CN117425856A

CN117425856A - Photosensitive coloring resin composition, cured product, color filter and display device

Info

Publication number: CN117425856A
Application number: CN202280040328.9A
Authority: CN
Inventors: 大岛裕史
Original assignee: DNP Fine Chemicals Co Ltd
Current assignee: DNP Fine Chemicals Co Ltd
Priority date: 2021-06-25
Filing date: 2022-06-14
Publication date: 2024-01-19
Also published as: TW202307139A; WO2022270357A1; JPWO2022270357A1

Abstract

A photosensitive colored resin composition comprising a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, wherein the coloring material comprises a lake material of a triarylmethane dye.

Description

Photosensitive coloring resin composition, cured product, color filter and display device

Technical Field

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

Background

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The popularity of mobile displays (mobile phones, smartphones, tablet PCs (personal computer, personal computers)) is also increasing, and the market for liquid crystal displays is expanding. Organic light emitting display devices such as organic EL (Electroluminescence) displays which are highly visible due to self-luminescence are also attracting attention as next-generation image display devices.

Color filters may be used in these liquid crystal display devices and organic light emitting display devices. For example, with respect to formation of a color image of a liquid crystal display device, light passing through a color filter is directly colored into colors of respective pixels constituting the color filter, and the lights of these colors are combined to form the color image. As the light source at this time, an organic light-emitting element that emits white light and an inorganic light-emitting element that emits white light may be used in addition to the conventional cold cathode tube. In the organic light emitting display device, a color filter is used for color adjustment or the like.

Here, the color filter generally has: a substrate; a coloring layer formed on the substrate and including coloring patterns of three primary colors of red, green and blue; and a light shielding portion formed on the substrate so as to divide each of the coloring patterns.

As a method for forming a colored layer in a color filter, for example, a colored resin composition in which a binder resin, a photopolymerizable compound, and a photoinitiator are added to a coloring material dispersion liquid in which a coloring material is dispersed by a dispersing agent or the like is applied to a glass substrate, dried, exposed to light using a photomask, and developed to form a colored pattern, and the pattern is fixed by heating to form a colored layer. These processes are repeated for each color to form a color filter.

In recent years, there has been a growing demand for higher brightness of color filters, and it has been difficult to achieve a further demand for higher brightness of color filters using pigments.

In recent years, therefore, a dye having a higher transmittance than that of a pigment or a lake material obtained by making the dye insoluble by a precipitant has been studied and used as a coloring material for color filters.

However, the dye or lake material has the following problems compared with the pigment used as a coloring material for color filters at present: the heat resistance is poor, and the colored layer tends to fade when heated at high temperature in the color filter manufacturing process.

In contrast, patent document 1 discloses a color resin composition for a color filter, which contains a lake pigment, a dispersant, a hindered phenol antioxidant, a binder component, and a solvent, wherein the dispersant is a specific polymer obtained by forming a salt of at least a part of nitrogen sites with an acidic organic phosphorus compound, as a color resin composition for a color filter, which suppresses discoloration of a color layer due to high-temperature heating in a color filter manufacturing process, and which can form a color layer with high brightness.

On the other hand, patent document 2 discloses, as a photosensitive coloring composition containing an ultraviolet absorber, a coloring resin composition containing (a) a dye, (B) a solvent, and (C) a binder resin, characterized by further containing (D) an antioxidant and (E) an ultraviolet absorber. The problem of patent document 2 is to provide a contact hole capable of further forming a desired diameter while maintaining the brightness and heat resistance of the obtained pixel.

Patent document 3 discloses a photosensitive coloring composition, which is characterized in that: comprises a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) containing an acylphosphine oxide-based organic compound or an oxime ester-based organic compound, and at least 1 ultraviolet absorber (E) selected from the group consisting of benzotriazole-based organic compounds, triazine-based organic compounds, and benzophenone-based organic compounds, and the resin (B) comprises a photosensitive resin (B-1) obtained by copolymerizing the following (B1), (B2), and (B3) to obtain a copolymer (B6), reacting the obtained copolymer (B6) with an unsaturated monoacid (B4) to obtain a copolymer (B7), and further reacting the obtained copolymer (B7) with a polybasic acid anhydride (B5):

(b1) The method comprises the following steps 1 a compound having an alicyclic skeleton and an ethylenically unsaturated bond in the molecule;

(b2) The method comprises the following steps 1 a compound having an epoxy group and an ethylenically unsaturated bond in the molecule;

(b3) The method comprises the following steps Compounds having an ethylenically unsaturated bond other than (a 1) and (a 2).

Patent document 3 discloses a photosensitive coloring composition having high definition, which can cope with high image quality and low power consumption, and particularly a photosensitive coloring composition having high resolution and excellent adhesion without pattern peeling even if it is a thick film such as COA (Color Filter on Array) type.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2014-153569

Patent document 2: japanese patent laid-open No. 2015-98537

Patent document 3: japanese patent No. 5664299

Disclosure of Invention

Problems to be solved by the invention

With the higher definition of 4K/8K of a display, the pixel size is reduced, and a resist with higher brightness is required in response to the reduction of the aperture ratio (aperture ratio) of pixels, and a photosensitive colored resin composition capable of forming a pattern with a smaller line width is required.

However, when a dye is dissolved and used as in patent document 2, the heat resistance is particularly poor, and the luminance of a pixel is not sufficiently improved, and when a pigment is used as in patent document 3, the luminance of a pixel is not sufficiently improved.

Examples of the coloring material effective for increasing the brightness of the pixel include coloring materials of triarylmethane dyes. However, since the color lake of the triarylmethane dye has higher transmittance in the UV wavelength range than conventionally used pigments (for example, c.i. pigment blue 15:6 and c.i. pigment violet 23), the pattern line width tends to be large when a photoinitiator is blended in the same manner as in the conventional art. If the amount of photo initiator is reduced to make the pattern line width meet a predetermined value, or if an antioxidant is added as in patent document 1, or if the amount of antioxidant is increased, the photo curability of the pattern portion is insufficient, and the film thickness change from before to after development increases, so that the development residual film rate is reduced, and it is difficult to achieve both a fine line width design and a high development residual film rate.

Although patent document 1 describes a lake material for a triarylmethane dye, there is no suggestion for 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 in the photosensitive colored resin composition at a molecular level, the curability of the photocurable component is easily impaired, and if the photoinitiator is blended in the same manner as the pigment, the photocurability is insufficient, the line width is easily finer than the design, and the development residual film rate is easily lowered. Therefore, in order to obtain a desired fine line width in the photosensitive colored resin composition containing a dye, it is necessary to increase the amount of the photoinitiator or to use a photoinitiator having higher sensitivity, and thus the development residual film rate naturally increases. Therefore, there is no problem that it is difficult to achieve both a fine line width design and a high development residual film rate in a photosensitive colored resin composition containing a dye. Further, since the pigment is used in patent document 3, there is no problem that it is difficult to achieve both a fine line width design and a high development residual film rate.

As described above, in the case of using a lake material of a triarylmethane dye, unlike the case of using a pigment or the case of using a dye, there is a problem that it is difficult to combine a fine line width design and a high development residual film rate.

The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a photosensitive colored resin composition containing a lake material of a triarylmethane dye, which can form a colored layer having improved brightness, a fine line width, and suppressed film thickness variation before and after development. The present invention also provides a color filter and a display device using the photosensitive colored resin composition.

Means for solving the problems

The photosensitive coloring resin composition of the invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent,

the coloring material contains a coloring material of triarylmethane-based dye.

The color filter of the present invention comprises at least a substrate and a colored layer provided on the substrate, at least one of the colored layers being a cured product of the photosensitive colored resin composition of the present invention.

The display device of the present invention has the color filter of the present invention described above.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a photosensitive colored resin composition containing a lake material of a triarylmethane dye can be provided, which can form a colored layer having improved brightness, a fine line width, and suppressed film thickness variation before and after development. Further, according to the present invention, a color filter and a display device formed using the photosensitive colored resin composition can be provided.

Drawings

Fig. 1 is a schematic diagram showing an example of a color filter according to 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.

Detailed Description

The photosensitive colored resin composition, cured product, color filter, and display device of the present invention will be described in detail in order.

In the present invention, light includes electromagnetic waves having wavelengths in the visible light and non-visible light regions, and further includes radiation, including microwaves and electron beams, for example. Specifically, electromagnetic waves having a wavelength of 5 μm or less and electron beams.

In the present invention, (meth) acryl means any one of acryl and methacryl, (meth) acrylic means any one of acrylic and methacrylic, and (meth) acrylate means any one of acrylate and methacrylate.

In the present specification, "to" representing a numerical range is used in a meaning including numerical values described before and after the numerical value as a lower limit value and an upper limit value.

I. Photosensitive coloring resin composition

the coloring material contains a coloring material of triarylmethane-based dye.

The photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, and the coloring material is a triarylmethane dye-based lake material, so that a colored layer having improved brightness, a fine line width, and suppressed film thickness variation before and after development can be formed. The role of the effect is not clear, and is presumed as follows.

As described above, since the transmittance of ultraviolet rays of the pigment is low, the photocurable component is relatively difficult to cure in the photosensitive colored resin composition containing the pigment. Further, since the dye easily deteriorates the curability of the photocurable component, the photocurable component is also relatively difficult to cure in the photosensitive colored resin composition containing the dye. In contrast, since the color lake material of the triarylmethane-based dye has high transmittance of ultraviolet rays and does not deteriorate the curability of the photocurable component, the effect of being insoluble in a developer after photocuring is higher than that of a pigment or a dye, and thus the pattern line width tends to be large. In a photosensitive coloring resin composition of a lake material containing a triarylmethane dye, in order to set a pattern line width to a predetermined fine line width, it is necessary to effectively suppress a photo-curing reaction.

It is considered that when a color lake material of a triarylmethane dye having a high transmittance is used as a coloring material, the amount of photoinitiating agent is reduced so that the line width of the pattern becomes a predetermined value, the radical generation by photoreaction is reduced regardless of the film thickness direction, and therefore the photocurability of the pattern portion is insufficient, and the film thickness change from before to after development increases, and the development residual film rate decreases. Further, it is considered that when a lake material of a triarylmethane dye is used, an antioxidant is added or the amount thereof is increased in order to match the pattern line width with a predetermined value, radicals generated by photoreaction of a photoinitiator are deactivated regardless of the film thickness direction, and thus the photo-curability of the pattern portion is insufficient, and the film thickness change before to after development increases, and the development residual film rate decreases.

In contrast, in the present invention, an ultraviolet absorber is combined with a lake material of a triarylmethane dye. The ultraviolet absorber is thought to act according to the depth of the film, and thus can suppress the reduction in film thickness of the developed residual film and reduce the line width, because the ultraviolet absorber does not attenuate ultraviolet light on the film surface, and therefore does not reduce the developed residual film, and ultraviolet light attenuates as it reaches the deep portion of the film, and thus reduces the generation of radicals originating from the initiator.

Further, since the coloring material contains a coloring material of triarylmethane-based dye, the transmittance of the colored layer which is a cured product of the photosensitive colored resin composition of the present invention is high, and the chromaticity change caused by the process in the production of ultraviolet irradiation, post baking, or the like is suppressed. Therefore, the photosensitive colored resin composition of the present invention can improve the brightness of the finally obtained colored layer.

The photosensitive colored resin composition of 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 may further contain other components within a range that does not impair the effects of the present invention. For example, the photosensitive colored resin composition of the present invention may further contain a dispersant in order to improve the dispersibility of the coloring material.

The components of the photosensitive colored resin composition of the present invention will be described in detail below in order from the ultraviolet absorber.

[ ultraviolet absorber ]

The ultraviolet absorber in the present invention is a compound having an absorption maximum wavelength of 400nm or less and having no absorption for visible light having a wavelength of more than 420 nm. The ultraviolet absorber used in the present invention may be a compound having no absorption wavelength for visible light having a wavelength of more than 400 nm.

The structure of the ultraviolet absorber used in the present invention is not particularly limited. Examples of the ultraviolet absorber include: benzotriazole-based ultraviolet light absorber, triazine-based ultraviolet light absorber, benzophenone-based ultraviolet light absorber, benzoate-based ultraviolet light absorber, benzoic acid-based ultraviolet light absorber, anthranilic acid-based ultraviolet light absorber, salicylic acid-based ultraviolet light absorber, cinnamic acid-based ultraviolet light absorber, and the like.

For example, as the benzotriazole-based ultraviolet absorber, at least 1 ultraviolet absorber selected from the benzotriazole-based ultraviolet absorbers represented by the following general formula (a) can be mentioned.

[ chemical formula 1]

General formula (A)

(in the general formula (A), X ¹ 、X ² And X ³ Each independently represents a hydrogen atom, a hydroxyl group, -OR ^a Or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, R ^a Represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, X ¹ 、X ² And X ³ At least one of (C) represents hydroxy, -OR ^a Or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. X is X ⁴ Represents a hydrogen atom or a halogen atom. )

In the general formula (A), X ¹ 、X ² And X ³ And R is ^a The hydrocarbon group having 1 to 15 carbon atoms in (b) may be a linear or branched aliphatic hydrocarbon group or an aromatic hydrocarbon group, and examples thereof include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, phenyl, naphthyl, biphenyl, and the like. The number of carbon atoms of the hydrocarbon group may be 1 to 12 or 1 to 8. The hydrocarbon group may be an aliphatic hydrocarbon group, a linear or branched alkyl group, or a methyl group, a t-butyl group, a t-amyl group, a n-octyl group, a t-octyl group (1, 3-tetramethylbutyl group), or a 2-ethylhexyl group.

Examples of the substituent include: halogen atom, hydroxyl group, cyano group, or group containing carbonyl group, ester group, ether group, amide group, imide group, etc., may be acyl group, acyloxy group, alkoxy group, aryloxy group, glycidyl group, etc. Further, the substituent of the aromatic hydrocarbon group may be an alkyl group.

As the hydrocarbon group having a substituent, for example, 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 Methacryloxyethyl, etc., and may be 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl, 4-glycidoxyphenyl, 4-isocyanurate oxyphenyl, etc. above-C ₈ H ₁₇ 、-C ₁₂ H ₂₅ And the like may be straight or branched, respectively.

In the general formula (a), examples of the halogen atom include: chlorine atoms, fluorine atoms, bromine atoms, and the like.

Examples of the benzotriazole-based ultraviolet absorber include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate in combination with 2-ethylhexyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1, 1-ethyl) -1-phenyl) -1- (1, 3-hydroxy-phenyl) -1, 3-tetramethylbutyl) phenol, and the like.

For example, as the triazine ultraviolet light absorber, at least 1 ultraviolet light absorber selected from the triazine ultraviolet light absorbers represented by the following general formula (B) can be exemplified.

