WO2022270357A1

WO2022270357A1 - Photosensitive colored resin composition, cured product, color filter and display device

Info

Publication number: WO2022270357A1
Application number: PCT/JP2022/023796
Authority: WO
Inventors: 裕史大島
Original assignee: 株式会社Ｄｎｐファインケミカル
Priority date: 2021-06-25
Filing date: 2022-06-14
Publication date: 2022-12-29
Also published as: JPWO2022270357A1; TW202307139A; CN117425856A

Abstract

A photosensitive colored resin composition which contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorbent and a solvent, wherein the colorant contains a lake colorant of a triarylmethane-based dye.

Description

Photosensitive colored resin composition, cured product, color filter, display device

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. An organic light-emitting display device such as an organic EL display, which has high visibility due to self-luminescence, is also attracting attention as a next-generation image display device.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image in a liquid crystal display device, the light that has passed through the color filter is colored into the color of each pixel that constitutes the color filter, and the light of these colors is combined to form a color image. As a light source in that case, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. An organic light-emitting display device uses a color filter for color adjustment.

Here, the color filter is generally formed on a substrate, a colored layer formed on the substrate and composed of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. and a light shielding part.
As a method for forming a colored layer in a color filter, for example, a colored resin composition obtained by adding a binder resin, a photopolymerizable compound, and a photoinitiator to a coloring material dispersion liquid in which a coloring material is dispersed using a dispersant or the like is prepared. After being coated on a glass substrate and dried, it is exposed using a photomask and developed to form a colored pattern, which is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.

In recent years, as the demand for higher luminance of color filters has increased, it has become difficult for color filters using pigments to meet the current demand for higher luminance.
Therefore, in recent years, the use of dyes, which generally have a higher transmittance than pigments, and lake colorants in which dyes are made insoluble with a precipitant, has been studied as colorants for color filters.
However, dyes and lake colorants have poor heat resistance compared to pigments that have been used as colorants for color filters, and there is a problem that the colored layer tends to fade when heated to high temperatures in the color filter manufacturing process. there were.

On the other hand, in Patent Document 1, while using a lake pigment, as a colored resin composition for a color filter that can suppress the fading of the colored layer due to high temperature heating in the color filter manufacturing process and can form a high-luminance colored layer, It contains a lake pigment, a dispersant, a hindered phenolic antioxidant, a binder component, and a solvent, and the dispersant forms a salt of at least part of the nitrogen moiety and an acidic organophosphorus compound. A colored resin composition for color filters, which is a specific polymer, is disclosed.

On the other hand, as a photosensitive colored composition containing an ultraviolet absorber, Patent Document 2 describes a colored resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin, ) an antioxidant and (E) an ultraviolet absorber are disclosed. Patent Document 2 aims to provide a colored resin composition capable of forming a contact hole having a desired diameter while maintaining and improving the brightness and heat resistance of the resulting pixel.
Further, Patent Document 3 discloses a photopolymerization initiator containing a coloring agent (A), a resin (B), a photopolymerizable monomer (C), and an acylphosphine oxide-based organic compound or an oxime ester-based organic compound. (D) and an ultraviolet absorber (E) that is at least one selected from the group consisting of benzotriazole-based organic compounds, triazine-based organic compounds, and benzophenone-based organic compounds, and the resin (B) contains: (b1), (b2) and (b3):
(b1); a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule (b2); a compound having an epoxy group and an ethylenically unsaturated bond in one molecule (b3); A compound having an ethylenically unsaturated bond other than (a2) is copolymerized to obtain a copolymer (b6), and the obtained copolymer (b6) and the unsaturated monobasic acid (b4) are combined. Obtaining a copolymer (b7) by reacting, and further containing a photosensitive resin (B-1) obtained by reacting the obtained copolymer (b7) with a polybasic acid anhydride (b5) A photosensitive coloring composition is disclosed which is characterized by In Patent Document 3, a photosensitive coloring composition having high resolution that can correspond to high image quality and low power consumption, in particular, high resolution even in a thick film such as the COA method, and adhesion that does not cause pattern peeling It is an object to obtain an excellent photosensitive coloring composition.

JP 2014-153569 A JP 2015-98537 A Japanese Patent No. 5664299

Pixel sizes are becoming smaller as the resolution of displays increases to 4K/8K, and in response to the decrease in pixel aperture ratio (aperture ratio), there is a demand for resists with higher brightness and finer line widths. There is a need for a photosensitive colored resin composition that can be patterned.
However, when a dye is dissolved and used as in Patent Document 2, the heat resistance is particularly poor and it is insufficient to improve the luminance of pixels. Not enough for improvement.
As a coloring material effective for increasing the brightness of pixels, there is a lake coloring material of triarylmethane-based dyes. However, the lake colorant of the triarylmethane dye has a transmittance in the UV wavelength region that is lower than that of conventionally used pigments (for example, CI Pigment Blue 15:6, CI Pigment Violet 23). Therefore, if a photoinitiator is added as in the conventional method, the pattern line width tends to become thicker. In order to adjust the pattern line width to a predetermined value, if the amount of photoinitiator is reduced, an antioxidant is added as in Patent Document 1, or the amount of antioxidant added is increased, the photocurability of the pattern portion is improved. Insufficient, the change in film thickness after development becomes large and the development residual film ratio decreases, making it difficult to achieve both a fine line width design and a high development residual film ratio.
Although Patent Document 1 describes a lake colorant of triarylmethane-based dyes, it does not suggest the problem of achieving both a fine line width design and a high development residual film rate. Patent Document 2 describes a photosensitive colored resin composition containing a triarylmethane dye. However, since the dye is dispersed at the molecular level in the photosensitive colored resin composition, it tends to inhibit the curability of the photocurable component. tend to be thinner than designed, and the development residual film rate tends to decrease. Therefore, in a photosensitive colored resin composition containing a dye, it is necessary to increase the amount of photoinitiator or use a photoinitiator with higher sensitivity in order to obtain the desired fine line width, so the development residual film rate naturally improves. do. Therefore, in the case of a dye-containing photosensitive colored resin composition, the problem of difficulty in achieving both a fine line width design and a high development residual film rate does not exist in the first place. In addition, since a pigment is used in Patent Document 3, the problem of difficulty in achieving both a fine line width design and a high development residual film rate does not exist in the first place.
As mentioned above, when using a triarylmethane dye lake colorant, unlike when using pigments or dyes, it is difficult to achieve both a fine line width design and a high development residual film rate. I have a problem.

The present invention has been made in view of the above circumstances, and contains a triarylmethane-based dye lake colorant to improve brightness, have a narrow line width, and suppress changes in film thickness before and after development. An object of the present invention is to provide a photosensitive colored resin composition capable of forming a layer. Moreover, an object of this invention is to provide the color filter and display apparatus which were formed using the said photosensitive colored resin composition.

The photosensitive colored resin composition according to the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent,
The colorant contains a lake colorant of a triarylmethane-based dye.

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 a cured photosensitive colored resin composition according to the present invention. It is a thing.

A display device according to the present invention has the color filter according to the present invention.

According to the present invention, a photosensitive colored resin that contains a triarylmethane-based dye lake colorant and can form a colored layer with a thin line width and suppressed film thickness change before and after development while improving brightness. A composition can be provided. Moreover, according to this invention, the color filter and display apparatus which were formed using the said photosensitive colored resin composition can be provided.

FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.

Hereinafter, the photosensitive colored resin composition, cured product, color filter, and 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 non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present invention, (meth)acryloyl represents acryloyl and methacryloyl, (meth)acryl represents acrylic and methacrylic, and (meth)acrylate represents acrylate and methacrylate.
Also, in this specification, the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.

I. Photosensitive colored resin composition
The photosensitive colored resin composition according to the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent,
The colorant contains a lake colorant of a triarylmethane-based dye.

The photosensitive colored resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, and the colorant is a triaryl Since it is a lake colorant of a methane-based dye, it is possible to form a colored layer with a narrow line width and suppressed change in film thickness before and after development while improving brightness. Although the action that exhibits such an effect is not yet clarified, it is presumed as follows.

As described above, since pigments have a low transmittance to ultraviolet rays, it is relatively difficult to cure the photocurable component in a pigment-containing photosensitive colored resin composition. In addition, since the dye tends to inhibit the curability of the photocurable component, the photocurable component is relatively difficult to cure even in a photosensitive colored resin composition containing a dye. On the other hand, the triarylmethane-based dye lake colorant has a high transmittance of ultraviolet rays and does not inhibit the curability of the photocurable component, so the effect of insolubilizing it in the developer after photocuring is the pigment Since it is more expensive than dyes and dyes, the pattern line width tends to be thicker. In a photosensitive colored resin composition containing a triarylmethane-based dye lake colorant, it is necessary to effectively suppress the photo-curing reaction in order to make the pattern line width a predetermined fine line width.
As a coloring material, a triarylmethane dye lake coloring material with high transmittance is used, and if the amount of photoinitiator is reduced in order to match the pattern line width to a predetermined value, radicals are generated by photoreaction regardless of the film thickness direction. As a result, it is considered that the photocurability of the pattern portion is insufficient, and the change in film thickness from before development to after development becomes large, resulting in a decrease in the residual film ratio after development. In addition, when a triarylmethane-based dye lake colorant is used and an antioxidant is added or its amount is increased in order to adjust the pattern line width to a predetermined value, the radicals generated by the photoreaction of the photoinitiator can be removed from the film. Since the deactivation occurs regardless of the thickness direction, the photo-curing property of the pattern portion is insufficient, and the change in film thickness from before to after development is large, which is thought to reduce the residual film ratio after development.
On the other hand, in the present invention, an ultraviolet absorber is combined with a triarylmethane-based dye lake colorant. The UV absorber does not attenuate the UV rays on the surface of the film, so it does not reduce the residual film after development. Therefore, it is thought that the line width can be reduced while suppressing the decrease in the film thickness of the residual film after development.
Furthermore, since the colorant contains a triarylmethane-based dye lake colorant, the colored layer, which is a cured product of the photosensitive colored resin composition according to the present invention, has a high transmittance and is subjected to ultraviolet irradiation and post-baking. chromaticity change due to the manufacturing process is suppressed. Therefore, the photosensitive colored resin composition of the present invention can improve the luminance of the finally obtained colored layer.

The photosensitive colored resin composition according to the present invention contains at least a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, and the present invention. Other ingredients may be added as long as the effect is not impaired. For example, the photosensitive colored resin composition according to the present invention may further contain a dispersant in order to improve colorant dispersibility.
Hereinafter, each component of the photosensitive colored resin composition according to the present invention will be described in detail, starting with the ultraviolet absorber.

[Ultraviolet absorber]
The ultraviolet absorber in the present invention refers to a compound that has a maximum absorption wavelength of 400 nm or less and does not absorb visible light with a wavelength exceeding 420 nm. The ultraviolet absorber used in the present invention may be a compound that does not absorb visible light with a wavelength exceeding 400 nm.

The structure of the ultraviolet absorber used in the present invention is not particularly limited. Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, benzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, and salicylic acid-based ultraviolet absorbers. Absorbents, cinnamic acid-based UV absorbers, and the like can be mentioned.

For example, the benzotriazole-based UV absorber includes at least one UV absorber selected from the group consisting of benzotriazole-based UV absorbers represented by the following general formula (A).

(In general formula (A), X ¹ , X ² and X ³ are each independently a hydrogen atom, a hydroxyl group, —OR ^a , or an optionally substituted hydrocarbon having 1 to 15 carbon atoms R ^a represents an optionally substituted hydrocarbon group having 1 to 15 carbon atoms, and at least one of X ¹ , X ² and X ³ is a hydroxyl group, —OR ^a , or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms, and X ⁴ represents a hydrogen atom or a halogen atom.)

In general formula (A), the hydrocarbon group having 1 to 15 carbon atoms in X ¹ , X ² and X ³ and R ^a is a linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, dodecyl group, phenyl group, naphthyl group and biphenyl group. The hydrocarbon group may have 1 to 12 carbon atoms, or 1 to 8 carbon atoms. The hydrocarbon group may be an aliphatic hydrocarbon group, may be a linear or branched alkyl group, a methyl group, a t-butyl group, a t-pentyl group, an n-octyl group, a t-octyl group. (1,1,3,3-tetramethylbutyl group), 2-ethylhexyl group.
Examples of substituents include halogen atoms, hydroxyl groups, cyano groups, or groups containing carbonyl groups, ester groups, ether groups, amide groups, imide groups, etc., and acyl groups, acyloxy groups, alkoxy groups, aryloxy groups, glycidyl groups, and the like. Further, the substituent of the aromatic hydrocarbon group may be an alkyl group.
Examples of hydrocarbon groups having substituents include -C ₂ H ₃ (OH)-CH ₂ -O-C ₈ H ₁₇ , -C ₂ H ₃ (OH)-CH ₂ -O-C ₁₂ H ₂₅ , —CH(CH ₃ )—CO ₂ —C ₈ H ₁₇ , methacryloyloxyethyl, etc., and also 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl , 4-glycidyloxyphenyl, 4-isocyanuratephenyl, and the like. The —C ₈ H ₁₇ , —C ₁₂ H ₂₅ , etc. may each be linear or branched.
In general formula (A), the halogen atom includes a chlorine atom, a fluorine atom, a bromine atom, and the like.

