, so that it is estimated 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 lower from the viewpoint of operability during use, such as easy precision weighing.
The glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.
Moreover, the glass transition temperature (Tg) of a block part and a block copolymer can be calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the block portion. 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 is the sum from i = 1 to n. As the value of the homopolymer glass transition temperature (Tgi) of each monomer, the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.

  Moreover, the monomer whose glass transition temperature (Tgi) of the homopolymer of the monomer is 10 ° C. or higher from the viewpoint that the glass transition temperature of the dispersant used in the present invention is a specific value or higher and development adhesion is improved. Is preferably 75% by mass or more, and more preferably 85% by mass or more in the B block.

  In the block copolymer, the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. Is preferably in the range of 0.1 to 1.0 from the viewpoint of the dispersibility and dispersion stability of the coloring material.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, and preferably 2000 to 15000 from the viewpoint of improving colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000-12000.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC). The macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of the amino group 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 a salt formed with a salt-forming agent such as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Among them, the dispersibility of the colorant is that 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 preferred from the viewpoint of excellent dispersion stability. Specific examples of the organic acid compound used for such a dispersant include organic acid compounds described in JP 2012-236882 A and the like.
The halogenated hydrocarbon is preferably at least one of 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 in the case of using the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the content is 1 with respect to the total solid content of the photosensitive colored resin composition. It can be used in the range of from mass% to 40 mass%. Furthermore, it is preferable to mix | blend in 2 to 30 mass% with respect to the solid content whole quantity of the photosensitive coloring resin composition, and it is preferable to mix | blend especially in the ratio of 3 to 25 mass%. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a coloring material, and is excellent in the storage stability of the photosensitive coloring resin composition. Moreover, if it is below the said upper limit, developability will become favorable.

[Antioxidant]
The photosensitive colored resin composition according to the present invention preferably further contains an antioxidant from the viewpoint of improving heat resistance, suppressing fading of the coloring material, and improving luminance. The photosensitive colored resin composition according to the present invention contains an antioxidant in combination with an oxime ester photoinitiator, so that when the micropores are formed in a cured film, the excess in the micropores is not impaired. Since the radical chain reaction can be controlled, it is possible to more easily form micropores having a desired shape.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known ones. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. It is preferable to use a hindered phenol type antioxidant from the point which makes the shape of a point and a micropore favorable. It may be a latent antioxidant as described in WO2014 / 021023.

  As the hindered phenol-based antioxidant, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX 1010, 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: Sumilyzer MDP-S, Manufactured by Sumitomo Chemical Co., Ltd.), 6,6′-thiobis (2-tert-butyl-4-methylphenol) Trade name: Irganox 1081, manufactured by BASF), 3,5-di -tert- butyl-4-hydroxybenzyl phosphonic acid diethyl (trade name: Irugamodo 195, manufactured by BASF), and the like. Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .

  As content of antioxidant, it is preferable that antioxidant is 0.1 mass part or more and 10.0 mass part or less with respect to 100 mass parts of total solids in a colored resin composition, 0.5 It is more preferable that the amount is not less than 5.0 parts by mass. If it is more than the said lower limit, it is excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.

  When the antioxidant is used in combination with the oxime ester photoinitiator, the content of the antioxidant is 1 part by mass of the antioxidant with respect to 100 parts by mass of the total amount of the oxime ester photoinitiator. The amount is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 65 parts by mass or less. If it is in the said range, it is excellent in the effect of the said combination.

[Optional components]
The photosensitive colored resin composition of the present invention may contain various additives as necessary. Examples of the additives include 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 the surfactant and the plasticizer include those described in JP2013-029832A.

  In the photosensitive colored resin composition of the present invention, the P / V ratio ((color material component mass in the composition) / (solid content mass other than color material components in the composition) ratio) is a blue colored resin composition. In the case of a product, the P / V ratio is preferably 0.20 or more, more preferably 0.28 or more, and further preferably 0.35 or more from the viewpoint of desired color development. preferable. On the other hand, from the viewpoint of excellent solvent resolubility, development residue, development adhesiveness, development resistance, development cracking and unevenness generation suppression effect, contrast, and micropore flickering suppression, it is preferably 0.65 or less, It is more preferably 0.50 or less, and still more preferably 0.45 or less.