[ chemical formula 2]

General formula (B)

(in the general formula (B), Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ And Y ⁶ Each independently represents a hydrogen atom, a hydroxyl group, -OR ^b Or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, 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 、Y ⁵ And Y ⁶ At least one of (C) represents hydroxy, -OR ^b Or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. )

Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ And Y ⁶ And R is ^b The hydrocarbon group having 1 to 15 carbon atoms which may have a substituent may be the same as the above X ¹ 、X ² And X ³ And R is ^a The above hydrocarbon groups having 1 to 15 carbon atoms which may have a substituent are the same.

Y ² 、Y ⁴ And Y ⁶ At least one of (2) may be a hydroxyl group or a hydroxyphenyl triazine ultraviolet absorber.

Examples of the triazine ultraviolet light absorber include: 2- [4, 6-bis (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, as the benzophenone-based ultraviolet absorber, there can be mentioned a hydroxybenzophenone-based ultraviolet absorber, and there can be mentioned at least 1 ultraviolet absorber selected from the hydroxybenzophenone-based ultraviolet absorbers represented by the following general formula (C).

[ chemical formula 3]

General formula (C)

(in the general formula (C), Z ¹ Represents hydroxy, -OR ^c Or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, Z ² Represents a hydrogen atom, a hydroxyl group, -OR ^c Or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, Z ³ Represents a hydrogen atom or a hydroxyl group, R ^c Represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent. )

In the general formula (C), Z ¹ And Z ² And R is ^c The hydrocarbon group having 1 to 15 carbon atoms which may have a substituent may be the same as the above X ¹ 、X ² And X ³ And R is ^a The above hydrocarbon groups having 1 to 15 carbon atoms which may have a substituent are the same.

Examples of the benzophenone-based ultraviolet absorber include: 2, 4-dihydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-dihydroxy-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 is usually 2000 or less, preferably 1500 or less, more preferably 900 or less in terms of efficiently absorbing ultraviolet rays. In addition, since the polymer of the ultraviolet absorber has low ultraviolet absorption ability, a non-polymer compound having no repeating unit is preferable.

The ultraviolet absorber used in the present invention is preferably one having a transmittance of 45% or less at 365nm in a 0.002 mass% propylene glycol monomethyl ether acetate solution. As described above, when an ultraviolet absorber having a small transmittance at 365nm is used in combination with a triarylmethane dye lake, the intensity of ultraviolet light having a weak absorption of the triarylmethane lake and the highest irradiation intensity of the ultra-high pressure mercury lamp can be effectively reduced, and as a result, it is preferable to add an initiator in an amount sufficient to ensure the curability of the coating film surface to suppress the film thickness change after development, and to effectively reduce the photocurability inside the coating film so that the line width shift amount does not become excessive.

Regarding the transmittance of the ultraviolet absorber at 365nm, it is possible to prepare a 0.002 mass% propylene glycol monomethyl ether acetate solution of the ultraviolet absorber and measure the 0.002 mass% propylene glycol monomethyl ether acetate solution using an ultraviolet-visible near infrared spectrophotometer (for example, V-7100 of japan spectrophotometry).

The ultraviolet absorber used in the present invention has a transmittance of not more than 42%, more preferably not more than 40% at 365nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution.

In order to obtain the effect of the present invention, the ultraviolet absorber used in the present invention preferably has a solubility in a solvent used in the photosensitive colored resin composition at 25 ℃ of 1 mass% or more.

The ultraviolet absorber used in the present invention may be one having a solubility of 1 mass% or more in propylene glycol monomethyl ether acetate at 25 ℃.

Examples of the ultraviolet absorber used in the present invention include the following compounds as suitable ultraviolet absorbers: 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, 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' -dihydroxy-4-methoxybenzophenone, 2- (2-hydroxy-5-methacryloxyethyl) -2H-benzotriazole, (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, and the like.

Examples of the commercial products include: tinuvinPS, tinuvin329, tinuvin405, tinuvin477, tinuvin479, tinuvin571, tinuvin928 (manufactured by BASF, supra), kemisorb12, kemisorb71D, kemisorb73, kemisorb111 (manufactured by Chemipro Kasei, supra), RUVA-93 (manufactured by tsukamur chemistry, supra), and the like.

In the present invention, 1 or 2 or more ultraviolet absorbers may be used singly or in combination.

In the case of selecting and using an ultraviolet absorber having a transmittance of 45% or less at 365nm in a 0.002 mass% propylene glycol monomethyl ether acetate solution, 2 or more types may be used in combination. That is, even if the ultraviolet absorber used in the present invention contains an ultraviolet absorber having a transmittance of more than 45% at 365nm in 0.002 mass% propylene glycol monomethyl ether acetate solution alone, a mixture of 2 or more ultraviolet absorbers may be used as long as the transmittance at 365nm in 0.002 mass% propylene glycol monomethyl ether acetate solution is 45% or less.

The content of the ultraviolet absorber may be in the range of usually 0.2 to 4.0 mass%, preferably 0.3 to 3.0 mass%, and more preferably 0.5 to 2.0 mass% based on the total solid content of the photosensitive colored resin composition, for the purpose of obtaining a line width suppressing effect and adjusting the photocurability so as to be cured satisfactorily.

The solid component is all components except the solvent, and includes a liquid photopolymerizable compound and the like.

In order to obtain a line width suppressing effect and to adjust the photocurability so that the curing is performed well, the ratio of the total mass of the ultraviolet light absorbers to the total mass of the photoinitiators and the ultraviolet light absorbers is preferably in the range of 2.0 to 20.0 mass%, more preferably in the range of 4.0 to 18.0 mass%.

[ colorant ]

In order to obtain a photosensitive colored resin composition capable of forming a colored layer which is suppressed in chromaticity change and luminance decrease before and after a high-temperature heating step, and in which the luminance of a finally obtained colored layer is improved, the line width is small, and in which the film thickness change before and after development is suppressed, the coloring material of the present invention contains a coloring material of triarylmethane dye.

< lake Material of triarylmethane dye >

The lake material of the triarylmethane dye is preferably a lake material of the triarylmethane dye and a polyacid in terms of excellent heat resistance and light resistance and achieving high brightness of the color filter. Among these pigments, 1 or more pigments selected from the pigments represented by the following general formula (1) and the pigments represented by the following general formula (2) are preferable, and the pigments represented by the following general formula (1) are preferable in terms of forming a molecular aggregation state, exhibiting more excellent heat resistance, and enabling high brightness.

[ chemical formula 4]

General formula (1)

(in the general formula (1), A is an organic group having a valence of a and having no pi bond to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may contain a hetero atom B ^c- Represents a polyacid anion of valence c. R is R ⁱ ～R ^v Each independently represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R ⁱⁱ And R is R ⁱⁱⁱ 、R ^iv And R is R ^v May be bonded to form a ring structure. R is R ^vi And R is ^vii Each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. Ar (Ar) ¹ Represents a divalent aromatic group which may have a substituent. There are a plurality of R ⁱ ～R ^vii And Ar is a group ¹ Can respectively be used forEither 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 integers of 0 to 4 inclusive. There are a plurality of f and g each of which may be the same or different. )

[ chemical formula 5]

General formula (2)

(in the general formula (2), R ^I ～R ^VI Each independently represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R ^I And R is R ^II 、R ^III And R is R ^IV 、R ^V And R is R ^VI May be bonded to form a ring structure. R is R ^VII And R is ^VIII Each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. Ar (Ar) ² Represents a divalent aromatic heterocyclic group which may have a substituent, and a plurality of R's are present ^I ～R ^VIII And Ar is a group ² The respective may be the same or different. E (E) ^m- Represents an m-valent polyacid anion.

m represents an integer of 2 or more. k and l represent integers of 0 to 4 inclusive. There are a plurality of k and l each may be the same or different. )

Since the coloring material represented by the general formula (1) contains an anion having a valence of two or more and a cation having a valence of two or more, in the aggregate of the coloring material, the anion and the cation do not simply bond 1 molecule to 1 molecule, but form a molecular aggregate in which a plurality of molecules are aggregated via ionic bonds, and thus the apparent molecular weight is significantly increased as compared with the molecular weight of a conventional lake pigment. It is presumed that the formation of such molecular aggregates further improves the cohesive force in the solid state, reduces thermal movement, and suppresses dissociation of ion pairs and decomposition of cationic portions, which is less likely to discolor than conventional lake pigments.

In the general formula (1), a is an organic group having a valence of a, which is not pi-bonded to a carbon atom directly bonded to N (nitrogen atom), and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at a terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and a heteroatom such as O (oxygen atom), S (sulfur atom), or N (nitrogen atom) may be contained in a carbon chain. That is, the organic group means an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N and having a heteroatom such as O, S, N in the carbon chain, or an aromatic group having an aliphatic hydrocarbon group at the end directly bonded to N and having a heteroatom such as O, S, N in the carbon chain. Since the carbon atom directly bonded to N does not have pi bond, the color characteristics such as hue and transmittance of the cationic color development site are not affected by the linking group a or other color development site, and the same color as that of the monomer can be maintained.

In a, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be any of a straight chain, a branched chain, or a cyclic chain as long as the carbon atom at the terminal directly bonded to N does not have pi bond, and the carbon atom other than the terminal may have an unsaturated bond or a substituent, and O, S, N may be contained in the carbon chain. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, or the like may be included, and a hydrogen atom may be further substituted with a halogen atom or the like.

In a, the aromatic group having an aliphatic hydrocarbon group may be a monocyclic or polycyclic aromatic group containing an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, and may have a substituent, and may be a heterocyclic ring containing O, S, N.

Among them, a preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group in terms of the firmness of the skeleton.

Examples of the cyclic aliphatic hydrocarbon group include cyclohexane, cyclopentane, norbornane and bicyclo [ 2.2.2:]octane, tricyclo [5.2.1.0 ^2，6 ]Decane, adamantane groups, and the like. Examples of the aromatic group include groups containing a benzene ring and a naphthalene ring. For example, when A is a divalent organic group, examples thereof include a straight-chain, branched or cyclic alkylene group having 1 to 20 carbon atoms or And aromatic groups in which 2 alkylene groups having 1 to 20 carbon atoms are substituted with a xylylene group.

In the present invention, in terms of both the firmness and the degree of freedom of molecular movement and improving heat resistance, a is preferably an aliphatic hydrocarbon group having 2 or more cyclic aliphatic hydrocarbon groups, a saturated aliphatic hydrocarbon group at the end directly bonded to N, and O, S, N may be contained in the carbon chain. More preferably, a is an aliphatic hydrocarbon group having 2 or more cycloalkylene groups, having a saturated aliphatic hydrocarbon group at the end directly bonded to N, and further comprising O, S, N in the carbon chain, and further preferably has a structure in which 2 or more cyclic aliphatic hydrocarbon groups are linked by a linear or branched aliphatic hydrocarbon group.

The cyclic aliphatic hydrocarbon groups having 2 or more groups may be the same or different, and examples thereof include the same aliphatic hydrocarbon groups as those of the above-mentioned cyclic aliphatic hydrocarbon groups, and among them, cyclohexane and cyclopentane are preferable.

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

[ chemical formula 6]

General formula (1 a)

(in the general formula (1 a), R ^xi Represents an alkylene group having 1 to 3 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms as a substituent, R ^xii And R is ^xiii Each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p represents an integer of 1 to 3, and q and r each independently represent an integer of 0 to 4. At R ^xi 、R ^xii 、R ^xiii And R in the case where there are plural R ^xi 、R ^xii 、R ^xiii And r may be the same or different from each other. )

Excellent in both of the fastness and the thermal movement of the developed part and heat resistanceIn terms of height, R is preferred ^xi An alkylene group having 1 to 3 carbon atoms. Examples of such alkylene groups include: methylene, ethylene, propylene, and the like, among which methylene or ethylene is preferable, and methylene is more preferable.

Examples of the alkyl group having 1 to 4 carbon atoms include: the methyl group, ethyl group, propyl group, and butyl group may be linear or branched.

Further, examples of the alkoxy group having 1 to 4 carbon atoms include: methoxy, ethoxy, propoxy, and butoxy groups may be linear or branched.

R ^xii And R is ^xiii Examples of the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms include the above R ^xi May have the same substituent.

In the general formula (1 a), in terms of heat resistance, cyclohexane (cyclohexylene) is preferably 2 or more and 4 or less, that is, p is 1 or more and 3 or less, and among them, p is more preferably 1 or more and 2 or less.

In addition, the substituent R of cyclohexylene group ^xii And R is ^xiii The number of substitution is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, in terms of heat resistance. That is, q and r are preferably integers of 1 to 3, and q and r are preferably integers of 1 to 2.

Examples of suitable linking groups a include, but are not limited to, the following.

[ chemical formula 7]

R ⁱ ～R ^v The alkyl group in (a) is not particularly limited. Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group include a linear or branched alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group include a linear alkyl group having 1 to 5 carbon atoms in terms of brightness and heat resistanceChain or branched alkyl groups, and R may be mentioned ⁱ ～R ^v The alkyl in (2) is ethyl or methyl. The substituent that the alkyl group may have is not particularly limited, and examples thereof include: examples of the substituted alkyl group include aralkyl groups such as benzyl groups, and the like.

R ⁱ ～R ^v The aryl group in (a) is not particularly limited. Examples include: phenyl, naphthyl, and the like. Examples of the substituent that the aryl group may have include: alkyl, halogen atom, alkoxy, hydroxy, and the like.

Wherein R is as R in terms of chemical stability ⁱ ～R ^v Preferably independently of one another, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ And R is R ⁱⁱⁱ 、R ^iv And R is R ^v Bonding to form a pyrrolidine ring, a piperidine ring, a morpholine ring.

In terms of heat resistance, R is preferable ⁱⁱ ～R ^v At least one of them is cycloalkyl which may have a substituent, or aryl which may have a substituent. Thought to be through R ⁱⁱ ～R ^v At least one of them has cycloalkyl or aryl, and the intermolecular interaction due to steric hindrance is reduced, so that the influence of the developed part on heat can be suppressed, and the heat resistance is excellent.

In terms of heat resistance, R is preferable ⁱⁱ ～R ^v At least one of them is a substituent represented by the following general formula (1 b) or the following general formula (1 c).

[ chemical formula 8]

General formula (1 b)

(in the general formula (1 b), R ^xiv 、R ^xv And R ^xvi Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent. )

[ chemical formula 9]

General formula (1 c)

(in the general formula (1 c), R ^xvii 、R ^xviii And R ^xix Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent. )

As R ^xiv 、R ^xv 、R ^xvi 、R ^xvii 、R ^xviii And R ^xix Examples of the alkyl group having 1 to 4 carbon atoms include: the methyl group, ethyl group, propyl group, and butyl group may be linear or branched. Further, examples of the alkoxy group having 1 to 4 carbon atoms include: methoxy, ethoxy, propoxy, and butoxy groups may be linear or branched.