Benzotriazole-based UV absorbers include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3[ 3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-( 5-chloro-2H-benzotriazol-2-yl)phenyl]propionate mixture, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-( 3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy- 5′-t-octylphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2 -yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol and the like.

For example, triazine-based UV absorbers include at least one UV absorber selected from the group consisting of triazine-based UV absorbers represented by the following general formula (B).

(In general formula (B), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ each independently may have a hydrogen atom, a hydroxyl group, —OR ^b , or a substituent represents a hydrocarbon group having 1 to 15 carbon atoms, R ^b represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, Y ¹ , Y ² , Y ³ , Y ⁴ , At least one of Y ⁵ and Y ⁶ represents a hydroxyl group, —OR ^b , or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent.)

The optionally substituted hydrocarbon group having 1 to 15 carbon atoms in Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ and R ^b is the above X ¹ , X ² , X ³ , and R ^a may be the same as the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent.
At least one of Y ² , Y ⁴ and Y ⁶ may be a hydroxyl group and may be a hydroxyphenyltriazine-based UV absorber.

Examples of triazine-based UV absorbers include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2,4-bis'2- hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine and the like.

For example, benzophenone-based ultraviolet absorbers include hydroxybenzophenone-based ultraviolet absorbers, and at least one ultraviolet absorber selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbers represented by the following general formula (C): is mentioned.

(In general formula (C), Z ¹ represents a hydroxyl group, —OR ^c , or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms; Z ² represents a hydrogen atom, a hydroxyl group, —OR ^c or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms, Z ³ represents a hydrogen atom or a hydroxyl group, and R ^c optionally has a substituent represents a hydrocarbon group having 1 to 15 carbon atoms.)

In the general formula (C), the optionally substituted hydrocarbon group having 1 to 15 carbon atoms in Z ¹ and Z ² and R ^c is the above X ¹ , X ² and X ³ , and the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent for R ^a .

Benzophenone-based UV absorbers include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2-di -hydroxy-4-methoxybenzophenone and the like.

The weight average molecular weight of the ultraviolet absorber used in the present invention is usually 80 or more, preferably 150 or more, more preferably 300 or more, and usually 2000 or less, preferably 1500 or less, and more preferably 1500 or less, from the viewpoint of efficiently absorbing ultraviolet rays. is 900 or less. Moreover, since the polymer of the ultraviolet absorber has a low ultraviolet absorbing ability, a non-polymeric compound having no repeating unit is preferable.

The UV absorber used in the present invention preferably has a transmittance of 45% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution. When such an ultraviolet absorber with a small transmittance at a wavelength of 365 nm is used in combination with a triarylmethane dye lake colorant, the absorption by the triarylmethane lake colorant is weak and the irradiation intensity is the highest with an ultra-high pressure mercury lamp. It is possible to effectively weaken the intensity of high UV rays, and as a result, add a sufficient amount of initiator to ensure the curability of the coating film surface, suppressing changes in film thickness after development, and coating. This is preferable because it can effectively weaken the photocurability inside the film and facilitates adjustment so that the line width shift amount does not become too large.

The transmittance of the UV absorber at a wavelength of 365 nm was measured by preparing a 0.002% by mass propylene glycol monomethyl ether acetate solution of the UV absorber, and measuring the 0.002% by mass propylene glycol monomethyl ether acetate solution with UV-visible near-infrared spectrophotometry. It can be measured using a meter (for example, JASCO Corporation V-7100).

The UV absorber used in the present invention has a transmittance of 0.002 mass% propylene glycol monomethyl ether acetate solution at a wavelength of 365 nm of preferably 42% or less, and even more preferably 40% or less.

The ultraviolet absorbent used in the present invention preferably has a solubility of 1% by mass or more in the solvent used in the photosensitive colored resin composition at 25° C. from the viewpoint of obtaining the effects of the present invention.
The ultraviolet absorber used in the present invention may have a solubility of 1% by mass or more in propylene glycol monomethyl ether acetate at 25°C.

Examples of UV absorbers used in the present invention include 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H- Benzotriazole, 2-[4-[(2-hydroxy-3-(2′-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3 ,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(2H- benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-hydroxy-4-octyloxybenzophenone,
2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-dihydroxy- Suitable examples include 4-methoxybenzophenone, 2-(2-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole, (2-hydroxy-3-dodecyl-5-methylphenyl)benzotriazole and the like.
Commercially available products include, for example, TinuvinPS, Tinuvin329, Tinuvin405, Tinuvin477, Tinuvin479, Tinuvin571, Tinuvin928 (manufactured by BASF), Kemisorb12, Kemisorb71, Kemisorb71D, Kemisorb73, Kemisorb111 (manufactured by Pro-Kasei, Kemisorb-9, UVA-9). Otsuka Chemical Co., Ltd.) and the like.

In the present invention, the ultraviolet absorbers can be used singly or in combination of two or more.
Even when a UV absorber having a transmittance at a wavelength of 365 nm of 45% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution is selected and used, two or more of them may be mixed and used. That is, the ultraviolet absorber used in the present invention alone has a transmittance of 0.002% by mass at a wavelength of 365 nm exceeding 45% in a propylene glycol monomethyl ether acetate solution. If the transmittance at a wavelength of 365 nm is 45% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution, a UV absorber of a mixture thereof can be used.

The content of the ultraviolet absorber is usually 0.00% with respect to the total solid content of the photosensitive colored resin composition for the purpose of obtaining an effect of suppressing the line width and adjusting the photocurability so that the composition can be cured satisfactorily. It may be in the range of 2% by mass to 4.0% by mass, preferably in the range of 0.3% by mass to 3.0% by mass, more preferably 0.5% by mass to 2.0% by mass. is within the range of
In addition, the solid content is everything other than the solvent, and liquid photopolymerizable compounds and the like are also included.

Further, for the purpose of adjusting the photocurability so that the line width suppressing effect is obtained and the curing is performed well, the ratio of the total mass of the ultraviolet absorber to the total mass of the photoinitiator and the ultraviolet absorber is preferably 2. .0 mass % to 20.0 mass %, more preferably 4.0 mass % to 18.0 mass %.

[Color material]
The coloring material in the present invention suppresses changes in chromaticity and brightness reduction before and after the high-temperature heating process, and while improving the brightness of the finally obtained colored layer, has a fine line width and suppresses film thickness changes before and after development. In order to obtain a photosensitive colored resin composition capable of forming a colored layer, it contains a triarylmethane-based dye lake colorant.
<Lake colorant of triarylmethane dye>
The lake colorant of triarylmethane-based dyes is preferably a lake colorant of triarylmethane-based dyes and polyacid from the viewpoint of excellent heat resistance and light resistance and achieving high brightness of the color filter. As the lake colorant of the triarylmethane dye, among others, one or more selected from the colorant represented by the following general formula (1) and the colorant represented by the following general formula (2) is preferable, and a coloring material represented by the following general formula (1) is preferable because it forms a molecular association state, exhibits more excellent heat resistance, and can achieve high brightness.

(In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group has at least a saturated aliphatic carbonized Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain.B ^c- represents a c-valent polyacid anion. R ⁱ to R ^v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may combine to form a ring structure, and each of R ^vi and R ^vii is independently an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano Ar ¹ represents an optionally substituted divalent aromatic group, and a plurality of R ⁱ to R ^vii and Ar ¹ may be the same or different.
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. f and g represent an integer of 0 or more and 4 or less. A plurality of f and g may be the same or different. )

(In general formula (2), R ^I to R ^VI each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R ^I and R ^II , R ^III and R ^IV , and R ^V and R ^VI may combine to form a ring structure, R ^VII and R ^VIII each independently having an alkyl group optionally having a substituent or a substituent; represents an optionally substituted alkoxy group, a halogen atom or a cyano group, Ar ² represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of R ^I to R ^VIII and Ar ² are Each may be the same or different, and E ^m- represents an m-valent polyoxoate anion.
m represents an integer of 2 or more. k and l each represents an integer of 0 or more and 4 or less. A plurality of k and l may be the same or different. )

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

A in the general formula (1) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is saturated at least at the terminal directly bonded to N Represents an aliphatic hydrocarbon group having an aliphatic hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in the carbon chain may contain a heteroatom. That is, the organic group has at least a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and an aliphatic hydrocarbon group that may contain a heteroatom such as O, S, N in the carbon chain, Alternatively, it represents an aromatic group which has an aliphatic hydrocarbon group at the terminal directly bonded to N and may contain a heteroatom such as O, S, or N in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic coloring site are not affected by the linking group A or other coloring sites, and the monomer and Similar colors can be retained.

In A, at least an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic, provided that the terminal carbon atom directly bonded to N does not have a π bond. may be any of, carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, the carbon chain contains O, S, N good too. For example, it may contain a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, etc., and a hydrogen atom may be further substituted with a halogen atom or the like.
In addition, the aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to at least N , may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of the robustness of the skeleton.
Cyclic aliphatic hydrocarbon groups include groups containing cyclohexane, cyclopentane, norbornane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 ^2,6 ]decane, and adamantane. . Moreover, as an aromatic group, the group containing a benzene ring, a naphthalene ring, etc. are mentioned, for example. For example, when A is a divalent organic group, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group substituted with two alkylene groups having 1 to 20 carbon atoms such as xylylene group etc.

In the present invention, from the viewpoint of improving heat resistance by achieving both robustness and freedom of molecular motion, A has two or more cycloaliphatic hydrocarbon groups and a terminal directly bonded to N is preferably an aliphatic hydrocarbon group that has a saturated aliphatic hydrocarbon group in the carbon chain and may contain O, S, and N in the carbon chain. A has two or more cycloalkylene groups, has a saturated aliphatic hydrocarbon group at the end directly bonded to N, O, S, aliphatic hydrocarbon may contain N in the carbon chain Group is more preferable, and among them, it is more preferable to have a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group.
Two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples thereof include the same as the cyclic aliphatic hydrocarbon groups described above, with cyclohexane and cyclopentane being preferred.

In the present invention, from the viewpoint of heat resistance, it is preferable that A is a substituent represented by the following general formula (1a).

(In the general formula (1a), R ^xi is an alkyl group having 1 to 4 carbon atoms as a substituent, or an alkylene group having 1 to 3 carbon atoms and optionally having an alkoxy group having 1 to 4 carbon atoms. wherein R ^xii and R ^xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p is an integer of 1 to 3, q and r are each independently represents an integer of 0 to 4. When there are a plurality of R ^xi , R ^xii , R ^xiii and r, the plurality of R ^xi , R ^xii , R ^xiii and r may be the same or different. .)

An alkylene group having 1 or more and 3 or less carbon atoms in R ^xi is preferable from the viewpoint of excellent compatibility between fastness and thermal motion of the coloring site and improvement of heat resistance. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, etc. Among them, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group and butyl group, and may be linear or branched.
The alkoxy group having 1 to 4 carbon atoms includes methoxy group, ethoxy group, propoxy group and butoxy group, and may be linear or branched.

Examples of the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms in R ^xii and R ^xiii are the same as the substituents that R ^xi may have.

In general formula (1a), the number of cyclohexane (cyclohexylene groups) is 2 or more and 4 or less, that is, p is preferably 1 or more and 3 or less from the viewpoint of heat resistance, and p is preferably 1 or more and 2 or less. is more preferable.
The number of substituents R ^xii and R ^xiii in the cyclohexylene group is not particularly limited, but from the viewpoint of heat resistance, it is preferably 1 or more and 3 or less, and 1 or more and 2 or less. is more preferred. That is, q and r are preferably integers of 1 or more and 3 or less, and q and r are preferably integers of 1 or more and 2 or less.

Suitable specific examples of such a linking group A include, but are not limited to, the following.