[Method for producing photosensitive colored resin composition]
The method for producing the photosensitive colored resin composition of the present invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, an antioxidant, and, if desired. It is preferable from the point of improving the contrast that the colorant can be uniformly dispersed in the solvent by a dispersant, and contains various additive components used, and is prepared by mixing using a known mixing means. can do.
As a method for preparing the resin composition, for example, (1) First, a color material and a dispersant are added to a solvent to prepare a color material dispersion, and the alkali-soluble resin, light, A method of mixing a polymerizable compound, a photoinitiator, and various additive components used as desired; (2) In a solvent, a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator (3) In a solvent, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a photoinitiator are optionally used. A method in which various additive components are added and mixed, and then a color material is added and dispersed; (4) A color material dispersion is prepared by adding a color material, a dispersant, and an alkali-soluble resin to a solvent. The dispersion is further mixed with an alkali-soluble resin, a solvent, and light. And the like; and polymerizable compound, a photoinitiator, by adding various additive components optionally used, mixing method.
Among these methods, the above methods (1) and (4) are preferable from the viewpoint that the aggregation of the coloring material can be effectively prevented and dispersed uniformly.

  The method for preparing the color material dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) A dispersant is mixed and stirred in advance to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound. Let A method of mixing this with a coloring material and other components as necessary, and dispersing the mixture using a known stirrer or disperser; (2) Mixing and stirring a dispersant in a solvent to prepare a dispersant solution; A method of mixing a coloring material and, if necessary, an organic acid compound and, if necessary, other components and dispersing the mixture using a known stirrer or disperser; (3) mixing and stirring a dispersant in a solvent. Then, the dispersant solution is prepared, then the colorant and other components are mixed as necessary, and the mixture is made into a dispersion using a known stirrer or disperser, and then an organic acid compound is added as necessary. The method etc. are mentioned.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

  Since the photosensitive colored resin composition of the present invention can form a pattern with a desired line width while improving the luminance after repeating the high-temperature heating step, it is suitably used for color filter applications.

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 is obtained, for example, by forming a coating film of the photosensitive colored resin composition according to the present invention, drying the coating film, and then developing the film, if necessary. Can do. As a method for forming, exposing, and developing a coating film, for example, a method similar to the method used in forming a colored layer provided in the color filter according to the present invention described later can be used.
In addition, the cured product according to the present invention has improved brightness even after the high-temperature heating step, and a pattern is 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 cured product.

  Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic 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 part 2, and a colored layer 3.

[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 an opening of a light-shielding part on the substrate to be described later, and is usually composed of a colored pattern of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the photosensitive colored resin composition, but is usually preferably in the range of 1 μm to 5 μm.

The colored layer can be formed by the following method, for example.
First, the above-described photosensitive colored resin composition of the present invention is applied onto a substrate to be described later using an application means 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. Then, a wet coating film is formed. Of these, spin coating and die coating can be preferably used.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, so that a photopolymerizable compound such as an alkali-soluble resin and a polyfunctional monomer is irradiated with light. A polymerization reaction is performed to obtain a cured coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, 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 image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

[Shading section]
The light shielding part in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are 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 the photosensitive resist, etc. is there.

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

[substrate]
As the substrate, a transparent substrate or a silicon substrate, which will be described later, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing about 100 micrometers or more and 1 mm or less can be used, for example.
The color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, etc., in addition to the substrate, the light shielding portion, and the colored layer. Also good.

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.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter according to the present invention described above, 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 illustrating an example of a display device of the present invention, and is a schematic diagram illustrating an example of a liquid crystal display device. As illustrated in FIG. 2, the 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.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, 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]
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating 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 includes a color filter 10 and an organic light emitter 80. 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 method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As 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 configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
In addition, the acid value of the block copolymer before salt formation was calculated | required by the method according to the method of JISK0070: 1992.
The amine value of the block copolymer before salt formation was determined by a method according to the method described in JIS K 7237: 1995.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.
The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is determined by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology Co., Ltd.) according to the method described in JIS K7121. It 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, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA) and perbutyl O (manufactured by NOF Corporation). ) 6 parts by mass and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ° C., and after 2 hours from the completion of dropping of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing air, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, and the temperature was raised to 110 ° C. Then, 0.8 parts by mass of triethylamine was added and the mixture was heated at 110 ° C. for 15 hours. By addition reaction, an alkali-soluble resin A solution (weight average molecular weight (Mw) 9,000, acid value 90 mgKOH / g, solid content 40% by mass) was obtained.