Examples of the substituent that the alkyl group and the alkoxy group may have include: halogen atom, hydroxyl group, etc.

In the case of having the substituent represented by the above general formula (1 b), R is preferable in terms of heat resistance ^xiv 、R ^xv And R ^xvi At least one of (a) is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, more preferably R ^xiv And R is ^xv At least one of (a) is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.

In addition, in the case of having the substituent represented by the above general formula (1 c), R is preferable in terms of heat resistance ^xvii 、R ^xviii And R ^xix At least one of (a) is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent, more preferably R ^xvii And R is ^xviii At least one of (2) is an alkyl group having 1 to 4 carbon atoms which may have a substituent, orAn alkoxy group having 1 to 4 carbon atoms which has a substituent.

R ^vi And R is ^vii Each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. As R ^vi And R is ^vii The alkyl group in (a) is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include: the methyl group, ethyl group, propyl group, and butyl group may be linear or branched. The substituent that the alkyl group may have is not particularly limited, and examples thereof include: aryl, halogen atom, hydroxy, alkoxy, and the like.

In addition, as R ^vi And R is ^vii The alkoxy group in (a) is not particularly limited, but is preferably a straight-chain or branched alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include: methoxy, ethoxy, propoxy, and butoxy groups may be linear or branched. The substituent that the alkoxy group may have is not particularly limited, and examples thereof include: aryl, halogen atom, hydroxy, alkoxy, and the like.

As R ^vi And R is ^vii Examples of the halogen atom in (b) include: fluorine atom, chlorine atom, bromine atom, iodine atom.

R ^vi And R is ^vii The substitution numbers of (a), i.e., f and g, each independently represent an integer of 0 to 4, wherein 0 to 2 are preferable, and 0 to 1 are more preferable. There are a plurality of f and g each of which may be the same or different.

In addition, R ^vi And R is ^vii Any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the xanthene skeleton may be substituted, and among them, substitution with-NR is preferable ⁱⁱ R ⁱⁱⁱ or-NR ^iv R ^v The substitution position of the represented amino group is the meta position with respect to the reference.

Ar ¹ Divalent aromatic compounds of (3)The group is not particularly limited. Ar (Ar) ¹ The aromatic group in (a) may be a heterocyclic group in addition to an aromatic hydrocarbon group comprising a carbocyclic ring. Examples of the aromatic hydrocarbon in the aromatic hydrocarbon group include, in addition to benzene rings: condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetrahydronaphthalene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, and the like; and chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and the like. In the chain polycyclic hydrocarbon, O, S, N may be present in a chain skeleton such as diphenyl ether. On the other hand, examples of the heterocycle in the heterocyclic group include: 5 membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole and the like; 6 membered heterocyclic rings such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine and the like; benzofurans, benzothiophenes, indoles, carbazoles, coumarins, benzopyrones, quinolines, isoquinolines, acridines, daizines, quinazolines, quinoxalines, and the like. These aromatic groups may further have an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group which may be substituted with these, and the like as substituents.

1 there are multiple R's in the molecule ⁱ ～R ^vii And Ar is a group ¹ May be the same or different. By R ⁱ ～R ^vii And Ar is a group ¹ Can be adjusted to the desired color.

The valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. In this lake material, the cation has a valence a of 2 or more, and therefore, the heat resistance is excellent, wherein the valence a of the cation may be 3 or more. The upper limit of a is not particularly limited, but a is preferably 4 or less, more preferably 3 or less, in terms of ease of production.

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

In the colorant represented by the general formula (1), the anion part (B) ^c- ) The polyacid anion is a c-valent polyacid anion and is a divalent or more anion in terms of high brightness and excellent heat resistance.

As the polyacid anion obtained by condensing a plurality of oxo acids, isopolyacid anions (M _m O _n ) ^c- May also be a heteropolyacid anion (X) ₁ M _m O _n ) ^c- . In the above-mentioned ion, M represents a multi-atom, X represents a hetero atom, M represents a composition ratio of the multi-atom, and n represents a composition ratio of the oxygen atom. Examples of the polyatomic M include: mo, W, V, ti, nb, etc. Examples of the heteroatom X include: si, P, as, S, fe, co, etc. In addition, na may be contained in a part ⁺ Or H ⁺ And the like.

Among them, a polyacid containing 1 or more elements selected from tungsten (W) and molybdenum (Mo) is preferable in terms of excellent heat resistance.

Examples of such polyacids include: tungstate ions as isopoly acid [ W ] ₁₀ O ₃₂ ] ^4- Molybdic acid radical ion [ Mo ₆ O ₁₉ ] ^2- The method comprises the steps of carrying out a first treatment on the surface of the Or phosphotungstic acid radical ion [ PW ] as heteropoly acid ₁₂ O ₄₀ ] ^3- 、[P ₂ W ₁₈ O ₆₂ ] ^6- Silicotungstic acid radical ion [ SiW ] ₁₂ O ₄₀ ] ^4- Phosphomolybdic acid radical ion [ PMo ] ₁₂ O ₄₀ ] ^3- Silicon molybdate ion [ SiMo ₁₂ O ₄₀ ] ^4- Phosphotungstic molybdate ion [ PW _12-s Mo _s O ₄₀ ] ^3- (s is an integer of 1 to 11 inclusive), [ P ] ₂ W _18-t Mo _t O ₆₂ ] ^6- (t is an integer of 1 to 17 inclusive) tungsten silicide molybdate ion [ SiW ] _12-u Mo _u O ₄₀ ] ^4- (u is an integer of 1 to 11). Among the above, the heteropolyacid containing at least 1 kind of tungsten (W) and molybdenum (Mo) is preferable in terms of heat resistance and easiness of raw material obtaining, and the heteropolyacid further containing phosphorus (P) is more preferable.

Further, in terms of heat resistance, it is more preferably phosphotungstic molybdate ion [ PW ₁₀ Mo ₂ O ₄₀ ] ^3- 、[PW ₁₁ Mo ₁ O ₄₀ ] ^3- Phosphotungstic acid radical ion [ PW ₁₂ O ₄₀ ] ^3- Any of the above.

B in the general formula (1) represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent integers of 1 or more. When b is 2 or more, the number of cations present in the molecular aggregate may be 1 alone or 2 or more in combination. When d is 2 or more, the anions present in the molecular aggregate may be 1 type alone or 2 or more types in combination.

The lake material represented by the general formula (1) may be prepared, for example, by referring to the specification of international publication No. 2012/144520 and the specification of international publication No. 2018/003706.

On the other hand, in the general formula (2), R ^I ～R ^VI Each independently represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R ^I And R is R ^II 、R ^III And R is R ^IV 、R ^V And R is R ^VI May be bonded to form a ring structure. R is R ^I ～R ^VI R can be respectively identical to R of the above-mentioned general formula (1) ⁱ ～R ^v The same applies.

In the general formula (2), R ^VII And R is ^VIII Each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group, which may also be the same as R of the above general formula (1) ^vi And R is ^vii The same applies.

In the general formula (2), ar ² Represents a divalent aromatic heterocyclic group which may have a substituent, which Ar is ² Ar of the general formula (1) described above ¹ The aromatic heterocyclic groups in (a) are the same.

In the general formula (2), E ^m- Represents an m-valent polyacid anion which may be the same as the c-valent polyacid anion of the above general formula (1).

In the general formula (2), m represents the number of cations and the number of anions, and represents an integer of 2 or more. The number of cations in the general formula (2) may be 1 alone or 2 or more cations may be combined. The anions may be 1 kind alone or 2 or more kinds may be combined.

In addition, k and l in the general formula (2) may be the same as f and g of the above general formula (1).

The color lake represented by the general formula (2) can be prepared by referring to, for example, japanese patent application laid-open No. 2017-16099.

The coloring material of the triarylmethane dye used in the photosensitive coloring resin composition of the present invention is not limited to 1 or more selected from the coloring materials represented by the general formula (1) and the coloring materials represented by the general formula (2), and may be appropriately selected and used.

For example, it is possible to use: a lake material comprising a cation of a triarylmethane dye described in Japanese patent application laid-open No. 2015-96947, japanese patent application laid-open No. 2016-27149, and Japanese patent application laid-open No. 2017-16099 and various polyacid anions as described above; or a lake material of a triarylmethane-based dye and a polyacid described in Japanese patent application laid-open No. 2015-96947, 2016-27149, and 2017-16099.

In the photosensitive colored resin composition of the present invention, 1 or 2 or more kinds of the lake material of the triarylmethane-based dye may be used alone or in combination.

< other coloring materials >

The coloring material used in the present invention contains a coloring material of a triarylmethane-based dye as an essential component, and other coloring materials may be used in combination for adjusting the color tone within a range that does not impair the effect of the present invention.

As the other coloring material, known pigments, dyes, color pigments and the like may be used alone or 2 or more kinds may be mixed and used.

Among these, other coloring materials may be preferably used, but are not limited to, other blue coloring materials, violet coloring materials, and red coloring materials.

Examples of the other blue coloring material include known organic blue pigments such as c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6.

Examples of the violet colorant include known organic violet pigments such as c.j. pigment violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38.

Examples of the red or purplish red coloring material include xanthene dyes and coloring materials for xanthene dyes described in International publication No. 2020/071041, japanese patent application laid-open No. 2018-100323, international publication No. 2014/123125, and the like.

< colorant content >

In the photosensitive colored resin composition of the present invention, a coloring material other than a coloring material of a triarylmethane-based dye may be further contained in the coloring material within a range that does not impair the effects of the present invention, and the content of the coloring material of the triarylmethane-based dye is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and still more preferably 95% by mass or more and 100% by mass or less, relative to the total amount of the coloring material.

The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as a desired color development can be achieved in the case of producing a colored layer of a color filter, and is different depending on the type of the coloring material used, but is preferably in the range of 10 to 100nm, and more preferably 15 to 60nm. When the average primary particle diameter of the coloring material is in the above range, a display device including a color filter manufactured using the photosensitive colored resin composition of the present invention can be manufactured with high contrast and high quality.

The average dispersion particle diameter of the coloring material in the photosensitive colored resin composition varies depending on the type of the coloring material used, and is preferably in the range of 10 to 100nm, more preferably in the range of 15 to 60nm.

The average dispersion particle diameter of the coloring material in the photosensitive colored resin composition is the dispersion particle diameter of the coloring material particles dispersed in a dispersion medium containing at least a solvent, and can be measured by a laser scattering particle size distribution meter. As the measurement of the particle diameter by the laser scattering particle size distribution meter, the photosensitive colored resin composition may be appropriately diluted (for example, 1000 times or the like) with a solvent used for the photosensitive colored resin composition to a concentration that can be measured by the laser scattering particle size distribution meter, and the measurement may be performed by a dynamic light scattering method at 23 ℃ using the laser scattering particle size distribution meter (for example, nanotrac particle size distribution measuring apparatus UPA-EX150 manufactured by daily nectar corporation). The average distribution particle diameter herein is a volume average particle diameter.

The coloring material used in the present invention can be produced by a known method such as recrystallization or solvent salt milling. Further, a commercially available coloring material may be used by subjecting it to a pulverization treatment.

In the photosensitive colored resin composition of the present invention, the content of the coloring material is not particularly limited. The content of the coloring material is usually in the range of 3 to 65 mass%, preferably in the range of 4 to 60 mass%, and more preferably in the range of 15 to 60 mass%, with respect to the total solid content of the photosensitive colored resin composition, in terms of dispersibility and dispersion stability. When the lower limit is not less than the above, the colored layer has 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). In addition, when the upper limit value is less than or equal to the above, a colored layer having excellent storage stability and sufficient hardness and adhesion to a substrate can be obtained. In particular, when a colored layer having a relatively high coloring material concentration is formed, the total content of the coloring materials is preferably in the range of 20 to 65 mass%, more preferably in the range of 30 to 60 mass%, relative to the total solid content of the photosensitive colored resin composition.

[ alkali-soluble resin ]

The alkali-soluble resin in the present invention has an acidic group, and can be suitably selected from alkali-soluble resins which function as a binder resin and are soluble in an alkali developer used for pattern formation.

In the present invention, the alkali-soluble resin may have an acid value of 40mgKOH/g or more.

Preferred alkali-soluble resins in the present invention are resins having an acidic group, usually having a carboxyl group, and specifically, examples thereof include: acrylic resins such as acrylic copolymers having a carboxyl group and styrene-acrylic copolymers having a carboxyl group, and epoxy (meth) acrylate resins having a carboxyl group.

Among these, particularly preferred is an alkali-soluble resin having a carboxyl group in a side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain. In the case of containing a photopolymerizable functional group, the alkali-soluble resins or the alkali-soluble resins and a photopolymerizable compound such as a polyfunctional monomer may form a crosslinking bond in the curing step of the resin composition at the time of manufacturing the color filter. The cured film has further improved film strength and development resistance, and the cured film has suppressed heat shrinkage and excellent adhesion to the substrate.

The method of introducing the ethylenic unsaturated bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. Examples include: a method of introducing an ethylenically unsaturated bond into a side chain by adding a compound having both an epoxy group and an ethylenically unsaturated bond in a molecule, for example, glycidyl (meth) acrylate, to a carboxyl group of an alkali-soluble resin; and a method in which a structural unit having a hydroxyl group is introduced into a copolymer in advance, a compound having an isocyanate group and an ethylenically unsaturated bond in the molecule is added thereto, and an ethylenically unsaturated bond is introduced into a side chain.

Hereinafter, a monomer having a group having an ethylenically unsaturated bond (a monomer having an ethylenically unsaturated group) may be simply referred to as an ethylenically unsaturated monomer.

In addition, the alkali-soluble resin preferably further has a hydrocarbon ring in terms of excellent adhesion of the colored layer. When the alkali-soluble resin contains a hydrocarbon ring as a bulky group, shrinkage during curing is suppressed, peeling between the resin and the substrate is relaxed, and substrate adhesion is improved.

Examples of such hydrocarbon rings include: an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and combinations thereof, and the hydrocarbon ring may have a substituent such as an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, a halogen atom, or the like.

The hydrocarbon ring may be contained as a monovalent group or may be contained as a group having a valence of two or more.

Specific examples of the hydrocarbon ring include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, isobornane, tricyclo [5.2.1.0 (2, 6) ] decane (dicyclopentane), and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene, and the like; a chain polycyclic ring such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, or Cardo structure (9, 9-diaryl fluorene); and a group in which a part of these groups is substituted with a substituent.

Examples of the substituent include: alkyl, cycloalkyl, alkylcycloalkyl, hydroxy, carbonyl, nitro, amino, halogen atoms, and the like.