The alkyl groups in R ⁱ to R ^v are not particularly limited. Examples thereof include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and among them, linear or branched alkyl groups having 1 to 8 carbon atoms and 1 carbon atom. A linear or branched alkyl group of 1 to 5 is mentioned from the viewpoint of brightness and heat resistance, and an alkyl group in R ⁱ to R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group and the like. Examples of the substituted alkyl group include an aralkyl group such as a benzyl group. etc.
The aryl groups in R ⁱ to R ^v are not particularly limited. Examples include phenyl group and naphthyl group. Examples of substituents that the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, and a hydroxyl 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 are bonded. preferably form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

From the viewpoint of heat resistance, at least one of R ⁱⁱ to R ^v is preferably an optionally substituted cycloalkyl group or an optionally substituted aryl group. When at least one of R ⁱⁱ to R ^v has a cycloalkyl group or an aryl group, intermolecular interaction due to steric hindrance is reduced, so that the effect of heat on the coloring site can be suppressed, and heat resistance is improved. Considered to be excellent.

From the viewpoint of heat resistance, at least one of R ⁱⁱ to R ^v is preferably a substituent represented by general formula (1b) or general formula (1c) below.

(In general formula (1b), R ^xiv , R ^xv , and R ^xvi are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted It represents an alkoxy group having 1 or more and 4 or less carbon atoms.)

(In general formula (1c), R ^xvii , R ^xviii , and R ^xix are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted represents a good alkoxy group having 1 or more and 4 or less carbon atoms.)

Examples of the alkyl group having 1 to 4 carbon atoms in R ^xiv , R ^xv , R ^xvi , R ^xvii , R ^xviii , and R ^xix include a methyl group, an ethyl group, a propyl group, and a butyl group. There may be one or more branches. The alkoxy group having 1 to 4 carbon atoms includes methoxy group, ethoxy group, propoxy group and butoxy group, and may be linear or branched.
A halogen atom, a hydroxyl group, etc. are mentioned as a substituent which the said alkyl group and an alkoxy group may have.

When having a substituent represented by the general formula (1b), from the viewpoint of heat resistance, at least one of R ^xiv , R ^xv , and R ^xvi may have a substituent and has 1 to 4 carbon atoms. or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, and at least one of R ^xiv and R ^xv has 1 or more carbon atoms which may have a substituent It is more preferably an alkyl group of 4 or less, or an optionally substituted alkoxy group having 1 to 4 carbon atoms.

Further, when having a substituent represented by the general formula (1c), from the viewpoint of heat resistance, at least one of R ^xvii , R ^xviii and R ^xix may have 1 or more 4 carbon atoms which may have a substituent. It is preferably the following alkyl group or an optionally substituted alkoxy group having 1 to 4 carbon atoms, and at least one of R ^xvii and R ^xviii has 1 optionally substituted carbon atoms More preferably, it is an alkyl group of 4 or less, or an alkoxy group of 1 or more and 4 or less carbon atoms which may have a substituent.

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

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group for Ar ¹ may be a heterocyclic group in addition to a carbocyclic aromatic hydrocarbon group. The aromatic hydrocarbon in the aromatic hydrocarbon group includes condensed polycyclic aromatic hydrocarbons such as a benzene ring, naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring; biphenyl, terphenyl, Chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene are included. The chain polycyclic hydrocarbon may have O, S and N in the chain skeleton such as diphenyl ether. On the other hand, the heterocycle in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, and pyrazine; fused polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline; These aromatic groups may further have, as substituents, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group optionally substituted with these, or the like.

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

The valence a in A is the number of color-forming cation sites that constitute the cation, and a is an integer of 2 or more. In this lake colorant, since the valence a of the cation is 2 or more, the heat resistance is excellent. Among them, the valence a of the cation may be 3 or more. Although the upper limit of a is not particularly limited, a is preferably 4 or less, more preferably 3 or less, from the viewpoint of ease of production.

The cation in the coloring material represented by the general formula (1) preferably has a molecular weight of 1200 or more, more preferably 1300 or more, in terms of excellent heat resistance and easy suppression of color change during heating.

In the colorant represented by the general formula (1), the anion portion (B ^c− ) is a c-valent polyacid anion having a valence of 2 or more, from the viewpoint of high brightness and excellent heat resistance.

The polyacid anion in which a plurality of oxoacids are condensed may be an isopolyacid anion (M _m O _n ) ^c- or a heteropolyacid anion (X ₁ M _m O _n ) ^c- . In the above ionic formula, M is a poly atom, X is a hetero atom, m is a composition ratio of poly atoms, and n is a composition ratio of oxygen atoms. Examples of polyatoms M include Mo, W, V, Ti, and Nb. Examples of the heteroatom X include Si, P, As, S, Fe, Co, and the like. Also, a counter cation such as Na ⁺ or H ⁺ may be partially contained.
Among them, a polyacid containing one or more elements selected from tungsten (W) and molybdenum (Mo) is preferable because of its excellent heat resistance.
Such polyacids include, for example, isopolyacids such as tungstate ion [W ₁₀ O ₃₂ ] ⁴⁻ , molybdate ion [Mo ₆ O ₁₉ ] ²⁻ , and heteropolyacids such as phosphotungstate ion [ PW ₁₂ O ₄₀ ] ³⁻ , [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , silicotungstate ion [SiW ₁₂ O ₄₀ ] ⁴⁻ , phosphomolybdate ion [PMo ₁₂ O ₄₀ ] ³⁻ , silicomolybdate ion [ SiMo ₁₂ O ₄₀ ] ^4- , phosphorus tungstomolybdate ion [PW _12-s Mo _s O ₄₀ ] ^3- (s is an integer of 1 or more and 11 or less), [P ₂ W _18-t Mo _t O ₆₂ ] ^6- (t is an integer of 1 to 17), silicate ion [SiW _12-u Mo _u O ₄₀ ] ^4- (u is an integer of 1 to 11), and the like. Among the polyacids containing at least one of tungsten (W) and molybdenum (Mo), heteropolyacids are preferred among the above from the viewpoints of heat resistance and ease of raw material availability, and phosphorus (P ) is more preferred.
Furthermore, the heat-resistant tungstomolybdate ion [PW ₁₀ Mo ₂ O ₄₀ ] ³⁻ , [PW ₁₁ Mo ₁ O ₄₀ ] ³⁻ , or phosphotungstic acid ion [PW ₁₂ O ₄₀ ] ³⁻ . It is more preferable from the point of view of sex.

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

The lake colorant represented by general formula (1) can be prepared, for example, with reference to International Publication No. 2012/144520 and International Publication No. 2018/003706.

On the other hand, in general formula (2), R ^I to R ^VI each independently represent a hydrogen atom, an optionally substituted alkyl group or an ^optionally substituted aryl group; R ^II , R ^III and R ^IV , and R ^V and R ^VI may combine to form a ring structure. Each of R ^I to R ^VI may be the same as R ⁱ to R ^v in general formula (1) above.
In general formula (2), R ^VII and R ^VIII each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano group. It may be the same as R ^vi and R ^vii in general formula (1) above.
In the general formula ( ² ), Ar ² represents a divalent aromatic heterocyclic group which may have a substituent, and the Ar ² is an aromatic group heterocyclic group.
Further, in general formula (2), E ^m- represents an m-valent polyanion, and the m-valent polyanion is the same as the c-valent polyanion in general formula (1) above. good

In general formula (2), m represents the number of cations and the number of anions, and represents an integer of 2 or more. A plurality of cations in the general formula (2) may be used alone or in combination of two or more. Also, the anions may be used singly or in combination of two or more.
Also, k and l in general formula (2) may be the same as f and g in general formula (1) described above.
Incidentally, the lake colorant represented by the general formula (2), for example, can be prepared with reference to JP-A-2017-16099.

Further, as the triarylmethane-based dye lake colorant used in the photosensitive colored resin composition of the present invention, the colorant represented by the general formula (1) and the color represented by the general formula (2) The material is not limited to one or more selected from the materials, and can be appropriately selected and used.
For example, the cations of triarylmethane dyes described in JP-A-2015-96947, JP-A-2016-27149, and JP-A-2017-16099 and various polyacid anions such as those described above And lake colorant, JP 2015-96947, JP 2016-27149, and using a lake colorant of triarylmethane-based dye and polyacid described in JP-A-2017-16099 good too.

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

<Other colorants>
The coloring material used in the present invention contains a triarylmethane-based dye lake coloring material as an essential component, but in a range that does not impair the effects of the present invention, in order to adjust the color tone, it is further combined with other coloring materials. may be used.
As other coloring materials, known pigments, dyes, lake coloring materials and the like can be used singly or in combination of two or more.

As other colorants, other blue colorants, purple colorants, and red colorants are preferably used, but are not limited to these.
As other blue colorants, C.I. I. known organic blue pigments such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6;
As a purple colorant, C.I. I. known organic violet pigments such as Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38;
As red to reddish purple colorants, for example, WO 2020/071041, JP 2018-100323, WO 2014/123125, etc. xanthene dyes and xanthene-based dye lake colorants described in etc.

<Content ratio of coloring material>
In the photosensitive colored resin composition of the present invention, as long as the effects of the present invention are not impaired, the colorant may further contain other colorants other than the lake colorant of the triarylmethane dye. However, the content of the lake colorant of the triarylmethane dye is preferably 70% by mass or more and 100% by mass or less, relative to the total amount of the colorant, and is 80% by mass or more and 100% by mass or less. It is preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.

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

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

The coloring material used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. Alternatively, a commercially available coloring material may be used after undergoing fine processing.

The content of the coloring material in the photosensitive colored resin composition according to the present invention is not particularly limited. The content of the coloring material, from the viewpoint of dispersibility and dispersion stability, relative to the total solid content of the photosensitive colored resin composition, usually in the range of 3% to 65% by weight, preferably 4% to 60% by weight % by mass, more preferably 15% to 60% by mass. If it is at least the above lower limit, the colored layer will have a sufficient color density when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm). Moreover, if it is below the said upper limit, while being excellent in storage stability, the coloring layer which has sufficient hardness and adhesiveness with a board|substrate can be obtained. Especially when forming a colored layer having a high colorant concentration, the total content of the colorant is preferably 20% to 65% by mass, more preferably 20% by mass to 65% by mass, based on the total solid content of the photosensitive colored resin composition. It is in the range of 30% by mass to 60% by mass.

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

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

Moreover, the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is alleviated, and substrate adhesion is improved.
Examples of such hydrocarbon rings include aliphatic hydrocarbon rings which may have substituents, aromatic hydrocarbon rings which may have substituents, 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 may be contained as a divalent or higher group.

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

When an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is also preferably improved.
Moreover, when the cardo structure is included, it is particularly preferable from the viewpoint of improving the curability of the colored layer, suppressing the fading of the coloring material, and improving the solvent resistance (NMP swelling suppression).

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

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

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

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

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

Further, in a carboxyl group-containing copolymer such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having an ethylenically unsaturated bond, which is more preferably used as an alkali-soluble resin, the epoxy group and ethylene The compound having a polyunsaturated 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, relative to the charged amount of the carboxy group-containing ethylenically unsaturated monomer. more preferred.

The preferred mass 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. When it is 1,000 or more, the binder function after curing is improved, and when it is 50,000 or less, pattern formation becomes good during development with an alkaline developer.

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

From the standpoint of developability (solubility) in an alkaline aqueous solution used as a developer, it is preferable to select and use an alkali-soluble resin with an acid value of 30 mgKOH/g or more. The alkali-soluble resin preferably has an acid value of 40 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of developability (solubility) in an alkaline aqueous solution used as a developer and adhesion to a substrate. It is preferably 50 mgKOH/g or more and 280 mgKOH/g or less.

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

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

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

Alkali-soluble resin used in the photosensitive colored resin composition may be used alone, may be used in combination of two or more, the content is not particularly limited, photosensitive colored resin The content of the alkali-soluble resin is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 40% by mass or less, relative to the total solid content of the composition. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.

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

These polyfunctional (meth)acrylates may be used singly or in combination of two or more. Further, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional (meth)acrylate has three polymerizable ethylenically unsaturated bonds (three Functionality) or more is preferable, and poly(meth)acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri(meth)acrylate, penta Erythritol tri(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta (Meth)acrylate modified with succinic acid, dipentaerythritol hexa(meth)acrylate and the like are preferred.