(Synthesis Example 2: Synthesis of Block Copolymer 1)
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 part by mass of methyl isobutyrate were injected using a syringe. B block monomer 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by mass, 2- (trimethylsilyloxy) ethyl methacrylate (TMSMA) 29.1 parts by mass, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass Parts, 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 And dripped. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, diluted with PGMEA to obtain a solid content solution of 30% by mass. Add 32.5 parts by mass of water, raise the temperature to 100 ° C., react for 7 hours, deprotect the EEMA-derived structural unit to a methacrylic acid (MAA) -derived structural unit, and deprotect the TMSMA-derived structural unit. The structural unit was derived from 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, purified by filtration and vacuum drying, and the block copolymer 1 containing the structural unit represented by the general formula (I) (amine value 95 mgKOH / g, acid value 8 mgKOH / g, Tg38 ° C.). The weight average molecular weight Mw was 7730.

(Synthesis Example 3: Synthesis of salt-type block copolymer 2)
Add 250 parts by mass of THF and 0.75 part by mass of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 6.1 parts by mass of butyl lithium (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 monomer 2-ethylhexyl methacrylate (EHMA) 9 parts by mass, n-butyl methacrylate (BMA) 13.4 parts by mass, benzyl methacrylate (BzMA) 7.5 parts by mass, methyl methacrylate (MMA) 47 0.5 part by mass was dropped over 60 minutes using an addition funnel. After 30 minutes, 22.6 parts by weight of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. It was reprecipitated in hexane, purified by filtration and vacuum drying, and the block copolymer 2 containing the structural unit represented by the general formula (I) was obtained. (Amine value 95 mgKOH / g, acid value 0 mgKOH / g) The weight average molecular weight Mw was 7600.
50 parts by mass of the obtained block copolymer 2 was dissolved in 213 parts by mass of PGMEA. Thereto, 3.2 parts by mass of benzyl chloride was added and reacted at 90 ° C. for 12 hours to obtain a PGMEA solution (solid content 20%) of salt-type block copolymer 2.

(Synthesis Example 4: Synthesis of Blue Color Material 1)
(1) Synthesis of Intermediate 1 Referring to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g (inclusive) of Intermediate 1 represented by the following chemical formula (a) Rate 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent and elemental analysis values: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of Blue Color Material 1 Intermediate 5.00 g (4.58 mmol) was added to 300 ml of water and dissolved at 90 ° C. to obtain 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 Co., Ltd. was added to 100 mL of water and stirred at 90 ° C. An aqueous phosphotungstic acid solution was prepared. The intermediate 2 solution was mixed with an aqueous phosphotungstic acid solution at 90 ° C., and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of blue color material 1 represented by the following chemical formula (b).
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%)
Further, it was confirmed by ³¹ P-NMR that the polyacid structure of phosphotungstic acid was maintained after the blue colorant 1 was obtained.

(Synthesis Example 5: Synthesis of blue color material 2)
_{(1) K 6 (P 2} MoW 17 O 62) prepared NaWO 4 · _2H 2 _O of (Wako Pure Chemical Industries, _{Ltd.) 44.0g, Na 2 MoO 4 ·} 2H 2 O ( Kanto Chemical Co., Ltd.) 1 .90 g was dissolved in 230 g of purified water. To this solution, 64.9 g of 85% phosphoric acid was added with stirring using a dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction solution was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added with stirring. After further stirring for 1 hour, the precipitate was filtered off. The obtained solid was dried at 90 ° C. to obtain 29.4 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ).
(2) Synthesis of blue color material 2 C.I. I. Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.30 g was added to 350 ml of purified water and dissolved by stirring at 40 ° C. to prepare a BB7 solution. Separately, 10.0 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) prepared in the above (1) was dissolved in 40 ml of purified water. A K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution was added to the BB7 solution, and the solution was stirred at 40 ° C. for 1 hour. Next, the internal temperature was raised to 80 ° C., and the mixture was further stirred for 1 hour to be raked. After cooling, the mixture was filtered and washed with 300 ml of purified water three times. The obtained solid was dried at 90 ° C. to obtain 10.4 g of a blue color material 2 which is a black-blue solid and has an average primary particle size of 40 nm, which is a triarylmethane lake color material.