The case of containing an aliphatic hydrocarbon ring as the hydrocarbon ring is preferable in terms of improving the heat resistance and adhesion of the colored layer and improving the brightness of the obtained colored layer.

In addition, the inclusion of the Cardo structure is particularly preferable in terms of improving the curability of the colored layer, suppressing the discoloration of the coloring material, and improving the solvent resistance (NMP swelling suppression).

Acrylic resins such as acrylic copolymers containing structural units having carboxyl groups and styrene-acrylic copolymers having carboxyl groups are (co) polymers obtained by (co) polymerizing ethylenically unsaturated monomers having carboxyl groups and, if necessary, other monomers copolymerizable therewith, for example, by a known method.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include: (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω -carboxyl-polycaprolactone mono (meth) acrylate, and the like can be used. In addition, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as the carboxyl group precursor. Among them, (meth) acrylic acid is particularly preferable in terms of copolymerizability and cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin in the present invention is preferably a carboxyl group-containing copolymer such as an acrylic copolymer and a styrene-acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, more preferably an acrylic copolymer and a styrene-acrylic copolymer containing a carboxyl group, each of which contains a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring and a structural unit having an ethylenically unsaturated bond.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include: for the cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, and the like, at least 1 selected from the group consisting of cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, and styrene is preferably used in terms of the effect that the cross-sectional shape of the developed colored layer is maintained also in the heat treatment.

The carboxyl group-containing copolymer may further contain other structural units such as structural units having an ester group, e.g., methyl (meth) acrylate and ethyl (meth) acrylate. The structural unit having an ester group functions not only as a component that inhibits alkali solubility of the colored resin composition, but also as a component that improves solubility with respect to a solvent and further improves solvent resolubility.

The carboxyl group-containing copolymer can be prepared into an alkali-soluble resin having desired properties by appropriately adjusting the addition amount of each structural unit.

The amount of the carboxyl group-containing ethylenically unsaturated monomer to be added is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the monomers, in terms of obtaining a good pattern. On the other hand, in terms of suppressing film roughness or the like on the pattern surface after development, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50 mass% or less, more preferably 40 mass% or less, relative to the total amount of the monomers.

In addition, in the carboxyl group-containing copolymer such as the acrylic copolymer and the styrene-acrylic copolymer containing a structural unit having an ethylenic unsaturated bond which can be more preferably used as the alkali-soluble resin, the amount of the compound having both an epoxy group and an ethylenic unsaturated bond added to the carboxyl group-containing ethylenically unsaturated monomer is preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less.

The carboxyl group-containing copolymer preferably has a mass average molecular weight (Mw) in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When the content is 1,000 or more, the function of the cured adhesive is improved, and when the content is 50,000 or less, the pattern formation is improved when the development is performed with an alkaline developer.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, and an epoxy (meth) acrylate compound obtained by reacting an acid anhydride with a reaction product of an epoxy compound and a monocarboxylic acid having an unsaturated group is suitable.

The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be appropriately selected from those known in the art.

The epoxy (meth) acrylate resin having a carboxyl group is also preferably one having the hydrocarbon ring in the molecule, and particularly preferably contains a Cardo structure in terms of improving the curability of the colored layer, suppressing the discoloration of the coloring material, and improving the residual film rate of the colored layer.

The epoxy (meth) acrylate resin having a carboxyl group may be used alone or in combination of two or more.

In terms of developability (solubility) with respect to an alkaline aqueous solution used for the developer, an alkali-soluble resin having an acid value of 30mgKOH/g or more is preferably selected for use. The alkali-soluble resin preferably has an acid value of 40mgKOH/g or more and 300mgKOH/g or less, particularly preferably 50mgKOH/g or more and 280mgKOH/g or less, in terms of developability (solubility) with respect to an alkaline aqueous solution used for the developer and adhesion to a substrate.

In the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the equivalent amount of the ethylenically unsaturated bond is preferably in the range of 100 to 2000, particularly preferably in the range of 140 to 1500, in order to obtain the effects of improving the film strength of the cured film, improving the development resistance, and having excellent adhesion to the substrate. When the equivalent of the ethylenic unsaturated bond is 2000 or less, the development resistance and the adhesion are excellent. Further, when the ratio is 100 or more, the ratio of the structural unit having a carboxyl group to other structural units such as the structural unit having a hydrocarbon ring can be relatively increased, and therefore, the developability and heat resistance are excellent.

Here, the ethylenically unsaturated bond equivalent is the mass average molecular weight relative to 1 mol of ethylenically unsaturated bonds in the alkali-soluble resin, and is represented by the following formula (1).

Digital type (1)

Equivalent of ethylenically unsaturated bond (g/mol) =w (g)/M (mol)

(in the formula (1), W represents the mass (g) of the alkali-soluble resin, M represents the mole number (mol) of the ethylenic unsaturated bond contained in the alkali-soluble resin W (g))

The above-mentioned ethylenically unsaturated bond equivalent may be, for example, as per JIS K0070: the iodine value test method described in 1992 was calculated by measuring the number of ethylenically unsaturated bonds contained in 1g of the alkali-soluble resin.

The alkali-soluble resin used in the photosensitive colored resin composition may be 1 kind or 2 or more kinds, and the content thereof is not particularly limited, but the alkali-soluble resin is preferably in the range of 5 mass% to 60 mass%, more preferably in the range of 8 mass% to 40 mass%, with respect to the total solid content of the photosensitive colored resin composition. When the content of the alkali-soluble resin is not less than the above-mentioned lower limit, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is not more than the above-mentioned upper limit, film roughness and defects of patterns can be suppressed at the time of development.

[ 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 a compound having 2 or more ethylenically unsaturated bonds can be used suitably, and a polyfunctional (meth) acrylate having 2 or more acryl groups or methacryl groups is particularly preferable.

The polyfunctional (meth) acrylate may be appropriately selected from conventionally known polyfunctional (meth) acrylates. Specific examples thereof include multifunctional (meth) acrylates described in JP-A2013-029832.

These polyfunctional (meth) acrylates may be used alone or in combination of 1 or more than 2. In the case where excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional (meth) acrylate preferably has 3 or more (trifunctional) polymerizable ethylenically unsaturated bonds, and the poly (meth) acrylate of a polyhydric alcohol of three or more or a dicarboxylic acid modified product thereof is preferable, and specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.

The photopolymerizable compound used in the present invention is preferably a photopolymerizable compound containing an alkylene oxide, in particular, in terms of being capable of achieving both a high development residual film ratio and a small line width.

As the photopolymerizable compound containing an alkylene oxide, a photopolymerizable compound containing ethylene oxide and/or propylene oxide is preferably exemplified. It is presumed that in the case of containing the above photopolymerizable compound containing an alkylene oxide, active radicals are regenerated from peroxy radicals whose polymerization activity is lost by oxygen inhibition, and thus 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 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 the like, more specifically, may be mentioned: 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 pentaerythritol tetra (meth) acrylate, propylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified glycerol tri (meth) acrylate, ethylene oxide modified diglycerol tetra (meth) acrylate, and the like. Of these, ethylene oxide modified diglycerol tetra (meth) acrylate and ethylene oxide modified dipentaerythritol hexa (meth) acrylate are more preferably contained.

The photopolymerizable compound may be used alone or in combination of 1 or more than 2.

As the photopolymerizable compound, a photopolymerizable compound containing an alkylene oxide may be used in combination with a photopolymerizable compound containing no alkylene oxide.

The content of the photopolymerizable compound containing an alkylene oxide is preferably in the range of 3 to 50 mass%, more preferably in the range of 5 to 30 mass%, based on the total amount of the photopolymerizable compound.

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 mass%, more preferably in the range of 10 to 40 mass%, based on the total solid content of the photosensitive colored resin composition. When the content of the photopolymerizable compound is not less than the above-mentioned lower limit, the photocuring is sufficiently performed, and elution during development of the exposed portion can be suppressed, the line width deviation is suppressed, the solvent resistance is improved, and when the content of the photopolymerizable compound is not more than the above-mentioned 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 1 or 2 or more kinds of photoinitiators can be used in combination from various conventionally known initiators.

Examples of the photoinitiator include: aromatic ketones such as benzophenone, N-dimethylaminobenzophenone, 4 '-diethylaminobenzophenone (for example, hicure ABP, manufactured by chuangkou drug), and 4-methoxy-4' -dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; biimidazoles such as 2- (o-chlorophenyl) -4, 5-phenylimidazole dimer; halomethyl oxadiazole compounds such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole; halomethyl-S-triazines such as 2- (4-butoxy-naphthalen-1-yl) -4, 6-bis-trichloromethyl-S-triazine; oxime esters such as oxime ester photoinitiators described in 1, 2-octanedione-1- [4- (phenylthio) -,2- (o-benzoyl oxime) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (o-acetyl oxime), japanese patent application laid-open No. 2000-80068, japanese patent application laid-open No. 2001-233836, japanese patent application laid-open No. 2010-527339, japanese patent application laid-open No. 2010-527338, japanese patent application laid-open No. 2013-04153, and the like; α -amino ketones such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, irgacure 369, manufactured by BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (Irgacure 379EG, manufactured by BASF); thioxanthones such as diethyl-thioxanthone.

Among them, the photoinitiator used in the present invention preferably contains at least 1 selected from oxime esters and α -aminoketones in view of excellent sensitivity, and α -aminoketones are preferred in view of line width adjustment and development resistance at the time of pattern formation. The α -aminoketone having a tertiary amine structure is preferable because it has a tertiary amine structure as an oxygen quencher in the molecule, and therefore, free radicals generated from the initiator are less likely to be deactivated by oxygen, and sensitivity can be improved.

In addition, as the photoinitiator, it is also preferable to use an oxime ester in combination with an α -aminoketone in terms of suppressing water stains and improving sensitivity. When a component that improves the alkali developability is used, the water stain is a case where, after alkali development, a trace such as a water stain is generated after washing with pure water. Such water stains disappear after post baking, and therefore there is no problem as a product, but in the appearance inspection of the patterned surface after development, they are detected as speck anomalies, and there is a problem that normal products and abnormal products cannot be distinguished. Therefore, in the appearance inspection, if the inspection sensitivity of the inspection device is lowered, the yield of the final color filter product is lowered as a result, which is a problem.

In addition, as the photoinitiator, at least 1 selected from oxime esters and α -aminoketones is preferably combined with thioxanthones in terms of adjusting sensitivity, suppressing water stains, and improving development resistance.

The total content of the photoinitiators 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, and is preferably in the range of 0.1 to 12.0 mass%, more preferably in the range of 1.0 to 8.0 mass% relative to the total solid content of the photosensitive colored resin composition. If the content is not less than the above-mentioned lower limit, the photocuring proceeds sufficiently, dissolution of the exposed portion during development is suppressed, and the solvent resistance becomes good, while if it is not more than the above-mentioned upper limit, the reduction in brightness of the obtained colored layer due to yellowing can be suppressed.

In addition, regarding the content ratio of the photopolymerizable compound and the photoinitiator used in the photosensitive colored resin composition, the total content ratio of the photoinitiators is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the photopolymerizable compound, in terms of suppressing line width shift and improving solvent resistance.

The ratio of the total mass of the photoinitiators to the total mass of the photoinitiators and the ultraviolet absorbers is preferably in the range of 80 to 98 mass%, more preferably in the range of 82 to 96 mass%. If the content is not less than the above-mentioned lower limit, the photocurability can be sufficiently ensured even in the presence of the ultraviolet absorber, while if it is not more than the above-mentioned upper limit, the effect of line width adjustment by the ultraviolet absorber is easily obtained.

[ solvent ]

The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with the components in the photosensitive colored resin composition and can dissolve or disperse them. The solvent may be used alone or in combination of 2 or more.

Specific examples of the solvent include, for example: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl Carbitol Acetate (BCA); diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, and the like; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as gamma-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 including toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are suitably used in terms of the solubility of other components. Among them, the solvent used in the present invention is preferably 1 or more selected from 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 3-methoxybutyl acetate in terms of solubility of other components and coating suitability.

In the photosensitive colored resin composition of the present invention, the content of the solvent may be appropriately set within a range in which a colored layer can be formed with good precision. The amount of the solvent may be usually 55 to 95% by mass, and preferably 65 to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. The solvent content falling within the above range can provide excellent coating properties.

[ dispersant ]

In the photosensitive colored resin composition of the present invention, the coloring material may be dispersed in a solvent by a dispersant. In the present invention, the dispersant may be appropriately selected from conventionally known dispersants. As the dispersant, for example, it is possible to use: cationic, anionic, nonionic, amphoteric, silicone, fluorine-based, and the like. Among the surfactants, polymeric dispersants are preferred in terms of being uniformly and finely dispersible.

Examples of the polymer dispersant include: (co) polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts or (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates or modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long chain polyaminoamide phosphates; polyethyleneimine derivatives (amides or their bases obtained by reaction of poly (lower alkylene imine) with polyesters containing free carboxyl groups); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with 1 or more compounds selected from 3 compounds selected from polyesters, polyamides, or co-condensates of esters and amides (polyesteramides) having free carboxyl groups), and the like.

When the polymer dispersant is a copolymer, it may be any of a block copolymer, a graft copolymer, and a random copolymer, and from the viewpoint of dispersibility, a block copolymer and a graft copolymer are preferable.

The dispersant is not particularly limited, and a dispersant having good dispersibility may be appropriately selected and used according to the type of colorant, and when the colorant of the triarylmethane-based dye is dispersed, an acidic dispersant is preferably used as the dispersant.

As the acidic dispersant used for the dispersion of the lake material, at least 1 selected from, for example, a polymer having a structural unit represented by the general formula (I) described below, and a carboxyl group-containing block copolymer can be suitably used.

When a pigment is further used as a coloring material and dispersed, at least 1 selected from the group consisting of an acidic or basic polymer dispersant and a urethane-based dispersant may be used depending on the type of pigment, and an acidic or basic polymer dispersant may be used. In the case of dispersing the alkali-treated pigment, an acidic dispersant is preferably used as the acidic polymer dispersant, and in the case of dispersing the acid-treated pigment, an alkaline dispersant is preferably used as the alkaline polymer dispersant.

As the basic dispersant, for example, at least 1 selected from a polymer containing a repeating unit having a tertiary amine, and a salt polymer obtained by forming a salt of at least a part of amino groups in a polymer containing a repeating unit having a tertiary amine with an organic acid compound can be suitably used.

The urethane dispersant is a compound having 1 or more urethane bonds (-NH-COO-) in 1 molecule. As the urethane-based dispersant, for example, a reaction product of a polyisocyanate having 2 or more isocyanate groups in 1 molecule and a polyester having hydroxyl groups at one or both terminals can be suitably used.