Among them, the photopolymerizable compound used in the present invention preferably contains a photopolymerizable compound containing alkylene oxide from the viewpoint of achieving both a high residual film rate and a fine line width.
Photopolymerizable compounds containing alkylene oxide preferably include photopolymerizable compounds containing ethylene oxide and/or propylene oxide. When the photopolymerizable compound containing the alkylene oxide is contained, active radicals are regenerated from peroxy radicals that have lost polymerization activity due to oxygen inhibition, so it is presumed that curability is improved.
Examples of the photopolymerizable compound containing an alkylene oxide include alkylene oxide-modified pentaerythritol tri(meth)acrylate, alkylene oxide-modified pentaerythritol tetra(meth)acrylate, alkylene oxide-modified dipentaerythritol tetra(meth)acrylate, alkylene oxide-modified di Examples include pentaerythritol penta(meth)acrylate, alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, and alkylene oxide-modified glycerol di(meth)acrylate, and more specific examples. , ethylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified pentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, propylene oxide-modified pentaerythritol tri(meth)acrylate, propylene oxide-modified penta Erythritol tetra(meth)acrylate, propylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified glycerin tri(meth)acrylate, ethylene oxide-modified diglycerin tetra(meth)acrylate, and the like. Among them, it is more preferable to include ethylene oxide-modified diglycerin tetra(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate.

A photopolymerizable compound can be used individually by 1 type or in mixture of 2 or more types.
As the photopolymerizable compound, a photopolymerizable compound containing alkylene oxide and a photopolymerizable compound not containing alkylene oxide may be mixed and used.
The content when containing a photopolymerizable compound containing alkylene oxide is preferably in the range of 3% to 50% by mass, more preferably in the range of 5% to 30% by mass, based on the total amount of the photopolymerizable compound. is within.

The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but is preferably in the range of 5% to 60% by mass with respect to the total solid content of the photosensitive colored resin composition. , more preferably in the range of 10% by mass to 40% by mass. When the content of the photopolymerizable compound is at least the above lower limit, photocuring sufficiently proceeds, the exposed portion can be suppressed from elution during development, the line width shift is suppressed, the solvent resistance is improved, and When the content of the photopolymerizable compound is equal to or less than the above upper limit, the alkali developability is sufficient.

[Photoinitiator]
The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and can be used alone or in combination of two or more of conventionally known various initiators.
Examples of photoinitiators include benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (e.g., Haicure ABP, manufactured by Kawaguchi Yakuhin), fragrances such as 4-methoxy-4'-dimethylaminobenzophenone. ketones; benzoin ethers such as benzoin methyl ether; benzoins such as ethylbenzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer; Halomethyloxadiazole compounds such as (p-methoxystyryl)-1,3,4-oxadiazole; 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S- Halomethyl-S-triazines such as triazine; 1,2-octadione-1-[4-(phenylthio)-,2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010 -527338, oxime esters such as oxime ester photoinitiators described in JP-A-2013-041153; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (eg Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (eg Irgacure 369, manufactured by BASF), 2-(dimethylamino) α-aminoketones such as -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF); thioxanthones such as diethylthioxanthone can be mentioned.
Among them, the photoinitiator used in the present invention preferably contains at least one selected from oxime esters and α-aminoketones from the viewpoint of excellent sensitivity. α-aminoketones are preferred from the viewpoint of Since α-aminoketones having a tertiary amine structure have a tertiary amine structure that is an oxygen quencher in the molecule, radicals generated from the initiator are less likely to be deactivated by oxygen, and sensitivity can be improved. preferable.
Further, it is preferable to use α-aminoketones in combination with oxime esters as photoinitiators from the viewpoint of suppressing water staining and improving sensitivity. The term "water stain" means that when a component that enhances alkali developability is used, after alkali development and rinsing with pure water, water stain marks are produced. Such water stains disappear after post-baking, so there is no problem with the product. occur. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the visual inspection, the yield of the final color filter product will be lowered, which is a problem.
Further, it is preferable to combine thioxanthones with at least one selected from oxime esters and α-aminoketones as a photoinitiator from the viewpoint of adjusting sensitivity, suppressing water staining, and improving development resistance. .

The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, relative to the total solid content of the photosensitive colored resin composition, It is preferably in the range of 0.1% by mass to 12.0% by mass, more preferably in the range of 1.0% by mass to 8.0% by mass. When the content is at least the above lower limit, photocuring proceeds sufficiently to suppress the elution of the exposed portion during development, resulting in good solvent resistance. A decrease in brightness due to yellowing of the layer can be suppressed.
Further, the content ratio of the photopolymerizable compound and the photoinitiator used in the photosensitive colored resin composition is such that the line width shift is suppressed, the solvent resistance is improved, and the development residue is suppressed. From the viewpoint of improving the effect, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 40 parts by mass with respect to 100 parts by mass of the photopolymerizable compound. It is not more than 30 parts by mass, and more preferably not more than 30 parts by mass.
Further, the ratio of the total mass of the photoinitiator to the total mass of the photoinitiator and the ultraviolet absorber is preferably in the range of 80% by mass to 98% by mass, more preferably 82% by mass to 96% by mass. It is within the range of % by mass. When the content is at least the above lower limit, sufficient photocurability can be ensured even in the presence of the UV absorber, while when it is at most the above upper limit, the effect of line width adjustment by the UV absorber is likely to be obtained.

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

In the photosensitive colored resin composition according to the present invention, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It may generally be in the range of 55% by mass to 95% by mass, preferably in the range of 65% by mass to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.

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

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

The dispersant can be appropriately selected and used according to the type of the coloring material, and is not particularly limited, but when dispersing the triarylmethane dye lake coloring material, dispersing As the agent, it is preferable to use an acidic dispersant which is an acidic polymeric dispersant.
As the acidic dispersant used for dispersing the lake colorant, for example, at least one selected from a polymer having a structural unit represented by the general formula (I) described later and a carboxy group-containing block copolymer is preferably used. can be used.
When a pigment is further used as a coloring material and dispersed, at least one selected from the group consisting of acidic or basic polymer dispersants and urethane-based dispersants can be used depending on the type of pigment. Alternatively, a basic polymeric dispersant may be used. When dispersing a basic-treated pigment, it is preferable to use an acidic dispersant, which is an acidic polymer dispersant, and when dispersing an acidic-treated pigment, a base, which is a basic polymer dispersant It is preferred to use a polydispersant.
As the basic dispersant, for example, a polymer containing a repeating unit having a tertiary amine, and at least a portion of the amino groups in the polymer containing a repeating unit having a tertiary amine and an organic acid compound. At least one polymer selected from the group consisting of salt-formed polymers can be preferably used.
A urethane-based dispersant is a compound having one or more urethane bonds (--NH--COO--) in one molecule. As the urethane-based dispersant, for example, a reaction product of polyisocyanates having two or more isocyanate groups in one molecule and polyesters having hydroxyl groups at one end or both ends can be suitably used.

<Polymer Having Structural Unit Represented by Formula (I)>
A polymer having a structural unit represented by the following general formula (I) can be preferably used as a dispersant for the triarylmethane-based dye lake colorant. As an acidic dispersant, using a polymer having a structural unit represented by the following general formula (I) improves the dispersibility and heat resistance of the triarylmethane-based dye lake colorant, and the lake color after heating It is possible to suppress the chromaticity change of the material. Further, as the colorant, when a lake colorant and a pigment are used in combination, a polymer having a structural unit represented by the following general formula (I) is used as a dispersant to improve the dispersibility and storage stability of the pigment. It is possible to form a colored layer with improved adhesion to the substrate and improved coating film uniformity.
Since the polymer having a structural unit represented by the following general formula (I) is a polymer of ethylenically unsaturated monomers, the heat resistance of the skeleton is higher than that of polyether-based or polyester-based polymers, and , a plurality of acidic phosphorus compound groups (-P(=O)(- ^R12 )(OH)) present in the polymer and salts thereof (-P(=O)(- ^R12 )(O ^- X ⁺ ) ) is presumed to have a strong adsorptive power to the surface of the finely divided coloring material. In addition, when the surface of the coloring material is coated with at least one of acidic phosphorus compound groups and salts thereof, active oxygen such as peroxy radical attacks the pigment skeleton of the lake coloring material (hydrogen abstraction, substitution reaction, etc.). It is estimated that the deterioration (oxidative deterioration) of the rake colorant is suppressed.

(In general formula (I), L ¹¹ is a direct bond or a divalent linking group, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydroxyl group, a hydrocarbon group, —[CH(R ¹³ )—CH (R ¹⁴ )—O] _x1 —R ¹⁵ , —[(CH ₂ ) _y1 —O] _z1 —R ¹⁵ , or a monovalent group represented by —OR ^{16, where R 16} ^is a hydrocarbon group , -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , -C(R ¹⁷ )(R ¹⁸ )-C( R ¹⁹ )(R ²⁰ )-OH or a monovalent group represented by -CH ₂ -C(R ²¹ )(R ²² )-CH ₂ -OH.
R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is a hydrogen atom, a hydrocarbon group, —CHO, —CH ₂ CHO, —CO—CH=CH ₂ , —CO—C( CH ₃ )=CH ₂ or a monovalent group represented by -CH ₂ COOR ²³ , where R ²³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from an ether bond and an ester bond; and R ¹⁷ and R ¹⁹ may combine with each other to form a ring structure. When the cyclic structure is formed, the cyclic structure may further have a substituent R ²⁴ , and R ²⁴ is a hydrocarbon group or a hydrocarbon group having one or more selected from an ether bond and an ester bond. It is a hydrogen group. The hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 is an integer of 1 or more and 18 or less, y1 is an integer of 1 or more and 5 or less, and z1 is an integer of 1 or more and 18 or less. )

In general formula (I), L ¹¹ is a direct bond or a divalent linking group. Here, the fact that L ¹¹ is directly bonded means that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without a linking group interposed therebetween.
The divalent linking group for L ¹¹ is not particularly limited as long as it can link the carbon atom of the main chain skeleton and the phosphorus atom. The divalent linking group for L ¹¹ includes, for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), combinations thereof, and the like. In the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the phosphorus atom side of the side chain, on the contrary, -NH is the main chain --CO may be on the phosphorus atom side of the side chain.

Among them, from the viewpoint of dispersibility, L ¹¹ in general formula (I) is preferably a -CONH- group or a divalent linking group containing a -COO- group.
For example, when L ¹¹ is a divalent linking group containing a -COO- group, L ¹¹ is a -COO-L ¹¹ '- group (here, L ¹¹ ' is a carbon atom optionally having a hydroxyl group an alkylene group whose number is 1 or more and 8 or less, -[CH(R ^L11 )-CH(R ^L12 )-O] _x -, or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - O—, —[CH(R ^L13 )] _w —O—, wherein R ^L11 , R ^L12 and R ^L13 are each independently a hydrogen atom, a methyl group or a hydroxyl group, x is 1 or more and 18 or less; is an integer, y is an integer of 1 or more and 5 or less, z is an integer of 1 or more and 18 or less, and w is an integer of 1 or more and 18 or less.).

The alkylene group having 1 to 8 carbon atoms in L ¹¹ ′ may be linear, branched, or cyclic. Examples include a butylene group, various pentylene groups, various hexylene groups, various octylene groups, etc., and a portion of the hydrogen may be substituted with a hydroxyl group.
x is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less, and y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably is 2 or 3. z is an integer of 1 or more and 18 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less. w is an integer of 1 or more and 18 or less, preferably 1 or more and 4 or less.

Preferable specific examples of L ¹¹ in general formula (I) include -COO-CH ₂ CH(OH)CH ₂ -O-, -COO-CH ₂ CH ₂ -O-CH ₂ CH(OH)CH ₂ -O-, -COO-CH ₂ C(CH ₂ CH ₃ )(CH ₂ OH)CH ₂ -O- and the like, but are not limited thereto.

Examples of the hydrocarbon group for R ¹² include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aralkyl groups, and aryl groups.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl and n-butyl. group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, and lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer.
The aryl group includes phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group and the like, and may further have a substituent. The number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.
Moreover, the aralkyl group includes a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and the like, and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, and nitro groups.
In addition, the substituents of the aromatic ring such as the aryl group and the aralkyl group include linear and branched alkyl groups having 1 to 4 carbon atoms, alkenyl groups, nitro groups, halogen atoms, and the like. can be mentioned.
In addition, the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.
In R ¹² , x1 is the same as x, y1 is the same as y, and z1 is the same as z.
Examples of the hydrocarbon group for R ¹⁵ to R ²² include those similar to the hydrocarbon group for R ¹² above.

The hydrocarbon group having one or more selected from ether bond and ester bond in R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² means -R'-O-R'', -R '-(C=O)-O-R'' or -R'-O-(C=O)-R''(R' and R'' are a hydrocarbon group, or a hydrocarbon group combined with an ether bond and an ester bond. a group bonded by at least one of the bonds). One group may have two or more ether bonds and ester bonds. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aralkyl groups, and aryl groups, and examples of divalent hydrocarbon groups include alkylene groups, alkenylene groups, arylene groups, and combinations thereof. group.