(Production Example 1: Preparation of colorant dispersion 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 of Synthesis Example 1 (solid content 40% by mass), 2 salt-type block copolymer 2 solution of Synthesis Example 3 (solid content 20 (Mass%) 13.0 parts by mass was added and stirred.
There C. I. Pigment Blue 15: 6 (PB15: 6, product name FASTOGEN BLUE A510 manufactured by DIC Corporation) 13.0 parts by mass, particle size 2.0 mm Zirconia beads 100 parts by mass, paint shaker (Asada Tekko Co., Ltd.) as preliminary crushing The mixture was then shaken 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 the main crushing to obtain a colorant dispersion A.

(Production Example 2: Preparation of colorant dispersion B)
In Production Example 1, C.I. I. In place of Pigment Blue 15: 6, C.I. I. Colorant dispersion B was obtained in the same manner as in Production Example 1 except that CI Pigment Blue 15: 3 (PB15: 3, trade name: Chromofine Blue A-220JC, manufactured by Dainichi Seika Kogyo Co., Ltd.) was used.

(Production Example 3: Preparation of colorant dispersion C)
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 (solid content 40% by mass) of Synthesis Example 1, and the PGMEA solution of the block copolymer 1 of Synthesis Example 2 (amine value 95 mgKOH) / G, 45 mass% solid content) 10.0 parts by mass were added and stirred. Thereto was added 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.6 molar equivalent to the tertiary amino group of the block copolymer), and the mixture was stirred at room temperature for 30 minutes.
Thereto, 13.0 parts by mass of the blue color material 1 obtained in Synthesis Example 4 and 100 parts by mass of zirconia beads having a particle size of 2.0 mm were added and shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as preliminary crushing. After that, 200 parts of zirconia beads having a particle diameter of 0.1 mm were changed and dispersed for 4 hours with a paint shaker as the main crushing, and a colorant dispersion C was obtained.

(Production Example 4: Preparation of colorant dispersion D)
In Production Example 3, instead of using the blue color material 1 obtained in Synthesis Example 4, the color material dispersion was used in the same manner as in Production Example 3 except that the blue color material 2 obtained in Synthesis Example 5 was used. D was obtained.

(Production Example 5: Preparation of colorant dispersion E)
In Production Example 1, C.I. I. In place of Pigment Blue 15: 6, C.I. I. A colorant dispersion E was obtained in the same manner as in Production Example 1 except that CI Pigment Violet 23 (PV23, trade name Hostaperm Violet RL-NF, manufactured by Clariant) was used.

(Preparation Example 1: Preparation of photosensitive binder component CR-1)
Dipentaerythritol hexaacrylate (DPHA) (Aronix M402 (manufactured by Toagosei Co., Ltd.)) as a photopolymerizable compound with respect 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, Irgacure 907 (manufactured by BASF, α-aminoacetophenone photoinitiator) as an initiator, 1.1 parts by mass, SPI-04 (manufactured by Sanyo, oxime ester photoinitiator having a fluorene skeleton) 1 .3 parts by mass, Kayacure DETX-S (manufactured by Nippon Kayaku, thioxanthone photoinitiator) 0.3 part by mass, antioxidant IRGANOX 1010 (manufactured by BASF) 0.8 part by mass, PGMEA 38.1 parts by mass, A photosensitive binder component CR-1 was obtained.