< Polymer having structural Unit represented by the general formula (I) >

The polymer having a structural unit represented by the following general formula (I) can be preferably used as a dispersant for a lake material of the above triarylmethane-based dye. When a polymer having a structural unit represented by the following general formula (I) is used as the acidic dispersant, the dispersibility and heat resistance of the lake material of the triarylmethane dye can be improved, and the color change of the lake material after heating can be suppressed. In addition, when a coloring material is used in combination with a pigment as a coloring material, a polymer having a structural unit represented by the following general formula (I) is used as a dispersant, whereby a colored layer having improved dispersibility and storage stability of the pigment, improved adhesion to a substrate, and improved uniformity of a coating film can be formed.

Since the polymer having a structural unit represented by the following general formula (I) is a polymer of an ethylenically unsaturated monomer, it is presumed that the heat resistance of the skeleton is higher than that of a polyether-based or polyester-based polymer, and that a plurality of acidic phosphorus compound groups (-P (=O) (-R) are present in the polymer ¹² ) (OH)) and salts thereof (-P (=o) (-R) ¹² )(O ^- X ⁺ ) The adsorption force to the surface of the pigment with microparticles is stronger. In addition, it is presumed that when the surface of the coloring material is covered with at least one of an acidic phosphorus compound group and a salt thereof, attack (hydrogen abstraction, substitution reaction, etc.) of active oxygen such as a peroxy radical on the coloring material skeleton of the coloring material is suppressed, and degradation (oxidative degradation) of the coloring material is suppressed.

[ chemical formula 10]

(in the general formula (I), L ¹¹ R is a direct bond or a divalent linking group ¹¹ Is a hydrogen atom or methyl group, R ¹² Is hydroxy, hydrocarbyl, - [ CH (R) ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ 、-[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ or-O-R ¹⁶ Represented monovalent radicals, 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-CH ₂ -C(R ²¹ )(R ²² )-CH ₂ -a monovalent group represented by OH.

R ¹³ And R is ¹⁴ Each independently is a hydrogen atom or a methyl group, R ¹⁵ Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO、-CO-CH＝CH ₂ 、-CO-C(CH ₃ )＝CH ₂ or-CH ₂ COOR ²³ Represented monovalent radicals, R ²³ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R is R ¹⁷ 、R ¹⁸ 、R ¹⁹ 、R ²⁰ 、R ²¹ And R is ²² Each independently is a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having 1 or more kinds selected from the group consisting of an ether bond and an ester bond, R ¹⁷ And R is ¹⁹ Can be bonded to each other to form a ring structure. In the case of forming the above-mentioned cyclic structure, the cyclic structure may further have a substituent R ²⁴ ，R ²⁴ Is a hydrocarbon group or a hydrocarbon group having 1 or more kinds selected from the group consisting of an ether bond and an ester bond. The above-mentioned hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 represents an integer of 1 to 18, y1 represents an integer of 1 to 5, and z1 represents an integer of 1 to 18. )

In the general formula (I), L ¹¹ Is a direct bond or a divalent linking group. Here, L ¹¹ The term "direct bond" means that the phosphorus atom is directly bonded to a carbon atom of the main chain skeleton without a linking group.

As L ¹¹ As long as the divalent linking group in (a) is capable ofThe carbon atom of the main chain skeleton is not particularly limited as long as it is bonded to a phosphorus atom. As L ¹¹ Examples of the divalent linking group in (b) include: linear, branched or cyclic alkylene; a linear, branched or cyclic alkylene group having a hydroxyl group; arylene, -CONH-yl, -COO-yl, -NHCOO-yl, ether (-O-yl), thioether (-S-yl), combinations thereof, and the like. In the present invention, the bond of the divalent linking group is oriented arbitrarily. That is, in the case where the divalent linking group comprises-CONH-, can be-CO as the carbon atom side of the main chain and-NH as the phosphorus atom side of the side chain, conversely, -NH is on the carbon atom side of the main chain and-CO is on the phosphorus atom side of the side chain.

Wherein L in the formula (I) is as follows in terms of dispersibility ¹¹ Divalent linking groups containing-CONH-groups, or-COO-groups are preferred.

For example, at L ¹¹ In the case of divalent linking groups comprising-COO-groups, L is preferred ¹¹ is-COO-L ^11’ -a radical (here, L ^11’ Is an alkylene group having 1 to 8 carbon atoms which may have a hydroxyl group, - [ CH (R) ^L11 )-CH(R ^L12 )-O] _x -, or- [ (CH) ₂ ) _y -O] _z -(CH ₂ ) _y -O-、-[CH(R ^L13 )] _w -O-，R ^L11 、R ^L12 And R is ^L13 Each independently is a hydrogen atom, a methyl group, or a hydroxyl group. x represents an integer of 1 to 18 inclusive, y represents an integer of 1 to 5 inclusive, z represents an integer of 1 to 18 inclusive, and w represents an integer of 1 to 18 inclusive. ).

L ^11’ The alkylene group having 1 to 8 carbon atoms may be any of straight-chain, branched, and cyclic alkylene groups, and for example, methylene, ethylene, trimethylene, propylene, butylene, pentylene, hexylene, octylene, and the like, and a part of hydrogen may be substituted with a hydroxyl group.

x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3.z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2. w is an integer of 1 to 18, preferably 1 to 4.

As L in the general formula (I) ¹¹ Examples of suitable examples of (a) 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.

As R ¹² Examples of the hydrocarbon group in (a) include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group.

The alkyl group having 1 to 18 carbon atoms may be any of linear, branched, and cyclic, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, and the like.

The alkenyl group having 2 or more and 18 or less carbon atoms may be any of linear, branched, and cyclic. Examples of such alkenyl groups include: vinyl, allyl, propenyl, and the like. The position of the double bond of the alkenyl group is not limited, and it is preferable that the double bond is at the end of the alkenyl group in terms of reactivity of the obtained polymer.

Examples of the aryl group include: phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, more preferably 6 or more and 12 or less.

Further, examples of the aralkyl group include: benzyl, phenethyl, naphthylmethyl, biphenylmethyl, and the like, and may further have a substituent. The number of carbons of the aralkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 14 or less.

The alkyl group and the alkenyl group may have a substituent, and examples of the substituent include: F. halogen atoms such as Cl and Br, nitro groups, and the like.

Examples of the substituent of the aromatic ring such as aryl or aralkyl include straight-chain or branched alkyl groups having 1 to 4 carbon atoms: alkenyl, nitro, halogen atoms, and the like.

The preferred carbon number does not include a substituent.

The above R ¹² Wherein x1 is the same as x, y1 is the same as y, and z1 is the same as z.

As R ¹⁵ ～R ²² Examples of the hydrocarbon group include those mentioned above as R ¹² The hydrocarbon groups are the same.

R ¹⁷ 、R ¹⁸ 、R ¹⁹ 、R ²⁰ 、R ²¹ And R is ²² More than 1 hydrocarbon group selected from the group consisting of an ether bond and an ester bond is a group represented by-R '-O-R', -R '- (c=o) -O-R', or-R '-O- (c=o) -R' (R 'and R' are hydrocarbon groups, or a group to which a hydrocarbon group is bonded through at least one of an ether bond and an ester bond). There may be 2 or more ether linkages and ester linkages in 1 group. Examples of the case where the hydrocarbon group is monovalent include: examples of the alkyl group, alkenyl group, aralkyl group, and aryl group include the case where the hydrocarbon group is divalent: alkylene, alkenylene, arylene, and combinations thereof.

At R ¹⁷ And R is R ¹⁹ When the ring structure is formed by bonding, the number of carbon atoms forming the ring structure is preferably 5 or more and 8 or less, more preferably 6, that is, a 6-membered ring, and preferably a cyclohexane ring.

Substituent R ²⁴ The hydrocarbon group of (C) or the hydrocarbon group having 1 or more selected from the group consisting of an ether bond and an ester bond may be the same as R ¹⁷ 、R ¹⁸ 、R ¹⁹ 、R ²⁰ 、R ²¹ And R is ²² The hydrocarbon groups are the same.

The above R is excellent in dispersibility and dispersion stability of the dispersed particles ¹² Preferably hydroxy, hydrocarbyl, - [ CH (R) ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ 、-[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ or-O-R ¹⁶ The monovalent group represented by the formula (I) is more preferably a hydroxyl group, a methyl group, an ethyl group, a vinyl group, an aryl or aralkyl group which may have a substituent, a vinyl group, an allyl group, - [ CH (R) ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ 、-[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ or-O-R ¹⁶ A monovalent group represented by, and R ¹³ And R is ¹⁴ Each independently is a hydrogen atom or methyl, R ¹⁵ for-CO-ch=ch ₂ or-CO-C (CH) ₃ )＝CH ₂ Wherein R is ¹² More preferably aryl, vinyl, methyl and hydroxy which may have a substituent.

In addition, R is in terms of improving alkali resistance ¹² Preferably a hydrocarbon group, - [ CH (R) ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ Or- [ (CH) ₂ ) _y1 -O] _z1 -R ¹⁵ Represented monovalent groups. In the case of a structure in which a carbon atom is directly bonded to a phosphorus atom, it is presumed that a resin layer excellent in alkali resistance can be formed because hydrolysis is difficult. Wherein R is excellent in alkali resistance and in dispersibility and dispersion stability of the dispersed particles ¹² Preferably methyl, ethyl, aryl or aralkyl which may have a substituent, vinyl, allyl, - [ CH (R) ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ Or- [ (CH) ₂ ) _y1 -O] _z1 -R ¹⁵ A monovalent group represented by, and R ¹³ And R is ¹⁴ Each independently is a hydrogen atom or methyl, R ¹⁵ for-CO-ch=ch ₂ or-CO-C (CH) ₃ )＝CH ₂ . Wherein R is in terms of dispersibility ¹² More preferably an aryl group which may have a substituent.

In the general formula (I), X represents a hydrogen atom or an organic cation. Organic cations refer to cations whose cationic moiety comprises carbon atoms. Examples of the organic cation include: imidazolium cations, pyridinium cations, amidinium cations, piperidinium cations, pyrrolidinium cations, ammonium cations such as tetraalkylammonium cations and trialkylammonium cations, sulfonium cations such as trialkylsulfonium cations, phosphonium cations such as tetraalkylphosphonium cations, and the like. Among them, in terms of dispersibility and alkali developability, a protonated nitrogen-containing organic cation is preferable.

Among them, in the case where the organic cation has an ethylenically unsaturated bond, it is preferable in terms of being able to impart curability.

The structural unit represented by the general formula (I) may be contained in the polymer singly or in combination of 1 or more than 2.

In the polymer, the structural unit represented by the general formula (I) may include two structural units of a structural unit in which X is a hydrogen atom and a structural unit in which X is an organic cation. When these two structural units are contained, the ratio of the number of structural units in which X is an organic cation to the total number of structural units represented by the general formula (I) is preferably 0 to 50 mol% as long as good dispersibility and dispersion stability are exhibited.

The method for synthesizing the polymer having the structural unit represented by the general formula (I) is not particularly limited, and for example, the polymer having the structural unit represented by the general formula (I) can be synthesized by referring to Japanese patent application laid-open No. 2017-2191. The polymer having a structural unit represented by the general formula (I) is preferably 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, and is a polymer in which at least a part of the acidic phosphorus compound group can form a salt.

In an embodiment of the present invention, the polymer having a structural unit represented by the general formula (I) preferably further has a solvent affinity site in terms of dispersibility. Among these polymers, a graft copolymer having a structural unit represented by the above 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 above general formula (I) and a structural unit represented by the following general formula (III) is preferable in terms of excellent dispersibility and storage stability and capable of forming a high-contrast coating film even after long-term storage.

[ chemical formula 11]

(in the general formula (II), L ²¹ Represents a direct bond or a divalent linking group, R ²⁵ Represents a hydrogen atom or a methyl group, and Polymer represents a Polymer chain having a structural unit represented by the following general formula (IV).

In the general formula (III), R ²⁶ Is a hydrogen atom or 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-O-R ^30’ or-O-CO-R ^30″ Represented monovalent radicals, R ²⁸ And R is ²⁹ Each independently is a hydrogen atom or a methyl group, R ³⁰ Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO or-CH ₂ COOR ³¹ Represented monovalent radicals, 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 Represented monovalent radicals, R ^30″ Is alkyl with carbon number of more than 1 and less than 18, R ³¹ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The above-mentioned hydrocarbon group may have a substituent.

x2 and x2' represent integers of 1 to 18 inclusive, y2 and y2' represent integers of 1 to 5 inclusive, and z2' represent integers of 1 to 18 inclusive. )

[ chemical formula 12]

(in the general formula (IV), R ³² Is a hydrogen atom or 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-O-R ³⁷ or-O-CO-R ³⁸ Represented monovalent radicals, R ³⁴ And R is ³³ Each independently is a hydrogen atom or a methyl group, R ³⁶ Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO or-CH ₂ COOR ³⁹ Represented monovalent radicals, 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 ) _y4 -O] _z4 -R ³⁶ Represented monovalent radicals, R ³⁸ Is alkyl with carbon number of more than 1 and less than 18, R ³⁹ The hydrocarbon group may have a substituent, and may be a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

n represents an integer of 5 to 200 inclusive. x3 and x4 represent integers of 1 to 18, y3 and y4 represent integers of 1 to 5, and z3 and z4 represent integers of 1 to 18. )

(graft copolymer)

Examples of the preferable graft copolymer as the acidic dispersant include graft copolymers having a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II).

In the above general formula (II), L ²¹ Is a direct bond or a divalent linking group. As L ²¹ The divalent linking group in (b) is not particularly limited as long as it is capable of linking a carbon atom derived from an ethylenically unsaturated bond to a polymer chain. As L ²¹ Examples of the divalent linking group include those mentioned above for L ¹¹ The divalent linking groups of (a) are the same.

In the above general formula (II), polymer represents a Polymer chain having a structural unit represented by the above general formula (IV).

In the general formula (IV), R is ³³ The hydrocarbon group in (a) is preferably 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. These are For example, R is as defined above ¹² The same groups.

R ³⁶ Preferably a hydrogen atom, or an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO or-CH ₂ COOR ³⁹ Represented monovalent radicals, R ³⁷ Preferably alkyl, aralkyl, aryl, or- [ CH (R) ³⁴ )-CH(R ³⁵ )-O] _x4 -R ³⁶ 、-[(CH ₂ ) _y4 -O] _z4 -R ³⁶ 、-[CO-(CH ₂ ) _y4 -O] _z4 -R ³⁶ Represented monovalent groups. R is R ³⁸ Is alkyl with carbon number of more than 1 and less than 18, R ³⁹ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

R is as described above ³⁶ And R is ³⁷ Examples of the "alkyl", "aralkyl" and "aryl" having 1 to 18 carbon atoms in the above-mentioned formula include those mentioned for R ¹² The same groups.