When R ¹⁷ and R ¹⁹ combine to form a ring structure, the number of carbon atoms forming the ring structure is preferably 5 or more and 8 or less, and is preferably 6, that is, a 6-membered ring. More preferably, it forms a cyclohexane ring.
A hydrocarbon group or a hydrocarbon group having one or more selected from an ether ^bond and an ^ester ^bond ^for the ^substituent ^R ²⁴ is can be similar to

From the viewpoint of excellent dispersibility and dispersion stability of dispersed particles, R ¹² is a hydroxyl group, a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , -[ (CH ₂ ) _y1 —O] _z1 —R ¹⁵ or a monovalent group represented by —OR ¹⁶ is preferred, and has a hydroxyl group, a methyl group, an ethyl group, a vinyl group, or a substituent; aryl group or aralkyl group, vinyl group, allyl group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , or a monovalent group represented by -OR ¹⁶ , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is -CO-CH=CH ₂ or -CO-C(CH ₃ ) ═CH ₂ is more preferable, and among them, R ¹² is more preferably an aryl group, a vinyl group, a methyl group, or a hydroxyl group which may have a substituent.

In terms of improving alkali resistance, R ¹² is a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ or -[(CH ₂ ) _y1 -O ] It is preferably a monovalent group represented by _z1 - ^R15 . In the case of having a structure in which a carbon atom is directly bonded to a phosphorus atom, it is assumed that a resin layer having excellent alkali resistance can be formed because it is difficult to hydrolyze. Among them, R ¹² is a methyl group, an ethyl group, an optionally substituted aryl or aralkyl group, a vinyl group, an allyl group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 —R ¹⁵ or a monovalent group represented by —[(CH ₂ ) _y1 —O] _z1 —R ¹⁵ , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is —CO -CH=CH ₂ or -CO-C(CH ₃ )=CH ₂ is preferable from the viewpoint of excellent alkali resistance and excellent dispersibility and dispersion stability of dispersed particles. Among them, R ¹² is more preferably an aryl group which may have a substituent from the viewpoint of dispersibility.

Moreover, in general formula (I), X represents a hydrogen atom or an organic cation. An organic cation is one that contains a carbon atom in the cationic portion. Examples of organic cations include imidazolium cations, pyridinium cations, aminidium cations, piperidinium cations, pyrrolidinium cations, ammonium cations such as tetraalkylammonium cations and trialkylammonium cations, and sulfonium cations such as trialkylsulfonium cations. , phosphonium cations such as tetraalkylphosphonium cations. Among them, protonated nitrogen-containing organic cations are preferable from the viewpoint of dispersibility and alkali developability.
Among them, when the organic cation has an ethylenically unsaturated bond, it is preferable from the point of being able to impart curability.

The structural unit represented by general formula (I) may be contained singly or in combination of two or more in the polymer.

In the polymer, among the structural units represented by general formula (I), X may contain both a structural unit in which X is a hydrogen atom and a structural unit in which X is an organic cation. When both of the structural units are included, there is no particular limitation as long as good dispersibility and dispersion stability are exhibited, but X is an organic cation. It is preferably 0 or more and 50 mol % or less with respect to the total number of structural units of the structural units represented by .

The method for synthesizing a polymer having a structural unit represented by general formula (I) is not particularly limited. can be synthesized. A polymer having a structural unit represented by general formula (I) is a reaction product of a polymer having at least one of an epoxy group and a cyclic ether group in a side chain and an acidic phosphorus compound, At least part of the groups are preferably polymers that may form salts.

In the embodiment of the present invention, the polymer having the structural unit represented by general formula (I) preferably further has a solvent affinity site from the viewpoint of dispersibility. Such a polymer is, among others, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (II), or A block copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (III) is excellent in dispersibility and storage stability, and after long-term storage Even if it is, it is preferable from the point of being able to form a high-contrast coating film.

(In the general formula (II), L ²¹ is a direct bond or a divalent linking group, R ²⁵ is a hydrogen atom or a methyl group, Polymer is a polymer chain having a structural unit represented by the following general formula (IV) represents
In general formula (III), R ²⁶ is a hydrogen atom or a methyl group, R ²⁷ is a hydrocarbon group, -[CH(R ²⁸ )-CH(R ²⁹ )-O] _x2 -R ³⁰ , -[(CH ₂ ) _y2 -O] _z2 -R ³⁰ , —[CO-(CH ₂ ) _y2 -O] _z2 -R ³⁰ , —CO-OR ^30′ or —O—CO-R ^30″ groups, R ²⁸ and R ²⁹ are each independently a hydrogen atom or a methyl group, R ³⁰ is a hydrogen atom, a hydrocarbon group, —CHO, —CH ₂ CHO or —CH ₂ COOR a monovalent group represented by ³¹ and R ^30′ is a hydrocarbon group, —[CH(R ²⁸ )—CH(R ²⁹ )—O] _x2′ —R ³⁰ , —[(CH ₂ ) _y2′ —O] _z2′ —R ³⁰ , —[CO—(CH ₂ ) _y2′ —O] _z2′ —R ³⁰ , where R ^30″ is an alkyl group having 1 to 18 carbon atoms, and R ³¹ is hydrogen. It is an alkyl group having 1 to 5 atoms or carbon atoms. The hydrocarbon group may have a substituent.
x2 and x2' are integers of 1 to 18; y2 and y2' are integers of 1 to 5; z2 and z2' are integers of 1 to 18; )

(In general formula (IV), R ³² is a hydrogen atom or a methyl group, R ³³ is a hydrocarbon group, -[CH(R ³⁴ )-CH(R ³⁵ )-O] _x3 -R ³⁶ , -[( CH ₂ ) _y3 —O] _z3 —R ³⁶ , —[CO—(CH ₂ ) _y3 —O] _z3 —R ³⁶ , —CO—OR ³⁷ or —O—CO—R ³⁸ groups, R ³⁴ and R ³⁵ are each independently a hydrogen atom or a methyl group, R ³⁶ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO or —CH ₂ COOR ³⁹ ; R ³⁷ is a hydrocarbon group, --[CH(R ³⁴ )--CH(R ³⁵ )--O] _x4 --R ³⁶ , --[(CH ₂ ) _y4 --O] _z4 --R ³⁶ , --[CO--(CH ₂ ) a monovalent group represented by _y4 -O] _z4 -R ³⁶ , R ³⁸ is an alkyl group having 1 to 18 carbon atoms, R ³⁹ is a hydrogen atom or a It is an alkyl group, and the hydrocarbon group may have a substituent.
n represents an integer of 5 or more and 200 or less. x3 and x4 are integers of 1 to 18; y3 and y4 are integers of 1 to 5; z3 and z4 are integers of 1 to 18; )

(graft copolymer)
Examples of graft copolymers preferable as acidic dispersants include graft copolymers having a structural unit represented by general formula (I) and a structural unit represented by general formula (II). can be done.
In the general formula ⁽ II), L21 is a direct bond or a divalent linking group. The divalent linking group for L ²¹ is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated bond and the polymer chain. Examples of the divalent linking group for L ²¹ include the same divalent linking groups for L ¹¹ .

In the general formula (II), Polymer represents a polymer chain having a structural unit represented by the general formula (IV).
In general formula (IV), the hydrocarbon group for R ³³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. is preferred. These include, for example, those similar to R ¹² described above.

R ³⁶ is preferably a hydrogen atom or a monovalent group represented by an alkyl group, aralkyl group, aryl group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ having 1 to 18 carbon atoms, R ³⁷ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, --[CH(R ³⁴ )--CH(R ³⁵ )--O] _x4 --R ³⁶ , --[(CH ₂ ) _y4 -O] _z4 -R ³⁶ and --[CO--(CH ₂ ) _y4 -O] _z4 -R ³⁶ are preferred. R ³⁸ is an alkyl group having 1 to 18 carbon atoms, and R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Examples of the alkyl group, aralkyl group, and aryl group having 1 to 18 carbon atoms in R ³⁶ and R ³⁷ are the same as those for R ¹² described above.
Examples of the alkyl group for R ³⁸ and R ³⁹ are the same as those for R ¹² above.
When R ³⁶ , R ³⁷ and R ³⁹ are groups having an aromatic ring, the aromatic ring may further have a substituent. Examples of the substituent include linear, branched, and cyclic alkyl groups having 1 to 5 carbon atoms, alkenyl groups, nitro groups, and halogen atoms such as F, Cl, and Br. .
In addition, the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.
^In R33 and ^R37 , x3 and x4 are the same as x, y3 and y4 are the same as y, and z3 and z4 are the same as z.

Furthermore, the R ³³ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ may be alkoxy groups, hydroxyl groups, carboxy groups, amino groups, epoxy groups, It may be substituted with a substituent such as an isocyanate group or a hydrogen bond forming group. Further, after synthesizing a graft copolymer having these substituents, a polymerizable group may be added by reacting a compound having a functional group that reacts with the substituent and a polymerizable group. For example, adding a polymerizable group by reacting a graft copolymer having a carboxyl group with glycidyl (meth)acrylate or reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth)acrylate. can be done.

A polymer chain having a structural unit represented by general formula (IV) includes methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl among the structural units described above. (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl ( Those having structural units derived from meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, styrene, α-methylstyrene, vinylcyclohexane, and the like are preferred. However, it is not limited to these.

In the embodiment of the present invention, as the R ³³ and R ³⁷ , it is preferable to use one having excellent solubility in the organic solvent described later, and it is appropriately selected according to the organic solvent used in the colorant dispersion. I wish I could. Specifically, for example, when the organic solvent is an ether-alcohol acetate-based, ether-based, or ester-based organic solvent generally used as an organic solvent for a colorant dispersion, a methyl group, an ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, 2-ethoxyethyl group, cyclohexyl group, benzyl group and the like are preferred.
Here, the reason for setting R ³³ and R ³⁷ in this way is that the structural unit containing R ³³ and R ³⁷ has solubility in the organic solvent, and the acidic phosphorus compound group of the monomer and This is because the salt portion has a high adsorptivity to the particles such as the coloring material, so that the dispersibility and stability of the particles such as the coloring material can be made particularly excellent.

The weight-average molecular weight of the polymer chain in Polymer is preferably within the range of 500 or more and 15000 or less, more preferably within the range of 1000 or more and 8000 or less. Within the above range, a sufficient steric repulsion effect as a dispersing agent can be maintained, and an increase in the time required for dispersing particles such as a coloring material due to the steric effect can be suppressed.

In addition, as a guideline, the polymer chain in the polymer preferably has a solubility of 50 (g/100 g solvent) or more at 23°C in the organic solvent used in combination.

The polymer chain may be a homopolymer or a copolymer. Further, the polymer chains contained in the structural units represented by the general formula (II) may be used singly or in combination of two or more in the graft copolymer.

The structural unit represented by the general formula (I) is preferably contained in a total ratio of 3% by mass or more and 80% by mass or less with respect to all the structural units of the graft copolymer. It is more preferably 70% by mass or less, and even more preferably 20% by mass or more and 60% by mass or less. If the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity sites for the particles in the graft copolymer will be appropriate, and the organic solvent will be Since it is possible to suppress the decrease in the solubility for the coloring material, the adsorption to particles such as coloring materials is improved, and excellent dispersibility and dispersion stability can be obtained. In addition, since the acidic phosphorus compound group of the graft copolymer can be stably localized around the colorant, a color filter excellent in heat resistance and contrast can be obtained.
On the other hand, the structural unit represented by the general formula (II) is preferably contained at a ratio of 20% by mass or more and 97% by mass or less with respect to all the structural units of the graft copolymer, and 25% by mass. % or more and 95 mass % or less is more preferable, and 40 mass % or more and 90 mass % or less is even more preferable.
In addition, in the present invention, the content ratio of each constitutional unit in the copolymer is calculated from the charged amount when synthesizing the copolymer.

The weight average molecular weight of the graft copolymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 400,000, and in the range of 5,000 to 300,000. is more preferred. Within the above range, the particles such as the coloring material can be uniformly dispersed.

The graft copolymer used in the embodiment of the present invention further has other structural units in addition to the structural units represented by the general formula (I) and the structural units represented by the general formula (II). It's okay to be For example, an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected and copolymerized to introduce another structural unit. be able to.