(Preparation Example 2: Preparation of photosensitive binder component CR-2)
26.1 parts by mass of an alkali-soluble resin solution (propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of an epoxy acrylate having a fluorene skeleton, trade name V259ME, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., solid content 55.8%) In contrast, 18.2 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M403, manufactured by Toagosei Co., Ltd.), tri (2- (meth) acryloyloxyethyl) phosphate (Biscoat 3PA, Osaka Organic Chemistry) as a photopolymerizable compound 3.7 parts by mass for industrial use, 1.1 parts by mass of Irgacure 907 (manufactured by BASF, α-aminoacetophenone photoinitiator) as an initiator, SPI-04 (manufactured by Sanyo, oxime ester photoinitiator having a fluorene skeleton) Agent) 0.5 parts by mass, TR-PBG-3057 (ordinary) 0.8 parts by mass of Oxime ester photoinitiator with diphenyl sulfide skeleton, manufactured by Strong Electronics New Materials Co., Ltd., 0.3 parts by mass of Kayacure DETX-S (manufactured by Nippon Kayaku, thioxanthone photoinitiator), antioxidant IRGANOX1010 (made by BASF) 0.8 mass part and PGMEA 48.5 mass part were added, and photosensitive binder component CR-2 was obtained.

(Preparation Example 3: Preparation of photosensitive binder component CR-3)
In Preparation Example 1, instead of SPI-04 (manufactured by Sanyo, oxime ester photoinitiator having a fluorene skeleton), it was changed to OXE-02 (manufactured by BASF, oxime ester photoinitiator having a carbazole skeleton). Prepared photosensitive binder component CR-3 in the same manner as in Preparation Example 1.

(Preparation Example 4: Preparation of photosensitive binder component CR-4)
In Preparation Example 1, SPI-04 (Sanyo, oxime ester photoinitiator having a fluorene skeleton) 1.3 parts by mass SPI-04 (Sanyo, oxime ester photoinitiator having a fluorene skeleton) Agent) 0.5 parts by mass, TR-PBG-3057 (manufactured by Changzhou Power Electronics New Materials Co., Ltd., an oxime ester photoinitiator having a diphenyl sulfide skeleton) Same as Preparation Example 1, except for changing to 0.8 parts by mass Thus, a photosensitive binder component CR-4 was obtained.

(Example 1: Preparation of photosensitive colored resin composition)
4.0 parts by weight of colorant dispersion A, 22.6 parts by weight of colorant dispersion C, 24.6 parts by weight of photosensitive binder component CR-1 of Preparation Example 1, surfactant Megafac R08MH (manufactured by DIC) 0 0.02 part by mass and 48.8 parts by mass of PGMEA were mixed to obtain a photosensitive colored resin composition of Example 1.

(Examples 2 to 5, Comparative Examples 1 to 10: Preparation of photosensitive colored resin composition)
Examples 2 to 5 were the same as Example 1 except that the color material dispersion used was changed so that the color material ratios (mass ratios) shown in Table 1-1 to Table 1-3 were obtained. The photosensitive colored resin composition of Comparative Examples 1-10 was obtained.

(Example 6: Preparation of photosensitive colored resin composition)
A photosensitive colored resin composition of Example 6 was obtained in the same manner as in Example 1 except that the photosensitive binder component CR-1 in Example 1 was changed to the photosensitive binder component CR-2 in Preparation Example 2. .

(Examples 7 to 10, Comparative Examples 11 to 20: Preparation of photosensitive colored resin composition)
Examples 7 to 10 are the same as Example 6 except that the color material dispersion used is changed so that the color material ratios (mass ratios) shown in Table 2-1 to Table 2-3 are obtained. The photosensitive colored resin composition of Comparative Examples 11-20 was obtained.

(Example 11: Preparation of photosensitive colored resin composition)
A photosensitive colored resin composition of Example 11 was obtained in the same manner as in Example 1 except that the photosensitive binder component CR-1 of Example 1 was changed to the photosensitive binder component CR-3 of Preparation Example 3. .

(Example 12: Preparation of photosensitive colored resin composition)
A photosensitive colored resin composition of Example 12 was obtained in the same manner as in Example 1 except that the photosensitive binder component CR-1 in Example 1 was changed to the photosensitive binder component CR-4 in Preparation Example 4. .