R is as described above ³⁸ And R is ³⁹ The alkyl group in (a) may be the same as R ¹² The same groups.

The above R ³⁶ 、R ³⁷ And R is ³⁹ In the case of a group having an aromatic ring, the aromatic ring may further have a substituent. Examples of the substituent include straight-chain, branched-chain, and cyclic alkyl groups having 1 to 5 carbon atoms: halogen atoms such as alkenyl, nitro, F, cl, br, etc.

The preferred carbon number does not include a substituent.

The above R ³³ And R is ³⁷ Wherein 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.

Further, R is as described above ³³ 、R ³⁶ 、R ³⁷ 、R ³⁸ And R is ³⁹ The graft copolymer may be further substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group, within a range not to impair the dispersibility or the like of the graft copolymer. In addition, these can be synthesizedAfter the graft copolymer having a substituent, the graft copolymer is reacted with a compound having a functional group reactive with the substituent and a polymerizable group, thereby adding the polymerizable group. For example, a polymerizable group may be added by reacting a graft copolymer having a carboxyl group with glycidyl (meth) acrylate or by reacting a graft copolymer having an isocyanate group with hydroxyethyl (meth) acrylate.

Among the above structural units, the polymer chain having the structural unit represented by the general formula (IV) preferably has a structural unit derived from: methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, styrene, alpha-methylstyrene, vinylcyclohexane, and the like. However, these are not limited thereto.

In the embodiment of the present invention, R is as the above ³³ And R is ³⁷ Particularly, those having excellent solubility with the organic solvent described below are preferably used, and may be appropriately selected according to the organic solvent used for the colorant dispersion. Specifically, for example, when an ether alcohol acetate-based, ether-based, ester-based or other organic solvent which is generally used as an organic solvent for the colorant dispersion is used as the organic solvent, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl or the like is preferable.

Here, R is set in the above manner ³³ And R is ³⁷ The reason for (2) is that: comprises R as described above ³³ And R is ³⁷ The structural unit (c) has solubility in the organic solvent, and the acid phosphorus compound group of the monomer and the salt thereof have high adsorptivity to particles such as coloring material, so that the dispersibility and stability of the particles such as coloring material can be particularly excellent.

The weight average molecular weight of the Polymer chain in the Polymer is preferably in the range of 500 to 15000, more preferably in the range of 1000 to 8000. When the content is within the above range, it is possible to suppress an increase in the time required for dispersing particles such as a coloring material due to the steric effect while maintaining a sufficient steric repulsion effect as a dispersant.

In addition, as a standard, it is preferable that the solubility of the Polymer chain in the Polymer with respect to the organic solvent used in combination is 50 (g/100 g solvent) or more at 23 ℃.

The polymer chain may be a homopolymer or a copolymer. The polymer chain contained in the structural unit represented by the general formula (II) may be 1 kind alone or 2 or more kinds may be mixed in the graft copolymer.

The structural units represented by the general formula (I) are preferably contained in a proportion of 3 to 80 mass%, more preferably 10 to 70 mass%, still more preferably 20 to 60 mass%, based on the total of all the structural units of the graft copolymer. When the total content of the structural units represented by the general formula (I) in the graft copolymer falls within the above range, the proportion of the affinity sites for the particles in the graft copolymer becomes appropriate, and the decrease in solubility in the organic solvent can be suppressed, so that the adsorption of the particles such as the coloring material becomes good, and excellent dispersibility and dispersion stability can be obtained. In addition, the acidic phosphorus compound group of the graft copolymer can be stably localized around the colorant, so that 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 in an amount of 20 mass% or more and 97 mass% or less, more preferably 25 mass% or more and 95 mass% or less, and still more preferably 40 mass% or more and 90 mass% or less, relative to the total structural units of the graft copolymer.

In the present invention, the content of each structural unit in the copolymer is calculated from the amount added in the synthesis of the copolymer.

The weight average molecular weight of the graft copolymer is preferably in the range of 1000 to 500000, more preferably in the range of 3000 to 400000, and even more preferably in the range of 5000 to 300000. When the content is within the above range, particles such as a coloring material can be uniformly dispersed.

The graft copolymer used in the embodiment of the present invention may further have other structural units in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). For example, an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer or the like from which the structural unit represented by the above general formula (I) is derived may be appropriately selected and copolymerized to introduce other structural units.

(Block copolymer)

Examples of the block copolymer which is preferable as the acidic dispersant include a block copolymer having a block portion containing a structural unit represented by the above general formula (I) and a block portion containing a structural unit represented by the above general formula (III).

In the block copolymer, the block portion containing the structural units represented by the general formula (I) preferably contains 3 or more structural units represented by the general formula (I) in total. Among them, 3 or more and 200 or less are preferable, 3 or more and 50 or less are more preferable, and 3 or more and 30 or less are still more preferable in terms of improving dispersibility and improving heat resistance.

The structural unit represented by the general formula (I) may be 1 or 2 or more structural units as long as it functions as a coloring material affinity site. In the case where 2 or more structural units are contained, 2 or more structural units may be arranged randomly in a block portion containing the structural units represented by the above general formula (I).

In the block copolymer, the total content of the structural units represented by the general formula (I) is preferably 5 mass% or more and 80 mass% or less, more preferably 10 mass% or more and 70 mass% or less, and still more preferably 20 mass% or more and 60 mass% or less, with respect to the total structural units of the block copolymer.

When the ratio is within the above range, the proportion of the affinity site with the particle in the block copolymer becomes appropriate, and the decrease in solubility in the organic solvent can be suppressed, so that the adsorptivity to the particle such as the coloring material becomes good, and excellent dispersibility and dispersion stability can be obtained. In addition, the acidic phosphorus compound group of the block copolymer can be stably present around the coloring material, so that a color filter excellent in heat resistance and contrast can be obtained.

The block copolymer has a block containing a structural unit represented by the general formula (III), and thus, the solvent affinity is good, the dispersibility and dispersion stability of the colorant are good, the heat resistance is also good, and the resistance to N-methylpyrrolidone (NMP) (NMP resistance) is excellent.

In the 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-O-R ^30’ or-O-CO-R ^30″ Represented monovalent groups.

As R ²⁷ The hydrocarbon group in (2) may be the same as R ¹² The groups represented are the same.

In addition, R is as described above ³⁰ Is hydrogen atom, alkyl, -CHO, -CH ₂ CHO or-CH ₂ COOR ³¹ Represented monovalent radicals, 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 Represented monovalent radicals, R ^30″ Is alkyl with more than 1 and less than 18 carbon atoms, R ³¹ The hydrocarbon group may have a substituent, and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

R is as described above ³⁰ The hydrocarbon group in (2) may be set as the same as R ¹² The groups represented are the same.

The above R ²⁷ And R is ^30’ Wherein x2 and x2' are the same as x, y2 and y2' are the same as y, and z2' are the same as z.

R in the structural unit represented by the above general formula (III) ²⁷ May be the same as or different from each other.

As R as above ²⁷ And R is ^30’ Among them, those excellent in solubility with the solvents described below are preferably used, and examples thereof include those described above as R ³³ And R is ³⁷ The same ones.

In addition, R in the above general formula (IV) ²⁷ 、R ³⁰ 、R ^30’ 、R ^30″ And R is ³¹ The substituent may be substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group within a range that does not interfere with the dispersibility of the block copolymer, or may be added by reacting the block copolymer with a compound having the substituent after synthesizing the block copolymer. Further, after the block copolymer having these substituents is synthesized, it may be reacted with a compound having a functional group which reacts with the substituent and a polymerizable group, thereby adding a polymerizable group. For example, a block copolymer having a glycidyl group may be reacted with (meth) acrylic acid, or a block copolymer having an isocyanate group may be reacted with hydroxyethyl (meth) acrylate, thereby adding a polymerizable group.

The number of the structural units constituting the block portion including the structural unit represented by the general formula (III) is not particularly limited, and is preferably 10 or more and 200 or less, more preferably 20 or more and 100 or less, still more preferably 30 or more and 80 or less, in terms of effectively functioning the solvent affinity site and the colorant affinity site and improving the dispersibility of the colorant dispersion.

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

The block portion including the structural unit represented by the general formula (III) may be selected so as to function as a solvent affinity site, and the structural unit represented by the general formula (III) may include 1 or 2 or more structural units. In the embodiment of the present invention, in the case where the structural unit represented by the general formula (III) contains 2 or more structural units, the 2 or more structural units may be arranged randomly in the block portion containing the structural unit represented by the general formula (III).

In the block copolymer used as the dispersant, the ratio m/n of the number m of the structural units of the block portion including the structural unit represented by the general formula (I) to the number n of the structural units of the block portion including the structural unit represented by the general formula (III) is preferably in the range of 0.01 to 1, more preferably in the range of 0.1 to 0.7 in terms of dispersibility and dispersion stability of the colorant.

The order of bonding of the block copolymer is not particularly limited as long as the block copolymer has a block containing the structural unit represented by the general formula (I) and a block containing the structural unit represented by the general formula (III) and can stably disperse the coloring material, and it is preferable that the block containing the structural unit represented by the general formula (I) is bonded to only one end of the block copolymer in terms of excellent interaction with the coloring material and effective inhibition of aggregation of the dispersing agent with each other.

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, and still more preferably 6000 or more and 300000 or less, in view of improving dispersibility and excellent heat resistance.

The acid value of the polymer having the structural unit represented by the general formula (I) is preferably 20mgKOH/g or more, more preferably 30mgKOH/g or more, and still more preferably 40mgKOH/g or more, in terms of dispersibility and storage stability of the colorant. On the other hand, in view of excellent developability, the acid value of the polymer having the structural unit represented by the above general formula (I) is preferably 150mgKOH/g or less, more preferably 120mgKOH/g or less, and still more preferably 100mgKOH/g or less.

In the present invention, the acid value means the mg number of potassium hydroxide required for neutralizing the acid component contained in sample 1g, and may be determined in accordance with JIS K0070: 1992.

On the other hand, the above-mentioned carboxyl group-containing block copolymer may include a block copolymer containing an a block containing structural units derived from a carboxyl group-containing ethylenically unsaturated monomer such as (meth) acrylic acid and a B block containing structural units derived from an alkyl (meth) acrylate. In the carboxyl group-containing block copolymer, the B block containing a structural unit derived from an alkyl (meth) acrylate may be the same as the block portion containing a structural unit represented by the above general formula (III) of the block copolymer having a structural unit represented by the above general formula (I).

The content (mol%) of each structural unit in the copolymer in the dispersant can be determined from the amount of the raw material added at the time of production, and can be measured by using an analytical device such as NMR. The structure of the dispersant can be measured by NMR, various mass analyses, or the like. The dispersant may be decomposed by thermal decomposition or the like as needed, and the decomposed product thus obtained may be obtained by using high performance liquid chromatography, gas chromatography mass spectrometry, NMR, elemental analysis, XPS/ESCA (X-ray photoelectron spectroscopy/Electron Spectroscopy for Chemical Analysis, X-ray photoelectron spectroscopy/chemical analysis electron spectrum), TOF-SIMS (time of flight secondary ion mass spectrometry, time-of-flight secondary ion mass spectrometer) or the like.

In the present invention, the content of the dispersant may be appropriately selected depending on the type of the coloring material to be used, and further depending on the solid content concentration in the photosensitive colored resin composition described below.

The content of the dispersant is preferably in the range of 2 to 30 mass%, more preferably in the range of 3 to 25 mass%, relative to the total solid content of the photosensitive colored resin composition. When the content is not less than 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 further excellent. In addition, if the upper limit value is less than or equal to the above, the development property becomes good.

[ antioxidant ]

The photosensitive colored resin composition of the present invention preferably further contains at least 1 of an antioxidant and a latent antioxidant in terms of improving heat resistance and improving brightness.

The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known antioxidants. Specific examples of the antioxidant include, for example: hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like are preferably used in terms of the ability to form fine line patterns as in the design of line width mask line widths, and in terms of heat resistance.

The latent antioxidant used in the present invention is a compound having a protecting group which can be detached by heating, and the compound exhibits an antioxidant function by detachment of the protecting group. Among them, a latent antioxidant in which the protecting group is easily detached by heating at 150℃or higher is preferable. Examples of the latent antioxidant used in the present invention include latent antioxidants described in International publication No. 2014/021023 and International publication No. 2017/170263. Among them, a latent antioxidant in which a phenolic hydroxyl group of a hindered phenolic antioxidant is protected with a protecting group is exemplified as a suitable latent antioxidant, and more specifically, a structure obtained by substituting hydrogen of a phenolic hydroxyl group of a hindered phenolic antioxidant with a urethane protecting group such as t-butoxycarbonyl group is exemplified as a suitable latent antioxidant.

Examples of the hindered phenol-based antioxidant include: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010, manufactured by BASF corporation), 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 '-methylenebis (6-tert-butyl-4-methylphenol) (trade name: sumizer MDP-S, manufactured by Sumitomo chemical corporation), 6' -thiobis (2-tert-butyl-4-methylphenol) (trade name: irganox 1081, manufactured by BASF), diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: irgamod 195, manufactured by BASF), and the like. Among them, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX1010, manufactured by BASF corporation) is preferable in terms of heat resistance and light resistance.

The content of the antioxidant is preferably in the range of 0.1 to 10.0 mass%, more preferably in the range of 0.5 to 5.0 mass%, relative to the total solid content of the photosensitive colored resin composition. If the lower limit is not less than the above-mentioned lower limit, the heat resistance and the brightness are improved. On the other hand, if the upper limit value is less than or equal to the above, the colored resin composition of the present invention can be made into a photosensitive resin composition having high sensitivity.

[ thiol Compound ]

The photosensitive colored resin composition of the present invention preferably further contains a thiol compound in terms of a fine line width and an improvement in the effect of suppressing film thickness variation before and after development.

Since the thiol compound undergoes no polymerization inhibition by oxygen due to the thiol reaction, the surface curability is excellent and the development residual film rate is improved. The thiol compound has an effect of thickening the line width, but the use of the ultraviolet absorber in combination has a synergistic effect of both reducing the line width and improving the development residual film.

Examples of the thiol compound include a monofunctional thiol compound having 1 thiol group and a multifunctional thiol compound having 2 or more thiol groups. The use of a polyfunctional thiol is more preferable in terms of a fine line width and an improvement in the effect of suppressing the film thickness change before and after development.

Examples of the monofunctional thiol compound include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and the like.

Examples of the polyfunctional thiol compound include: 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and tetraethyleneglycol bis (3-mercaptopropionate), and the like.