(Block copolymer)
A block copolymer preferable as an acidic dispersant includes, for example, a block portion containing a structural unit represented by the general formula (I) and a block portion containing a structural unit represented by the general formula (III). A block copolymer having
In the block copolymer, the block portion containing the structural unit represented by the general formula (I) preferably contains a total of 3 or more structural units represented by the general formula (I). . Among them, from the viewpoint of improving the dispersibility and improving the heat resistance, it preferably contains 3 to 200, more preferably 3 to 50, and further contains 3 to 30. is more preferred.
The structural unit represented by the general formula (I) may function as a coloring material affinity site, and may consist of one type or may contain two or more types of structural units. When two or more types of structural units are included, two or more types of structural units may be randomly arranged in the block portion containing the structural units represented by the general formula (I).

In the block copolymer, the total content of the structural units represented by the general formula (I) is 5% by mass or more and 80% by mass or less with respect to all the structural units of the block copolymer. , more preferably 10% by mass or more and 70% by mass or less, and even more preferably 20% by mass or more and 60% by mass or less.
If it is within the above range, the ratio of the affinity sites with the particles in the block copolymer becomes appropriate, and the decrease in the solubility in the organic solvent can be suppressed, so that the adsorption to the particles such as the coloring material becomes good, Excellent dispersibility and dispersion stability are obtained. In addition, since the acidic phosphorus compound group of the block copolymer can be stably localized around the colorant, a color filter excellent in heat resistance and contrast can be obtained.

By having a block portion containing a structural unit represented by the general formula (III), the block copolymer has good solvent affinity, good dispersibility and dispersion stability of the coloring material, and heat resistance. In addition, it has excellent resistance to N-methylpyrrolidone (NMP) (NMP resistance).

In general formula (III), R ²⁷ is a hydrocarbon group, -[CH(R ²⁸ )-CH(R ²⁹ )-O] _x2 -R ³⁰ , -[(CH ₂ ) _y2 -O] _z2 -R ³⁰ , —[CO—(CH ₂ ) _y2 —O] _z2 —R ³⁰ , —CO—OR ^30′ or —O—CO—R ^30″ .
The hydrocarbon group for R ²⁷ can be the same as those shown for R ¹² above.

Further, R ³⁰ is a hydrogen atom, a hydrocarbon group, —CHO, —CH ₂ CHO or —CH ₂ COOR ³¹ and is a monovalent group represented by —CH 2 COOR 31, and R ^30′ is a hydrocarbon group, —[CH( R ²⁸ )—CH(R ²⁹ )—O] _x2′ —R ³⁰ , —[(CH ₂ ) _y2′ —O] _z2′ —R ³⁰ , —[CO—(CH ₂ ) _y2′ —O] _z2′ a monovalent group represented by —R ³⁰ , where R ^30″ is an alkyl group having 1 to 18 carbon atoms, and R ³¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; , the hydrocarbon group may have a substituent.
The hydrocarbon group for R ³⁰ can be the same as those shown for R ¹² above.
In R ²⁷ and R ^30′ , x2 and x2′ are the same as x, y2 and y2′ are the same as y, and z2 and z2′ are the same as z.
Moreover, R ²⁷ in the structural unit represented by the general formula (III) may be the same or different.

As the above R ²⁷ and R ^30′ , among others, those having excellent solubility in the solvent described later are preferably used, and examples thereof include those similar to the above R ³³ and R ³⁷ .
R ²⁷ , R ³⁰ , R ^30′ , R ^30″ and R ³¹ in the general formula (IV) are alkoxy groups, hydroxyl groups, carboxy groups, It may be substituted with a substituent such as an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group, and after the synthesis of the block copolymer, it is reacted with a compound having the substituent to obtain the substituted Alternatively, after synthesizing a block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group are reacted to form a polymerizable group. For example, a block copolymer having a glycidyl group is reacted with (meth)acrylic acid, or a block copolymer having an isocyanate group is reacted with hydroxyethyl (meth)acrylate. A polymerizable group can be added.

The number of structural units constituting the block portion containing the structural unit represented by the general formula (III) is not particularly limited, but the solvent affinity site and the colorant affinity site act effectively to form a colorant dispersion. From the viewpoint of improving the dispersibility, it is preferably 10 or more and 200 or less, more preferably 20 or more and 100 or less, and even more preferably 30 or more and 80 or less.

In the block copolymer, the content of the structural unit represented by general formula (III) is preferably 30% by mass or more and 95% by mass or less with respect to the total structural units of the block copolymer, It is more preferably 40% by mass or more and 90% by mass or less.

The block portion containing the structural unit represented by general formula (III) may be selected so as to function as a solvent affinity site, and the structural unit represented by general formula (III) consists of one type. There may be one, or two or more structural units may be included. In an embodiment of the present invention, when the structural unit represented by general formula (III) contains two or more structural units, the block portion containing the structural unit represented by general formula (III) contains two types of The above structural units may be arranged randomly.

In the block copolymer used as a dispersant, the number m of structural units of the block portion containing the structural unit represented by general formula (I) and the block portion containing the structural unit represented by general formula (III) The ratio m/n of the unit number n of the constituent units is preferably in the range of 0.01 or more and 1 or less, and is in the range of 0.1 or more and 0.7 or less. It is more preferred from the viewpoint of properties and dispersion stability.

The order of bonding of the block copolymer includes a block portion containing a structural unit represented by the general formula (I) and a block portion containing a structural unit represented by the general formula (III), and a coloring material. It is not particularly limited as long as it can be stably dispersed, but the block portion containing the structural unit represented by the general formula (I) is bound to only one end of the block copolymer. However, it is preferable from the viewpoint that it is excellent in interaction with the colorant and can effectively suppress the aggregation of the dispersants.

The weight average molecular weight of the block copolymer is not particularly limited, but is preferably 2500 or more and 500000 or less, more preferably 3000 or more and 400000 or less, from the viewpoint of good dispersibility and excellent heat resistance. It is preferably 6,000 or more and 300,000 or less.

The acid value of the polymer having the structural unit represented by the general formula (I) is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, from the viewpoint of the dispersibility and storage stability of the coloring material. more preferably 40 mgKOH/g or more. On the other hand, from the viewpoint of excellent developability, the acid value of the polymer having the structural unit represented by the general formula (I) is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less. , 100 mgKOH/g or less.
In the present invention, the acid value refers to the number of mg of potassium hydroxide required to neutralize the acid component contained in 1 g of sample, and can be measured according to JIS K 0070:1992.

On the other hand, the carboxy group-containing block copolymer includes an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer such as (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester. It may contain a block copolymer containing a B block containing. In the carboxy group-containing block copolymer, the B block containing structural units derived from (meth)acrylic acid alkyl ester is represented by the general formula (III) of the block copolymer having the structural unit represented by the general formula (I). ) may be the same as the block part containing the structural unit represented by ).

The content ratio (mol%) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials charged at the time of production, and can be measured using an analyzer such as NMR. Also, the structure of the dispersant can be measured using NMR, various mass spectrometry, and the like. In addition, if necessary, the dispersant is decomposed by thermal decomposition or the like, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc. can ask.

In the present invention, the content of the dispersant may be appropriately selected according to the type of coloring material used, the solid content concentration in the photosensitive colored resin composition described later, and the like.
The content of the dispersant is preferably in the range of 2% by mass to 30% by mass, more preferably in the range of 3% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. be. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable.

[Antioxidant]
The photosensitive colored resin composition of the present invention preferably further contains at least one of an antioxidant and a latent antioxidant from the viewpoint of improving heat resistance and luminance.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern according to the design of the line width and from the viewpoint of heat resistance.
The latent antioxidant used in the present invention is a compound having a protective group that can be eliminated by heating, and is a compound that exerts an antioxidant function when the protective group is eliminated. Among them, those from which the protective group is easily eliminated by heating at 150° C. or higher are preferable. Examples of latent antioxidants used in the present invention include latent antioxidants as described in WO2014/021023 and WO2017/170263. Among them, a latent antioxidant in which the phenolic hydroxyl group of the hindered phenolic antioxidant is protected by a protecting group is preferable, and more specifically, a phenolic antioxidant of the hindered phenolic antioxidant A structure in which the hydrogen of the hydroxyl group is substituted with a carbamate-based protective group such as a t-butoxycarbonyl group is preferred.

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

The content of the antioxidant is preferably in the range of 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to the total solid content of the photosensitive colored resin composition. It is within the range of 5.0% by mass. If it is at least the above lower limit, it is excellent in terms of improving heat resistance and improving brightness. On the other hand, if it is the above upper limit or less, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

[thiol compound]
The photosensitive colored resin composition of the present invention preferably further contains a thiol compound from the viewpoint of improving the effect of suppressing changes in film thickness before and after development with a fine line width.
A thiol compound is excellent in surface curability and improves the rate of residual film after development because the enthiol reaction is not inhibited by oxygen. The thiol compound also has the effect of thickening the line width at the same time, but by using it in combination with the ultraviolet absorber, it has a synergistic effect of achieving both a thin line width and an improvement in the residual film after development.
Examples of thiol compounds include monofunctional thiol compounds having one thiol group and polyfunctional thiol groups having two or more thiol groups. It is more preferable to use a polyfunctional thiol from the viewpoint of improving the effect of suppressing film thickness change before and after development with a fine line width.
Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercapto propionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate and the like.
Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), di pentaerythritol hexakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) and the like.
The thiol compound may be used alone or in combination of two or more. Among them, pentaerythritol tetrakis (3-mercaptobutyrate) improves the effect of suppressing changes in film thickness before and after development with a narrow line width. preferred from
The content of the thiol compound is usually in the range of 0.5% by mass to 10% by mass, preferably 1% by mass to 5% by mass, based on the total solid content of the photosensitive colored resin composition. When it is at least the above lower limit, the effect of suppressing film thickness change before and after development is excellent. On the other hand, when the content is equal to or less than the above upper limit, the photocurable red resin composition of the present invention tends to have good developability and suppressed line width shift.

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

<Method for producing a photosensitive colored resin composition>
The method for producing a photosensitive colored resin composition of the present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, a solvent, and optionally a dispersant or the like. It can be prepared by mixing various additive components using a known mixing means.
As a method for preparing the resin composition, for example, (1) first, a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and an alkali-soluble resin and a light are added to the dispersion. A method of mixing a polymerizable compound, a photoinitiator, an ultraviolet absorber, and optionally various additive components; (2) a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator in a solvent; and a UV absorber, and a method of simultaneously adding and mixing various additive components used as desired; (3) an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a UV absorber in a solvent; (4) A method of adding a dispersing agent or the like and various additive components used as desired and mixing, and then adding and dispersing a coloring material; A coloring material dispersion is prepared by addition, and an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various additive components that are optionally used are added to the dispersion. and a method of mixing; and the like.
Among these methods, the above methods (1) and (4) are preferable because they can effectively prevent the aggregation of the colorant and uniformly disperse the colorant.

A method for preparing a colorant dispersion can be appropriately selected from conventionally known dispersion methods and used.
Examples of dispersing machines for dispersing treatment include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills. As preferable dispersing conditions for the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

[Use]
The photosensitive colored resin composition according to the present invention contains a triarylmethane-based dye lake colorant to improve brightness, and has a narrow line width, and can form a colored layer in which film thickness changes before and after development are suppressed. Therefore, it can be suitably used for color filters.

[Cured product of photosensitive colored resin composition]
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 can be obtained by forming a coating film of the photosensitive colored resin composition according to the present invention, drying the coating film, exposing it, and developing it. The method of forming, exposing, and developing the coating film may be, for example, the same method as that used in the formation of the colored layer provided in the color filter according to the present invention, which will be described later.
In addition, the cured product according to the present invention is a colored layer in which the film thickness change before and after development is suppressed with a thin line width while improving the brightness by containing a triarylmethane dye lake colorant, and a color filter is suitably used as a colored layer of

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

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

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

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

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

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

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

[substrate]
As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
Although the thickness of the transparent substrate is not particularly limited, a thickness of about 100 μm to 1 mm, for example, can be used depending on the application of the color filter of the present invention.
The color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, columnar spacers, etc., in addition to the above substrate, light shielding portion and colored layer.

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 liquid crystal display devices and organic light-emitting display devices.

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

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, the IPS method, the OCB method, and the MVA method. Any of these methods can be suitably used in the present invention.
Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be 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. After the liquid crystal layer is formed by the above method, the liquid crystal cell is gradually cooled to room temperature, thereby aligning the enclosed liquid crystal.

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

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

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the invention.
The mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.