[Evaluation method]
<Brightness evaluation, heat resistance evaluation>
Each of the photosensitive colored resin compositions of Examples and Comparative Examples has a post-baking chromaticity of y = 0.093 on a glass substrate (NH Techno Glass Co., Ltd., “NA35”) having a thickness of 0.7 mm. It was applied using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (blue colored film) was obtained by irradiating ultraviolet rays of 60 mJ / cm ² using an ultrahigh pressure mercury lamp without passing through a photomask. The obtained film was post-baked in a clean oven at 230 ° C. for 25 minutes, and the luminance was measured using “Microspectrometer OSP-SP200” manufactured by Olympus Corporation. Thereafter, the obtained film was further post-baked in a clean oven at 240 ° C. for 25 minutes, and 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 baking for 25 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 luminance after post-baking at 230 ° C. for 25 minutes and the luminance after the heat resistance test (after 230 ° C. for 25 minutes + 240 ° C. for 25 minutes + 240 ° C. for 25 minutes).
Further, the change in chromaticity of the colored film was evaluated from 240 minutes to 50 minutes after 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
ΔEab is 3 or less, A is ΔEab is more than 3 and less than 5 is B, ΔEab is more than 5 and less than 10 is C, and ΔEab is more than 10 is D. It is evaluated that the smaller the value of ΔEab, the better the heat resistance.

(Evaluation of line width shift, micropore evaluation)
The colored resin compositions of Examples and Comparative Examples were each applied on a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater so that the film thickness was 3 μm. did. Then, after heating and drying on a hot plate at 80 ° C. for 3 minutes, a fine line pattern (pattern for line width shift evaluation) having an opening width of 90 μm and an independent fine line having an opening size of 90 μm × 300 μm are placed in the center at 20 μm × 20 μm. UV light of 60 mJ / cm ² was irradiated using a super high pressure mercury lamp through a photomask pattern having a pattern (pattern for evaluating micropores) in which a chrome mask was arranged. Then, the glass plate on which the colored layer was formed was shower-developed using 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and post-baked for 30 minutes in a 230 ° C. clean oven. Among 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 line when the opening width of the photomask was 90 μm and the design line width was 95 μm was measured. Moreover, the following reference | standard evaluated about the shape of a micropore, and the wobble of the peripheral part of a micropore.

[Line width shift]
The line width shift value (μm), which is a deviation from the design line width, was calculated by the following formula.
Line width shift value (μm) = Measured line width (μm) −95 (μm)
A: Line width shift value of −2 μm or more and 2 μm or less B: Line width shift value of −4 μm or more and less than −2 μm C: Line width shift value of less than −4 μm or more than 2 μm Desired line as the deviation from the design line width is smaller It is evaluated that a pattern can be formed with a width.
[Micropore shape]
A: The deviation of the dimension of the minute holes formed in the colored layer is smaller than 2% in absolute value with respect to the dimension of the chromium mask arranged in the independent thin line pattern. B: The chromium mask arranged in the independent thin line pattern. Deviations in the size of the micropores formed in the colored layer with respect to the dimension of 2 to 6% in absolute value C: formed in the colored layer with respect to the dimension of the chrome mask arranged in the independent fine line pattern Deviation of the dimension of the formed micropore is larger than 6% and not more than 8% in absolute value. D: The dimension deviation of the microhole formed in the colored layer is different from the dimension of the chromium mask arranged in the independent thin line pattern. The absolute value is larger than 8%. Note that the dimensional deviation was calculated as an average value of the dimensional deviation of each side.
[Biritsuki]
A: Ten-point average roughness of the peripheral portion of the micropore formed in the colored layer is smaller than 0.1 B: Ten-point average roughness of the peripheral portion of the micropore formed in the colored layer is 0.1 or more and 0 Less than 4 C: Ten-point average roughness of the peripheral edge of the micropore formed in the colored layer is not less than 0.4 and less than 0.6 D: Ten-point average roughness of the peripheral edge of the micropore formed in the colored layer 0.6 or more The ten-point average roughness was measured in accordance with JIS B0601.