The thiol compound may be used alone or in combination of 2 or more, and pentaerythritol tetrakis (3-mercaptobutyrate) is preferable in terms of a fine line width and an improvement in the effect of suppressing the film thickness change before and after development.

The content of the thiol compound is usually in the range of 0.5 to 10 mass%, preferably 1 to 5 mass% relative to the total solid content of the photosensitive colored resin composition. When the thickness is equal to or larger than the lower limit, the effect of suppressing the film thickness variation before and after development is excellent. On the other hand, when the ratio is not more than the upper limit, the photocurable colored resin composition of the present invention can be easily formed into a colored layer having excellent developability and suppressed line width deviation.

[ other Components ]

The photosensitive colored resin composition of the present invention may contain various additives as required. Examples of the additive include: polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, adhesion promoters, and the like.

Specific examples of the surfactant and the plasticizer include those described in Japanese patent application laid-open No. 2013-029832.

< method for producing photosensitive colored resin composition >

The method for producing the photosensitive colored resin composition of the present invention can be produced by mixing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, a solvent, and optionally a dispersant or the like or various additive components by a known mixing method.

Examples of the method for producing the resin composition include: (1) A method comprising preparing a colorant dispersion by adding a colorant and a dispersant to a solvent, and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various optional additives into the dispersion; (2) A method of simultaneously adding and mixing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various optional additives to a solvent; (3) A method in which an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and optionally a dispersant or various additive components are added to a solvent, and mixed, and then a colorant is added to disperse the mixture; (4) A method in which a colorant dispersion is prepared by adding a colorant, a dispersant, and an alkali-soluble resin to a solvent, and the dispersion is further mixed with an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various optional additives; etc.

Among these methods, the methods (1) and (4) described above are preferable in that aggregation of the coloring material can be effectively prevented and uniformly dispersed.

The method for preparing the colorant dispersion may be appropriately selected from conventionally known dispersion methods.

As a dispersing machine for carrying out the dispersing treatment, there can be mentioned: roller mills such as a double-roller mill and a three-roller mill; ball mills such as a ball mill and a vibration ball mill; coating regulator, continuous disk bead mill, continuous annular bead mill, etc. The bead diameter used in the dispersion conditions of the bead mill is preferably 0.03mm to 2.00mm, more preferably 0.10mm to 1.0mm.

[ use ]

The photosensitive colored resin composition of the present invention contains a lake material of a triarylmethane dye, and can form a colored layer having improved brightness, a fine line width, and suppressed film thickness variation before and after development, and thus can be suitably used for color filter applications.

[ cured product of photosensitive colored resin composition ]

The cured product of the present invention is a cured product of the photosensitive colored resin composition of the present invention.

The cured product of the present invention can be obtained by forming a coating film of the photosensitive colored resin composition of the present invention, drying the coating film, and then exposing and developing the dried coating film. As a method of forming a coating film, exposing, and developing, for example, the same method as used in forming a colored layer provided in the color filter of the present invention described below can be used.

The cured product of the present invention is a coloring layer which contains a lake material of a triarylmethane dye, has improved brightness and a small line width, and is suppressed in film thickness variation before and after development, and can be suitably used as a coloring layer of a color filter.

III color filter

The color filter of the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, at least one of the colored layers being a cured product of the photosensitive colored resin composition of the present invention.

Such a color filter according to the present invention will be described with reference to the accompanying drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present invention. According to fig. 1, a color filter 10 of the present invention includes a substrate 1, a light shielding portion 2, and a coloring layer 3.

[ coloring layer ]

At least one of the colored layers used in the color filter of the present invention is a colored layer of a cured product of the photosensitive colored resin composition of the present invention.

The colored layer is generally formed in an opening of a light shielding portion on a substrate described below, and generally includes a colored pattern of 3 colors or more.

The arrangement of the colored layers is not particularly limited, and may be, for example, a typical arrangement such as a stripe type, a mosaic type, a delta type, or a 4-pixel arrangement type. The width, area, etc. of the colored layer may be arbitrarily set.

The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the photosensitive colored resin composition, and the like, and is preferably in the range of 1 to 5 μm in general.

The colored layer can be formed by, for example, the following method.

First, the photosensitive colored resin composition of the present invention described above is coated on a substrate described below by a coating method such as spray coating, dip coating, bar coating, roll coating, spin coating, die coating, or the like, to form a wet coating film. Among them, spin coating and die coating can be suitably used.

Next, the wet coating film is dried using a heating plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, whereby an alkali-soluble resin, a polyfunctional monomer, or the like is subjected to photopolymerization to produce a cured coating film. Examples of the light source used for exposure include: ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and electron beams. The exposure amount can be appropriately adjusted according to the light source used, the thickness of the coating film, and the like.

In addition, after the exposure, a heat treatment may be performed in order to promote the polymerization reaction. The heating conditions may be appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.

Then, the unexposed portions are dissolved and removed by development treatment using a developer, whereby a coating film is formed in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. A surfactant or the like may be added to the alkali solution in an appropriate amount. In addition, the development method may employ a usual method.

After the development treatment, the development solution is usually washed, and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected according to the application of the coating film.

[ light-shielding portion ]

The light shielding portion in the color filter of the present invention is formed in a pattern on a substrate described below, and may be the same as a light shielding portion used as a light shielding portion in a normal color filter.

The pattern shape of the light shielding portion is not particularly limited, and examples thereof include: stripe, matrix, etc. The light shielding portion may be a metal thin film of chromium or the like obtained 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, and organic pigments in the resin binder. In the case of the resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.

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 about 0.5 to 2 μm in the case of a light shielding portion obtained by dispersing or dissolving a black pigment in a binder resin.

[ substrate ]

As the substrate, a transparent substrate, a silicon substrate, a substrate having an aluminum, silver/copper/palladium alloy film or the like formed thereon, which will be described later, can be used. Other color filter layers, resin layers, transistors such as TFTs (thin-film transistors), circuits, and the like may be formed on these substrates.

The transparent substrate used in the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used in a normal color filter can be used. Specifically, there may be mentioned: transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plate, or transparent flexible materials such as transparent resin film, optical resin plate, and flexible glass.

The thickness of the transparent substrate is not particularly limited, and for example, a transparent substrate of about 100 μm to 1mm can be used according to the application of the color filter of the present invention.

In addition to the substrate, the light shielding portion, and the coloring layer, the color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, and the like.

IV. display device

The display device of the present invention is characterized by having the color filter of the present invention described above. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from conventionally known display devices, and examples thereof include a liquid crystal display device, an organic light emitting display device, and the like.

[ liquid Crystal display device ]

As a liquid crystal display device of the present invention, for example, a liquid crystal display device having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate is mentioned.

Such a liquid crystal display device of the present invention will be described with reference to the accompanying 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, the liquid crystal display device 40 of the present invention has: a color filter 10, a counter substrate 20 including a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and may be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used for a liquid crystal display device may be employed. Examples of such a driving method include: TN (Twisted Nematic) mode, IPS (In-Plane Switching) mode, OCB (optically compensated bend, optically compensatory bend) mode, MVA (Multi-Domain Vertical Alignment ) mode, and the like. Any of these may be suitably used in the present invention.

The counter substrate may 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 anisotropies, and mixtures thereof can be used according to the driving method or the like of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method which is 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 cooled slowly to normal temperature, whereby the enclosed liquid crystal can be aligned.

[ organic light-emitting display device ]

As the organic light emitting display device of the present invention, for example, an organic light emitting display device having the above-described color filter of the present invention and an organic light emitter can be cited.

Such an organic light emitting display device of the present invention will be described with reference to the accompanying 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 emitter 80. The organic protective layer 50 and the inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

Examples of the lamination method of the organic light-emitting body 80 include: a method of sequentially forming 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 on the upper surface of the color filter; or a method of bonding the organic light-emitting element 80 formed on another substrate to the inorganic oxide film 60. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light-emitting body 80, and other structures can be appropriately used as known ones. The organic light emitting display device 100 manufactured in the above-described manner may be applied to, for example, a passive driving type organic EL display or an active driving 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 be a configuration generally known as an organic light-emitting display device using a color filter.

Examples

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these descriptions.

The mass average molecular weight (Mw) of the copolymer before salt formation can be determined as a standard polystyrene equivalent by GPC (gel permeation chromatography) according to the measurement method described in the above description of the present invention.

[ solubility test of ultraviolet absorber in PGMEA ]

For the solubility test of the ultraviolet absorber in PGMEA, 0.5g of each ultraviolet absorber was measured at 25 ℃, added to 9.5g of PGMEA, stirred with a stirrer for 1 hour, and then visually evaluated.

O: no residue of dissolution

X: has dissolved residues

[ measurement of transmittance at 365nm wavelength of ultraviolet absorber ]

Regarding the transmittance of the ultraviolet light absorber at 365nm, a 0.002 mass% propylene glycol monomethyl ether acetate solution of each ultraviolet light absorber was prepared, and the 0.002 mass% propylene glycol monomethyl ether acetate solution was measured using an ultraviolet-visible near infrared spectrophotometer (for example, V-7100 of japan light splitting co.).

Table 1 shows the results of measurement of transmittance at 365nm wavelength of the ultraviolet absorber.

TABLE 1

Table 1.

Ultraviolet absorber	PGMEA solubility	Transmittance at 365nm
			Ultraviolet absorber U1	○	38.8％
Ultraviolet absorber U2	○	77.9％
			Ultraviolet absorber U3	○	14.9％
Ultraviolet absorber U4	○	16.0％
			Ultraviolet absorber U5	○	29.4％
Ultraviolet absorber U6	○	34.5％
			Ultraviolet absorber U7	○	65.8％
Ultraviolet absorber U8	○	46.9％
			Ultraviolet absorber U9	○	30.2％
Ultraviolet absorber U10	○	16.5％
			Ultraviolet absorber U11	○	39.1％

Ultraviolet absorber (U1): kemisorb71, manufactured by Chemipro Kasei

Ultraviolet absorber (U2): kemisorb12, manufactured by Chemipro Kasei

Ultraviolet absorber (U3): kemisorb111, manufactured by Chemipro Kasei

Ultraviolet absorber (U4): kemisorb73, manufactured by Chemipro Kasei

Ultraviolet absorber (U5): tinuvinPS, BASF manufacture

Ultraviolet absorber (U6): tinuvin928 manufactured by BASF

Ultraviolet absorber (U7): tinuvin405 manufactured by BASF

Ultraviolet absorber (U8): tinuvin479 manufactured by BASF

Ultraviolet absorber (U9): tinuvin329 manufactured by BASF

Ultraviolet absorber (U10): tinuvin477 manufactured by BASF

Ultraviolet absorber (U11): RUVA-93, chemical manufacture of tsukamurella

Synthesis example 1 Synthesis of lake 1

(1) Synthesis of intermediate 1

Referring to the process for producing intermediate A-2, intermediate B-1 and compound 1-3 described in Japanese patent application laid-open No. 2018-3013, intermediate 1 (yield 87%) represented by the following chemical formula (a) was obtained.

The obtained compound was confirmed to be the target compound according to the analysis results described below.

MS (ESI) (m/z): 677 (+), divalent

Elemental analysis values: CHN (Carbon-Hydrogen-Nitrogen, carbon Nitrogen) found (81.81%, 7.31%, 5.85%); theoretical value (81.77%, 7.36%, 5.90%)

[ chemical formula 13]

Chemical formula (a)

(2) Synthesis of lake 1

2.59g (0.76 mmol) of 12 tungsten phosphoric acid-n hydrate produced by Kanto chemical was dissolved in a mixture of 40mL of methanol and 40mL of water under heating, and 1.6g (1.19 mmol) of the intermediate 1 was added thereto and stirred for 1 hour. The precipitate was obtained by filtration and washed with water. The obtained precipitate was dried under reduced pressure, whereby lake material 1 represented by the following chemical formula (b) was obtained (yield 95%).

· ³¹ P NMR(d-dmso、ppm)δ-15.15

•MS(MALDI)(m/z)：1355(M ⁺ )、2879(MH ₂ ^- )

Elemental analysis values: CHN observed values (35.55%, 3.24%, 2.61%); theoretical value (35.61%, 3.20%, 2.57%)

Fluorescent X-ray analysis: moW measured ratio (0%, 100%); theoretical value (0%, 100%)

[ chemical formula 14]

Chemical formula (b)

Synthesis example 2 Synthesis of lake 2

(1)K ₆ (P ₂ MoW ₁₇ O ₆₂ ) Is prepared from

NaWO is used ₄ ·2H ₂ 44.0g of O (manufactured by Wako pure chemical industries, ltd.) and Na ₂ MoO ₄ ·2H ₂ 1.90g of O (manufactured by Kanto chemical Co., ltd.) was dissolved in 230g of purified water. 85% phosphoric acid was added to the solution with stirring using a dropping funnel64.9g. The obtained solution was heated under reflux for 8 hours. The reaction mixture was cooled to room temperature, and 1 drop of bromine water was added thereto, followed by stirring and adding 45g of potassium chloride thereto. After stirring for a further 1 hour, the precipitate was isolated by filtration. The obtained solid was dried at 90℃to thereby obtain 29.4g of K ₆ (P ₂ MoW ₁₇ O ₆₂ )。

(2) Synthesis of lake 2

5.30g of C.I. basic blue 7 (BB 7) (manufactured by Tokyo chemical Co., ltd.) was poured into 350ml of purified water, and stirred and dissolved at 40℃to prepare a BB7 solution. Alternatively, K prepared in the above (1) is added ₆ (P ₂ MoW ₁₇ O ₆₂ ) 10.0g was dissolved in 40ml of purified water. Adding K into BB7 solution ₆ (P ₂ MoW ₁₇ O ₆₂ ) The solution was stirred directly at 40℃for 1 hour. Then, the internal temperature was raised to 80℃and stirred for 1 hour to effect the precipitation. After cooling, filtration was carried out and the mixture was washed 3 times with 300ml of purified water. The obtained solid was dried at 90℃to thereby obtain 10.4g of lake 2 as a lake of triarylmethane-based dye and polyacid having an average primary particle diameter of 40nm as a black-blue solid.

( Synthesis example 3: synthesis of acidic dispersant A1 (Polymer having at least 1 selected from structural units represented by the above general formula (I)) )

(1) Synthesis of macromer MM-1

80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was charged into a reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was stirred under a nitrogen flow to heat the mixture to 90 ℃. A mixed solution of 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 parts by mass of α, α' -Azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the mixture was reacted for 3 hours. Then, the nitrogen flow was stopped, the reaction solution was cooled to 80 ℃, 8.74 parts by mass of Karenz MO1 (manufactured by sho and electrician) was added, 0.125 part by mass of dibutyltin dilaurate, 0.125 part by mass of p-methoxyphenol, and 10 parts by mass of PGMEA, and stirred for 3 hours, thereby obtaining a 49.5 mass% solution of macromer MM-1. GPC measurement of the obtained macromonomer MM-1 revealed a mass average molecular weight (Mw) 4010, a number average molecular weight (Mn) 1910, and a molecular weight distribution (Mw/Mn) of 2.10.