[Solubility test of UV absorber in PGMEA]
For the solubility test of the UV absorber in PGMEA, 0.5 g of each UV absorber was weighed at 25° C., added to 9.5 g of PGMEA, stirred with a stirrer for 1 hour, and visually evaluated.
〇: No undissolved ×: Undissolved

[Measurement of the transmittance of the ultraviolet absorber at a wavelength of 365 nm]
The transmittance of the ultraviolet absorber at a wavelength of 365 nm was obtained by preparing a 0.002% by mass propylene glycol monomethyl ether acetate solution of each ultraviolet absorber, and subjecting the 0.002% by mass propylene glycol monomethyl ether acetate solution to ultraviolet-visible-near-infrared spectroscopy. It was measured using a photometer (eg, JASCO Corporation V-7100).
Table 1 shows the measurement results of the transmittance of the ultraviolet absorbent at a wavelength of 365 nm.

UV absorber (U1): Kemisorb71, Chemipro Kasei UV absorber (U2): Kemisorb12, Chemipro Kasei UV absorber (U3): Kemisorb111, Chemipro Kasei UV absorber (U4): Kemisorb73, Chemipro Kasei UV absorber Agent (U5): TinuvinPS, BASF UV absorber (U6): Tinuvin928, BASF UV absorber (U7): Tinuvin405, BASF UV absorber (U8): Tinuvin479, BASF UV absorber (U9): Tinuvin329 , BASF UV absorber (U10): Tinuvin477, BASF UV absorber (U11): RUVA-93, Otsuka Chemical

(Synthesis Example 1: Synthesis of lake colorant 1)
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate A-2, Intermediate B-1, and Compound 1-3 described in JP-A-2018-3013, the following chemical formula (a) is used. Intermediate 1 was obtained (87% yield).
The obtained compound was confirmed to be the target compound from the following analysis results.
・MS (ESI) (m / z): 677 (+), divalent ・Elemental analysis value: CHN measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%) , 7.36%, 5.90%)

(2) Synthesis of lake colorant 1 Kanto Chemical 12 tungstophosphoric acid n-hydrate 2.59 g (0.76 mmol) was dissolved by heating in a mixture of 40 mL of methanol and 40 mL of water, and the intermediate 1 1.6 g (1.19 mmol) was added and stirred for 1 hour. The precipitate was filtered and washed with water. The resulting precipitate was dried under reduced pressure to obtain a lake coloring material 1 represented by the following chemical formula (b) (yield 95%).
The obtained compound was confirmed to be the target compound from the following analysis results.
・31P NMR (d-dmso, ppm) δ-15.15
・MS (MALDI) (m/z): 1355 (M ⁺ ), 2879 (MH ₂ ⁻ )
Elemental analysis values: CHN measured values (35.55%, 3.24%, 2.61%); theoretical values (35.61%, 3.20%, 2.57%)
・Fluorescent X-ray analysis: MoW actual measurement ratio (0%, 100%); theoretical value (0%, 100%)

(Synthesis Example 2: Synthesis of lake colorant 2)
(1) Preparation of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) 44.0 g of NaWO _{4.2H 2 O (manufactured by Wako Pure Chemical Industries) and 1.90 g of Na 2 MoO 4.2H 2} _O ₍ _manufactured _by Kanto Chemical) were purified. Dissolved in 230 g of water. 64.9 g of 85% phosphoric acid was added to this solution with stirring using a dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction liquid was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added while stirring. After stirring for an additional hour, the precipitate was filtered off. The solid obtained was dried at 90° C. to obtain 29.4 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ).
(2) Synthesis of lake colorant 2 C.I. I. 5.30 g of Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) 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 (1) above was dissolved in 40 ml of purified water. The K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution was added to the BB7 solution and stirred at 40° C. for 1 hour. Then, the internal temperature was raised to 80° C., and the mixture was further stirred for 1 hour to form a lake. After cooling, it was filtered and washed with 300 ml of purified water three times. By drying the obtained solid at 90° C., 10.4 g of a lake colorant 2, which is a blackish-blue solid having an average primary particle size of 40 nm and which is a lake colorant of triarylmethane-based dye and polyacid, was obtained. .

(Synthesis Example 3: Synthesis of acidic dispersant A1 (polymer having at least one selected from structural units represented by general formula (I)))
(1) Synthesis of macromonomer MM-1 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added to a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was charged and heated to 90° C. while stirring under a nitrogen stream. 50.0 parts by weight of methyl methacrylate, 30.0 parts by weight of n-butyl methacrylate, 20.0 parts by weight of benzyl methacrylate, 4.0 parts by weight of 2-mercaptoethanol, 30 parts by weight of PGMEA, α,α'-azo A mixed solution of 1.0 parts by mass of bisisobutyronitrile (abbreviated as AIBN) was added dropwise over 1.5 hours, and the reaction was continued for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80° C., and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, and 0.125 parts by mass of p-methoxyphenol were mixed. and 10 parts by mass of PGMEA were added and stirred for 3 hours to obtain a 49.5% by mass solution of the macromonomer MM-1. The obtained macromonomer MM-1 had a mass average molecular weight (Mw) of 4010, a number average molecular weight (Mn) of 1910 and a molecular weight distribution (Mw/Mn) of 2.10 as a result of GPC measurement.

(2) Synthesis of graft copolymer A1 A reactor equipped with a cooling pipe, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA and stirred under a nitrogen stream. Warmed to a temperature of 90°C. 67.34 parts by weight of the macromonomer MM-1 solution (solid content 33.33 parts by weight), 16.67 parts by weight of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by weight of n-dodecyl mercaptan, 25.0 parts by weight of PGMEA , a mixed solution of 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes. By aging at room temperature for 1 hour, a 25.0% by mass solution of graft copolymer A1 was obtained. As a result of GPC measurement, the resulting graft copolymer A1 had a mass average molecular weight (Mw) of 10,570, a number average molecular weight (Mn) of 4,370, and a molecular weight distribution (Mw/Mn) of 2.42.

(3) Production of polymer (acidic dispersant A1) having at least one selected from structural units represented by general formula (I) Condenser, addition funnel, nitrogen inlet, mechanical stirrer, digital A reactor equipped with a thermometer was charged with 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name “PPA” manufactured by Nissan Chemical Industries), and heated to 90°C while stirring under a nitrogen stream. .
100.0 parts by mass of the graft copolymer A1 was added dropwise over 30 minutes, followed by heating and stirring for 2 hours to obtain a polymer having at least one selected from structural units represented by the general formula (I). A combined (acidic dispersant A1) solution (solid content: 25.0% by mass) was obtained. The progress of the esterification reaction between GMA and PPA in the obtained acidic dispersant A1 was confirmed by acid value measurement and ¹ H-NMR measurement (it was confirmed that the epoxy-derived peak disappeared). The acid value of the obtained acidic dispersant A1 was 98 mgKOH/g.

(Synthesis Example 4: Acidic dispersant A2 (a block copolymer containing an A block containing a structural unit derived from a carboxy group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from a (meth)acrylic acid alkyl ester) ) synthesis)
With reference to Example 1 described in WO 2016/132863, a block of 20 parts by weight of methyl methacrylate (MMA), 40 parts by weight of n-butyl methacrylate (BMA), and 20 parts by weight of methacrylic acid (MAA) , 20 parts by mass of BMA, and 20 parts by mass of MMA and 40 parts by mass of BMA, a triblock copolymer was synthesized. The resulting block copolymer had a weight average molecular weight (Mw) of 11000, a molecular weight distribution (Mw/Mn) of 1.50 and an acid value of 130 mgKOH/g.

(Synthesis Example 5: Synthesis of latent antioxidant)
0.01 mol of a phenol compound represented by the following chemical formula (c), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine are mixed, and 0.025 mol of 4-dimethylaminopyridine is added at room temperature under a nitrogen atmosphere. C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added for oil-water separation. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The resulting white powdery crystals were dried under reduced pressure at 60° C. for 3 hours to obtain a latent antioxidant (compound A). The structure of the obtained latent antioxidant was confirmed by IR and NMR.

(Comparative Synthesis Example 1: Synthesis of triarylmethane dye 1)
Triarylmethane dye 1 was synthesized in the same manner as dye A described in Example 1 of JP-A-2011-133844.
First, (tosyl)trifluoromethanesulfonylimidic acid triethylamine salt was synthesized as described in Example 1 of JP-A-2011-133844.
Next, C.I. I. Basic Blue 7 (N-[4-[[4-(diethylamino)phenyl][4-(ethylamino)-1-naphthyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-ethylethanamide Chloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 g was dissolved in 30 mL of methanol, and 3.93 g of (tosyl)trifluoromethanesulfonylimidic acid triethylamine salt was added while stirring, followed by further stirring at room temperature for 1 hour. The methanol in the solution was concentrated with an evaporator, 100 mL of water was added, and the precipitate was collected by filtration and washed with water. The cake was dried under reduced pressure to obtain a triarylmethane dye 1.

(Preparation Example 1: Preparation of alkali-soluble resin P1)
A polymerization tank was charged with 300 parts by mass of PGMEA, heated to 100° C. under a nitrogen atmosphere, and then charged with 67.6 parts by mass of benzyl methacrylate (BzMA), 67.6 parts by mass of MMA, and 36.4 parts by mass of methacrylic acid (MAA). , 3 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 9 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 the temperature at 100° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization two hours after the completion of dropping the mixture for forming the main chain.
Next, while blowing in air, 28.4 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, and the temperature was raised to 110°C. Addition reaction was carried out for 15 hours to obtain an alkali-soluble resin P1 solution (weight average molecular weight (Mw) 9000, acid value 75 mgKOH/g, solid content 40% by mass).
The weight average molecular weight was measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. Moreover, the method for measuring the acid value was based on JIS K 0070.

(Example 1: Production of photosensitive colored resin composition 1)
(1) Preparation of Colorant Dispersion Liquid 1 61 parts by mass of PGMEA, 5 parts by mass of alkali-soluble resin P1 solution (solid content: 40% by mass) of Preparation Example 1, and acidic dispersant A1 solution of Synthesis Example 3 are placed in a 225 mL mayonnaise bottle. 24 parts by mass (solid content: 25.0% by mass) was added and stirred.
10 parts by mass of triarylmethane-based lake colorant 1 of Synthesis Example 1 and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are added thereto, and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing. Then, 200 parts of zirconia beads having a particle size of 0.1 mm were used, and dispersion was carried out for 4 hours using a paint shaker as main pulverization to obtain a coloring material dispersion liquid 1.

(2) Preparation of photosensitive binder component B1 26.5 parts by mass of the alkali-soluble resin P1 solution (solid content 40% by mass) obtained in Preparation Example 1, a photopolymerizable compound (trade name Aronix M-403, Dipenta Erythritol penta and hexaacrylate, Toagosei) 17.7 parts by mass, photopolymerizable compound (trade name Aronix M-305, pentaerythritol tri and tetraacrylate, Toagosei) 7.06 parts by mass, photoinitiator As photoinitiator 1 (I1): 1.96 parts by mass of Irgacure 907 (manufactured by BASF, α-aminoacetophenone photoinitiator) and photoinitiator 2 (I2): OXE-02 (manufactured by BASF, having a carbazole skeleton 1.96 parts by mass of oxime ester photoinitiator), 0.392 parts by mass of UV absorber (UV absorber 1 (U1): Kemisorb71, manufactured by Chemipro Kasei), and IRGANOX1010 (manufactured by BASF) as an antioxidant. 0.392 parts by mass and 44.1 parts by mass of PGMEA were added to obtain a photosensitive binder component B1.
(3) Preparation of photosensitive colored resin composition 1 3.44 parts by mass of the colorant dispersion 1 obtained above, 3.50 parts by mass of the photosensitive binder component B1, and 3.06 parts by mass of PGMEA were mixed. , the photosensitive colored resin composition of Example 1 was prepared.

(Examples 2 to 27: Production of photosensitive colored resin compositions 2 to 27)
In Example 1, instead of the photosensitive binder component B1, except that each of the photosensitive binder components B2 to B27 were prepared and used as shown in Table 2, the photosensitive colored resin composition 1 of Example 1 and Similarly, photosensitive colored resin compositions 2 to 27 were obtained.

(Example 28: Production of photosensitive colored resin composition 28)
In Example 2, in the colorant dispersion liquid 1, the colorant was changed from the triarylmethane-based lake colorant 1 of Synthesis Example 1 to the triarylmethane-based lake colorant 2 of Synthesis Example 2. Example 2 A photosensitive colored resin composition 28 was obtained in the same manner as above.

(Comparative Examples 1 to 5: Production of Comparative Photosensitive Colored Resin Compositions 1 to 5)
In Example 1, instead of the photosensitive binder component B1, except that each of the photosensitive binder components CB1 to CB5 were prepared and used as shown in Table 3, the photosensitive colored resin composition 1 of Example 1 and Comparative photosensitive colored resin compositions 1 to 5 were obtained in the same manner.