[Summary of results]
From the results of the table, the photosensitive coloring resin compositions of Examples 1 to 12 in which the coloring material combines the phthalocyanine pigment and the coloring material represented by the general formula (1) at a specific ratio are 230 ° C. Both the brightness after the post-baking for 25 minutes and the brightness after the heat test (after the post-baking at 230 ° C. for 25 minutes + 240 ° C. for 25 minutes + 240 ° C. for 25 minutes) improved the high temperature heating process (post baking) It was revealed that it is possible to form a pattern with a desired line width while improving the luminance later.
On the other hand, any of the comparative examples in which the phthalocyanine pigment is combined with a rake color material different from the color material represented by the general formula (1) has poor heat resistance, and even when used in the same ratio as in the examples, The brightness after the high-temperature heating process (post-baking) was low. In addition, in the comparative example in which the violet pigment is combined with the phthalocyanine pigment, although the heat resistance itself is not a problem, the brightness after the high-temperature heating process (post-baking) is low, and the shift value from the design line width is large and the desired line width is obtained. It was difficult to obtain a pattern.

  Among the examples, when comparing Examples 1 and 6, 11 and 12, Examples 2 and 7, Examples 3 and 8, Examples 4 and 9, and Examples 5 and 10, it is an aliphatic hydrocarbon ring. It has been clarified that when an alkali-soluble resin containing a structure and a phosphorus atom-containing polyfunctional (meth) acrylate are used, the heat resistance is improved and the luminance after the finally obtained heat test is improved. Moreover, by comparing Example 1, 6, 11 and 12, an oxime ester photoinitiator having a fluorene skeleton or an oxime ester photoinitiator having a diphenyl sulfide skeleton is used as the oxime ester photoinitiator. It was revealed that the luminance after the finally obtained heat resistance test was improved. In addition, when two oxime ester photoinitiators are used and an oxime ester photoinitiator having a fluorene skeleton and an oxime ester photoinitiator having a diphenyl sulfide skeleton are used in combination, the shape of the micropores is improved. Was revealed.

DESCRIPTION OF SYMBOLS 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 emitter 100 Organic light emitting display device

Claims (10)

A photosensitive colored resin composition containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The color material includes a phthalocyanine pigment and a color material represented by the following general formula (1),
The content of the color material represented by the following general formula (1) is 20% by mass to 85% by mass with respect to the total content of the phthalocyanine pigment and the color material represented by the following general formula (1). Photosensitive coloring resin composition.

(In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N has no π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain, and B ^c- represents a c-valent anion. R ^{i to} R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R ⁱⁱ , R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, and R ^vi and R ^vii each independently represents an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom, or .Ar ¹ represents cyano group represents a divalent aromatic group which may have a substituent Each plurality of ^R i ^{to R vii} and Ar ¹ may be the same or different.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. f and g represent an integer of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less. A plurality of e, f and g may be the same or different. )   The phthalocyanine pigment is C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 15: 3, and C.I. I. The photosensitive coloring resin composition of Claim 1 which is 1 or more types selected from the group which consists of pigment blue 15: 4.   The photosensitive coloring resin composition of Claim 1 or 2 in which the said photoinitiator contains an oxime ester system photoinitiator.   The photosensitive coloring resin composition of any one of Claims 1-3 in which the said photoinitiator contains an at least 2 sort (s) of oxime ester system photoinitiator.   The photosensitive coloring resin composition of any one of Claims 1-4 in which the said photoinitiator contains the oxime ester system photoinitiator which has a fluorene skeleton.   The photosensitive colored resin composition according to any one of claims 1 to 5, wherein the photoinitiator includes an oxime ester photoinitiator having a fluorene skeleton and an oxime ester photoinitiator having a diphenyl sulfide skeleton. Furthermore, the photosensitive coloring resin composition of any one of Claims 1-6 containing antioxidant. The cured product of the photosensitive colored resin composition according to any one of claims 1-7. A substrate, and at least comprising a color filter and a colored layer provided on the substrate, curing at least one of the photosensitive colored resin composition according to any one of claims 1 to 7, the colored layer Color filters that are things. A display device comprising the color filter according to claim 9 .

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