(Comparative Examples 6-8: Production of comparative photosensitive colored resin compositions 6-8)
(1) Preparation of Colorant Dispersion C1 In a 225 mL mayonnaise bottle, 65 parts by mass of PGMEA, 15 parts by mass of the alkali-soluble resin P1 solution (solid content: 40% by mass) of Preparation Example 1, and the acidic dispersant A2 of Synthesis Example 4 are added. 10 parts by mass of PGMEA solution (solid content: 20.0% by mass) was added and stirred.
Add 8.8 parts by mass of PB15:6, 1.2 parts by mass of PV23, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm, and shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing. Then, 200 parts of zirconia beads having a particle size of 0.1 mm were used, and dispersion was carried out for 4 hours using a paint shaker as main pulverization to obtain a colorant dispersion C1.
(2) Preparation of Comparative Photosensitive Colored Resin Compositions 6 to 8 In Example 1, photosensitive binder components CB6 to CB8 were prepared as shown in Table 3 instead of the photosensitive binder component B1.
2.56 parts by mass of the colorant dispersion C1, 3.58 parts by mass of the photosensitive binder component, and 3.85 parts by mass of PGMEA were mixed to obtain comparative photosensitive colored resin compositions 6 to 8.

(Comparative Examples 9-11: Production of Comparative Photosensitive Colored Resin Compositions 9-11)
In Example 1, photosensitive binder components CB9 to CB11 were prepared as shown in Table 3 instead of photosensitive binder component B1.
0.333 parts by weight of a dye (triarylmethane dye 1 of Comparative Synthesis Example 1), 4.17 parts by weight of a photosensitive binder component, and 5.50 parts by weight of PGME are mixed, and a comparative photosensitive colored resin composition 9 ~11 was obtained.

[Evaluation method]
Each of the photosensitive colored resin compositions of Examples and Comparative Examples was spun onto a 0.7 mm-thick glass substrate (NH Techno Glass, "NA35") so that the film thickness after post-baking was 2.2 μm. After coating using a coater, drying was performed by heating at 80° C. for 3 minutes using a hot plate. After that, through a photomask forming a line of 40 μm, ultraviolet rays of 60 mJ/cm ² are irradiated using an ultra-high pressure mercury lamp, and then a 0.05% by mass potassium hydroxide aqueous solution is used as an alkaline developer to shower for 60 seconds. Developed. After that, the substrate was post-baked in a clean oven at 230° C. for 30 minutes to prepare a patterned substrate having a colored layer formed in a 40 μm line pattern on the glass substrate.

<Suppression of Line Width Increase in Colored Layer>
The width of the fine line pattern of the colored layer in the area corresponding to the opening width of 40 μm of the chromium mask used during exposure was measured with an optical microscope at 5 points, and the amount of line width shift was evaluated from the difference between the average line width and the target line width. did.
(Line width increase suppression evaluation criteria)
AA: The difference is within 5.0 μm from the target line width A: The difference is over 5.0 μm and within 7.0 μm from the target line width B: The difference is 7.0 μm from the target line width More than 0 μm and within 10.0 μm C: The difference from the target line width is more than 10.0 μm If the evaluation result is A, the line width increase suppression is good, and if the evaluation result is AA, the line width increase is suppressed. Are better.

<Evaluation of residual film rate after development>
Each of the photosensitive colored resin compositions of Examples and Comparative Examples was spun onto a 0.7 mm-thick glass substrate (NH Techno Glass, "NA35") so that the film thickness after post-baking was 2.2 μm. After coating using a coater, drying was performed by heating at 80° C. for 3 minutes using a hot plate. After that, ultraviolet rays of 60 mJ/cm ² were irradiated using an ultra-high pressure mercury lamp without passing through a photomask, and then the film thickness T1 of the resist coating film was measured using a film thickness meter. Next, shower development was performed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and the film thickness T2 after development was measured.
It was calculated as the development residual film ratio=T2/T1 [%].
(Evaluation criteria for residual film rate after development)
AA: Development residual film rate is 98% or more A: Development residual film rate is 97% or more and less than 98% B: Development residual film rate is 94% or more and less than 97% C: Development residual film rate is less than 94% Evaluation result is A If the evaluation result is AA, the residual film ratio after development is excellent.

<Brightness, heat resistance evaluation>
Each of the photosensitive colored resin compositions of Examples and Comparative Examples was placed on a glass substrate (manufactured by NH Techno Glass, "NA35") having a thickness of 0.7 mm so that the chromaticity after post-baking was y = 0.088. was applied using a spin coater. After that, it is dried by heating on a hot plate at 80°C for 3 minutes, irradiated with ultraviolet rays of 60 mJ/cm ² using an ultra-high pressure mercury lamp without passing through a photomask, and then post-baked in a clean oven at 230°C for 30 minutes. A cured film (colored film) was obtained by doing so. The luminance (Y), L, a, and b (L ₀ , a ₀ , b ₀ ) of the colored substrate thus obtained were measured using an Olympus Spectrophotometer OSP-SP200 and evaluated according to the following evaluation criteria. did.
Next, the substrate on which the cured film was formed was post-baked in a clean oven at 230° C. for 30 minutes, and then the step of cooling for 30 minutes was repeated three times. (L ₁ , a ₁ , b ₁ ) were measured. From the measured values, the color difference (ΔEab) before and after treatment was calculated according to the following formula.
Color difference (ΔEab) = {(L ₁ -L ₀ ) ² +(a ₁ -a ₀ ) ² +(b ₁ -b ₀ ) ² } ^1/2

(Luminance evaluation criteria)
AA: Brightness (Y) is 10.6 or more A: Brightness (Y) is 10.0 or more and less than 10.6 B: Brightness (Y) is 9.5 or more and less than 10.0 C: Brightness (Y) is 9.0 Less than 5 If the evaluation result is A, the luminance is good, and if the evaluation result is AA, the luminance is excellent.

(Heat resistance evaluation criteria)
AA: ΔEab is less than 3.0 A: ΔEab is 3.0 or more and less than 5.0 B: ΔEab is 5.0 or more and less than 8.0 C: ΔEab is 8.0 or more If the evaluation result is A, heat resistance is If the evaluation result is AA, the heat resistance is excellent.

Abbreviations in the table are as follows.
Photoinitiator 1 (I1): Irgacure 907, manufactured by BASF, α-aminoacetophenone photoinitiator Photoinitiator 2 (I2): OXE-02, manufactured by BASF, oxime ester photoinitiator having a carbazole skeleton UV absorber (U1): Kemisorb71, Chemipro Kasei UV absorber (U2): Kemisorb12, Chemipro Kasei UV absorber (U3): Kemisorb111, Chemipro Kasei UV absorber (U4): Kemisorb73, Chemipro Kasei UV absorber (U5) ): TinuvinPS, BASF UV absorber (U6): Tinuvin928, BASF UV absorber (U7): Tinuvin405, BASF UV absorber (U8): Tinuvin479, BASF UV absorber (U9): Tinuvin329, BASF UV absorber (U10): Tinuvin477, BASF UV absorber (U11): RUVA-93, Otsuka Chemical antioxidant (A1): IRGANOX1010, BASF latent antioxidant (LA1): Latent of Synthesis Example 5 Antioxidant Resin P1: Alkali-Soluble Resin P1 of Preparation Example 1
M1: photopolymerizable compound, Aronix M-403, dipentaerythritol penta and hexaacrylate, manufactured by Toagosei,
M2: photopolymerizable compound, Aronix M-305, pentaerythritol tri- and tetraacrylate, manufactured by Toagosei,
M3: photopolymerizable compound, Aronix M-460, diglycerin ethylene oxide-modified acrylate, manufactured by Toagosei Co., Ltd.,
M4: Photopolymerizable compound, Kayarad DPEA-12, ethylene oxide-modified (12) dipentaerythritol hexaacrylate, Nippon Kayaku thiol: Karenz MT PE1, Showa Denko

In addition, the numerical value of a photoinitiator, an ultraviolet absorber, an antioxidant, and a thiol is a solid content ratio.
L1 (lake colorant 1): lake colorant 1 of triarylmethane-based dye of Synthesis Example 1
L2 (lake colorant 2): lake colorant 2 of triarylmethane-based dye of Synthesis Example 2
Pigments: PB15:6 (C.I. Pigment Blue 15:6) and PV23 (C.I. Pigment Violet 23)
Dye: Triarylmethane-based dye 1 of Comparative Synthesis Example 1

[Summary of results]
The photosensitive colored resin composition of Examples 1 to 28 in which an ultraviolet absorber is combined with a lake colorant of triarylmethane dye has a thin line width while improving the brightness, and the film thickness change before and after development is suppressed. It was shown that it is possible to form a colored layer.
Further, in the examples, if an ultraviolet absorber is used in combination with the triarylmethane-based dye lake colorant, the amount of initiator to the target value of the line width shift amount of 5 μm or less while maintaining the development residual film rate was also shown to be adjustable with
In addition, among the examples, it was shown that the line width shift amount is difficult to increase when an ultraviolet absorber having a transmittance at a wavelength of 365 nm of 40% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution is used. .
Also, among the examples, it was shown that when a photopolymerizable compound containing alkylene oxide is contained, it is easy to achieve both a high residual film rate after development and a fine line width.
On the other hand, in the photosensitive colored resin composition of Comparative Example 1 that does not contain an ultraviolet absorber, even if it contains an antioxidant and a latent antioxidant in the same manner as in Examples, the line width shift amount is large, and the line It was shown that the width became thicker and a colored layer could not be formed with a desired fine line width.
In the photosensitive colored resin composition of Comparative Example 1 containing no ultraviolet absorber, the photosensitive colored resin composition of Comparative Examples 2 and 3 in which the amount of photoinitiator was reduced in order to narrow the line width, the line width shift amount was slightly reduced, but the development residual film rate was deteriorated.
In the photosensitive colored resin composition of Comparative Example 1 containing no ultraviolet absorber, in the photosensitive colored resin composition of Comparative Examples 4 and 5 in which the amount of antioxidant was increased to narrow the line width, the line width shift amount was reduced, but the development residual film rate was deteriorated.
On the other hand, the photosensitive colored resin compositions of Comparative Examples 6 to 8 using a pigment without using a triarylmethane dye lake colorant were similar to the examples using a triarylmethane dye lake colorant. In order to achieve the line width shift amount, it was necessary to use a large amount of the photoinitiator. In that case, the development residual film rate was not a problem, but the luminance was low.
Further, without using a triarylmethane dye lake colorant, the photosensitive colored resin compositions of Comparative Examples 9 to 11 using a triarylmethane dye were implemented using a triarylmethane dye lake colorant. In order to obtain the same line width shift amount as in the example, it is necessary to use a large amount of photoinitiator. It was shown to be less bright.

REFERENCE SIGNS LIST 1 substrate 2 light shielding part 3 colored layer 5 micropores 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 electrons Injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display

Claims

Containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent,
A photosensitive colored resin composition, wherein the colorant contains a lake colorant of a triarylmethane-based dye.
The photosensitive colored resin composition according to claim 1, which further contains a dispersant.
The photosensitive colored resin composition according to claim 1 or 2, further containing at least one of an antioxidant and a latent antioxidant.
The photosensitive colored resin composition according to any one of claims 1 to 3, further comprising a thiol compound.
The photosensitive colored resin composition according to any one of claims 1 to 4, wherein the triarylmethane-based dye lake colorant contains a colorant represented by the following general formula (1).

(In the general formula (1), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group has at least a saturated aliphatic carbonized Represents an aliphatic hydrocarbon group having a hydrogen group, or an aromatic group having the aliphatic hydrocarbon group, and may contain a heteroatom in the carbon chain.B c- represents a c-valent polyacid anion. R i to R v each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ii and R iii , R iv and R v may combine to form a ring structure, R vi and R vii are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano Ar 1 represents an optionally substituted divalent aromatic group, and a plurality of R i to R vii and Ar 1 may be the same or different.
a and c represent integers of 2 or more, and b and d represent integers of 1 or more. f and g represent an integer of 0 or more and 4 or less. A plurality of f and g may be the same or different. )
The photosensitive colored resin composition according to any one of claims 1 to 5, wherein the ultraviolet absorber has a transmittance of 40% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
The photosensitive colored resin composition according to any one of claims 1 to 6, wherein the photopolymerizable compound contains a photopolymerizable compound containing alkylene oxide.
A cured product of the photosensitive colored resin composition according to any one of claims 1 to 7.
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 claim 8.
A display device having the color filter according to claim 9.