(2) Synthesis of graft copolymer A1

85.0 parts by mass of PGMEA was charged into a reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the temperature was raised to 90℃while stirring under a nitrogen flow. The mixed solution of 67.34 parts by mass (solid content 33.33 parts by mass) of the above-mentioned macromonomer MM-1 solution, 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecyl mercaptan, 25.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, the mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and further cured at the same temperature for 1 hour, thereby obtaining a 25.0 mass% solution of the graft copolymer A1. The GPC measurement of the obtained graft copolymer A1 revealed a mass average molecular weight (Mw) 10570, a number average molecular weight (Mn) 4370 and a molecular weight distribution (Mw/Mn) of 2.42.

(3) Production of Polymer (acid dispersant A1) having at least 1 selected from structural units represented by the above general formula (I)

27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA", manufactured by Nissan chemical Co., ltd.) were charged into a reactor equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated to 90℃while stirring the mixture under a nitrogen flow.

100.0 parts by mass of the graft copolymer A1 was added dropwise over 30 minutes, and heated and stirred for 2 hours, whereby a polymer (acid dispersant A1) solution (solid content 25.0% by mass) having at least 1 kind of structural unit selected from the structural units represented by the above general formula (I) was obtained. By determination of the acid number and ¹ the H-NMR measurement confirmed the progress of the esterification reaction between GMA and PPA of the obtained acidic dispersant A1 (confirmed the disappearance of the peak derived from the epoxy group). Acid value of the obtained acid dispersant A1Is 98mgKOH/g.

( Synthesis example 4: : synthesis of acidic dispersant A2 (Block copolymer containing A Block containing structural units derived from carboxyl-containing ethylenically unsaturated monomer and B Block containing structural units derived from alkyl (meth) acrylate) )

Referring to example 1 described in International publication No. 2016/132863, a triblock copolymer having a block of 20 parts by mass of Methyl Methacrylate (MMA), 40 parts by mass of n-Butyl Methacrylate (BMA), 20 parts by mass of methacrylic acid (MAA), 20 parts by mass of BMA, and a block of 20 parts by mass of MMA and 40 parts by mass of BMA was synthesized. The weight average molecular weight (Mw) of the obtained block copolymer was 11000, the molecular weight distribution (Mw/Mn) was 1.50, and the acid value was 130mgKOH/g.

Synthesis example 5 Synthesis of latent antioxidant

0.01mol of a phenol compound represented by the following chemical formula (c), 0.05mol of di-t-butyl dicarbonate and 30g of pyridine were mixed, and 0.025mol of 4-dimethylaminopyridine was added thereto under a nitrogen atmosphere at room temperature, followed by stirring at 60℃for 3 hours. After cooling to room temperature, the reaction solution was poured into 150g of ion-exchanged water, and 200g of chloroform was added thereto to separate oil from water. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off, whereby 100g of methanol was added to the residue to crystallize the residue. The white powdery crystals obtained were dried under reduced pressure at 60℃for 3 hours to obtain a latent antioxidant (compound A). The structure of the obtained latent antioxidant was confirmed by IR and NMR.

[ chemical formula 15]

Chemical formula (c)

Comparative Synthesis example 1 Synthesis of triarylmethane dye 1

In the same manner as in dye A described in example 1 of Japanese patent application laid-open No. 2011-133844, triarylmethane dye 1 was synthesized.

First, as described in example 1 of Japanese patent application laid-open No. 2011-133844, (tosyl) trifluoromethanesulfonyl imide salt was synthesized.

Then, 5g of C.I. basic blue 7 (N- [4- [ [4- (diethylamino) phenyl ] [4- (ethylamino) -1-naphthyl ] methylene ] -2, 5-cyclohexadiene-1-ylidene ] -N-ethylethanaminium chloride) (manufactured by Tokyo formation) was dissolved in 30mL of methanol, and 3.93g of (tosyl) trifluoromethanesulfonyl imide triethylamine salt was added thereto with stirring, followed by stirring at room temperature for 1 hour. The methanol in the solution was concentrated by an evaporator, 100mL of water was added thereto, and the precipitate was obtained by filtration and washed with water. The cake was dried under reduced pressure to obtain triarylmethane dye 1.

Preparation example 1 preparation of alkali-soluble resin P1

To the polymerization vessel, 300 parts by mass of PGMEA was added, and after the temperature was raised to 100 ℃ under a nitrogen atmosphere, 67.6 parts by mass of benzyl methacrylate (BzMA), 67.6 parts by mass of MMA, 36.4 parts by mass of methacrylic acid (MAA), 3 parts by mass of PERBUTYLO (manufactured by daily oil), 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 at 100℃and after 2 hours from the completion of the dropping of the above-mentioned mixture for forming a main chain, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor was added to stop the polymerization.

Then, 28.4 parts by mass of Glycidyl Methacrylate (GMA) as an epoxy group-containing compound was added while blowing air, the temperature was raised to 110 ℃, 0.8 parts by mass of triethylamine was added, and the addition reaction was performed at 110 ℃ for 15 hours to obtain an alkali-soluble resin P1 solution (weight average molecular weight (Mw) 9000, acid value 75mgKOH/g, solid content 40 mass%).

In the method for measuring the weight average molecular weight, polystyrene was used as a standard substance, THF (tetrahydrofuran) was used as an eluent, and the weight average molecular weight was measured by a Shodex GPC system-21H (Shodex GPC System-21H). The method for measuring the acid value was carried out based on JIS K0070.

Example 1 production of photosensitive colored resin composition 1

(1) Preparation of colorant Dispersion 1

A225 mL mayonnaise bottle was charged with 61 parts by mass of PGMEA, 5 parts by mass of the alkali-soluble resin P1 solution of preparation example 1 (40% by mass of the solid content), and 24 parts by mass of the acid dispersant A1 solution of Synthesis example 3 (25.0% by mass of the solid content), and stirred.

10 parts by mass of the triarylmethane-based toner 1 of Synthesis example 1 and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were charged therein, and the mixture was subjected to shaking by a paint shaker (manufactured by shallow Tian Tiegong Co.) for 1 hour as pre-crushing, followed by changing to 200 parts of zirconia beads having a particle diameter of 0.1mm, and then subjected to dispersion by the paint shaker for 4 hours as main crushing, to obtain a toner dispersion 1.

(2) Preparation of photosensitive adhesive component B1

26.5 parts by mass of the alkali-soluble resin P1 solution (solid content 40% by mass) obtained in preparation example 1, 17.7 parts by mass of a photopolymerizable compound (trade name ARONIX M-403, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by east Asia synthesis), 7.06 parts by mass of a photopolymerizable compound (trade name ARONIX M-305, pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by east Asia synthesis) and photoinitiator 1 (I1) as a photoinitiator were added: irgacure 907 (manufactured by BASF, α -aminoacetophenone-based photoinitiator) 1.96 parts by mass and photoinitiator 2 (12): 1.96 parts by mass of OXE-02 (oxime ester photoinitiator having a carbazole skeleton, manufactured by BASF), 0.392 part by mass of an ultraviolet absorber (ultraviolet absorber 1 (U1): kemisorb71, manufactured by Chemipro Kasei), 0.392 part by mass of IRGANOX1010 (manufactured by BASF) as an antioxidant, and 44.1 parts by mass of PGMEA were each prepared to obtain a photosensitive adhesive component B1.

(3) Preparation of photosensitive colored resin composition 1

The photosensitive colored resin composition of example 1 was prepared by mixing 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.

( Examples 2 to 27: production of photosensitive colored resin compositions 2 to 27 )

Photosensitive colored resin compositions 2 to 27 were obtained in the same manner as the photosensitive colored resin composition 1 of example 1 except that each of the photosensitive adhesive components B2 to B27 was prepared and used in place of the photosensitive adhesive component B1 as shown in table 2 in example 1.

Example 28 production of photosensitive colored resin composition 28

In example 2, a photosensitive colored resin composition 28 was obtained in the same manner as in example 2, except that the colorant in the colorant dispersion 1 was changed from the triarylmethane-based colorant 1 of synthesis example 1 to the triarylmethane-based colorant 2 of synthesis example 2.

( Comparative examples 1 to 5: production of comparative photosensitive colored resin compositions 1 to 5 )

Comparative photosensitive colored resin compositions 1 to 5 were obtained in the same manner as the photosensitive colored resin composition 1 of example 1 except that each of the photosensitive adhesive components CB1 to CB5 was prepared and used in place of the photosensitive adhesive component B1 as shown in table 3 in example 1.

( Comparative examples 6 to 8: production of comparative photosensitive colored resin compositions 6 to 8 )

(1) Preparation of colorant Dispersion C1

A225 mL mayonnaise bottle was charged with 65 parts by mass of PGMEA, 15 parts by mass of the alkali-soluble resin P1 solution of preparation example 1 (40% by mass of the solid content), and 10 parts by mass of the PGMEA solution of the acid dispersant A2 of Synthesis example 4 (20.0% by mass of the solid content), and stirred.

Into which 8.8 parts by mass of PB15: 6. 1.2 parts by mass of PV23 and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were subjected to shaking by a paint shaker (manufactured by shallow Tian Tiegong Co.) for 1 hour as pre-crushing, followed by changing to 200 parts by weight of zirconia beads having a particle diameter of 0.1mm, and then subjected to dispersion by the paint shaker for 4 hours as main crushing, whereby a colorant dispersion C1 was obtained.

(2) Preparation of comparative photosensitive colored resin compositions 6 to 8

In example 1, each of the photosensitive adhesive components CB6 to CB8 was prepared as shown in table 3 instead of the photosensitive adhesive component B1.

2.56 parts by mass of the colorant dispersion liquid 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 to 11: production of comparative photosensitive colored resin compositions 9 to 11 )

In example 1, each of the photosensitive adhesive components CB9 to CB11 was prepared as shown in table 3 instead of the photosensitive adhesive component B1.

The dye (triarylmethane dye 1 of comparative synthesis example 1) was mixed in an amount of 0.333 parts by mass, the photosensitive binder component 4.17 parts by mass, and PGME 5.50 parts by mass, to obtain comparative photosensitive colored resin compositions 9 to 11.

[ evaluation method ]

The photosensitive colored resin compositions of examples and comparative examples were each coated on a GLASS substrate (manufactured by NH TECHNO GLASS, "NA 35") having a thickness of 0.7mm using a spin coater so that the film thickness after post baking became 2.2. Mu.m, and then dried by heating at 80℃for 3 minutes using a heating plate. Thereafter, a photomask having 40 μm lines was formed thereon, and 60mJ/cm was irradiated with an ultra-high pressure mercury lamp ² Then, using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, spray development was carried out for 60 seconds. Thereafter, the resultant substrate was post-baked in a clean oven at 230℃for 30 minutes, whereby a pattern-formed substrate was produced in which a colored layer was formed on a glass substrate in a pattern of 40 μm lines.

< suppression of linewidth increase of colored layer >

The width of the thin line pattern of the colored layer at the portion corresponding to the opening width of 40 μm of the chromium mask used at the time of exposure at 5 was measured with an optical microscope, and the line width offset was evaluated based on the difference between the average line width and the target line width.

(evaluation criterion for line width increase inhibition)

AA: the difference is within 5.0 μm with respect to the target line width;

a: the difference is more than 5.0 μm and within 7.0 μm with respect to the target line width;

b: the difference is more than 7.0 μm and within 10.0 μm with respect to the target line width;

c: the difference exceeds 10.0 μm with respect to the target line width.

If the evaluation result is a, the line width increase inhibition is good, and if the evaluation result is AA, the line width increase inhibition is excellent.

< evaluation of residual film developing Rate >

The photosensitive colored resin compositions of examples and comparative examples were each coated on a GLASS substrate (manufactured by NH TECHNO GLASS, "NA 35") having a thickness of 0.7mm using a spin coater so that the film thickness after post baking became 2.2. Mu.m, and then dried by heating at 80℃for 3 minutes using a heating plate. Thereafter, 60mJ/cm of the film was irradiated with an ultra-high pressure mercury lamp without interposing a photomask ² After that, the film thickness T1 of the resist coating film was measured using a film thickness meter. Then, the film was developed by spraying with a 0.05 mass% aqueous potassium hydroxide solution as an alkaline developer for 60 seconds, and the film thickness T2 after the development was measured.

Calculated as developing residual film ratio=t2/t1% ].

(evaluation criterion of residual film developing Rate)

AA: the developing residual film rate is more than 98 percent;

A: the developing residual film rate is more than 97% and less than 98%;

b: the developing residual film rate is more than 94% and less than 97%;

c: the residual film developing rate is less than 94%.

If the evaluation result is a, the developing residual film ratio is good, and if the evaluation result is AA, the developing residual film ratio is excellent.

< evaluation of brightness and Heat resistance >

The photosensitive colored resin compositions of examples and comparative examples were each coated on a GLASS substrate (manufactured by NH techon GLASS, manufactured by "NA 35") having a thickness of 0.7mm using a spin coater so that the chromaticity after post baking became y=0.088. Thereafter, the film was dried by heating on a heating plate at 80℃for 3 minutes, and irradiated with an ultra-high pressure mercury lamp at 60mJ/cm without interposing a photomask ² Followed by post-baking in a clean oven at 230 ℃ for 30 minutes, thereby obtaining a cured film (colored film). The brightness (Y), L, a, b of the colored substrate obtained was measured using a "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus CorpL ₀ 、a ₀ 、b ₀ ) The evaluation was performed according to the following evaluation criteria.

Then, the substrate on which the cured film was formed was post-baked in a clean oven at 230℃for 30 minutes, left to cool for 30 minutes, the above procedure was repeated 3 times, and L, a, b (L ₁ 、a ₁ ，b ₁ ). From the measured values, the color difference (Δeab) before and after the treatment was calculated according to the following equation.

Color difference (Δeab) = { (L ₁ -L ₀ ) ² +(a ₁ -a ₀ ) ² +(b ₁ -b ₀ ) ² } ^1/2

(brightness evaluation reference)

AA: the brightness (Y) is more than 10.6;

a: the brightness (Y) is more than 10.0 and less than 10.6;

b: the brightness (Y) is 9.5 or more and less than 10.0;

c: the brightness (Y) is less than 9.5.

If the evaluation result is a, the brightness is good, and if the evaluation result is AA, the brightness is excellent.

(Heat resistance evaluation criterion)

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, the heat resistance is good, and if the evaluation result is AA, the heat resistance is excellent.

TABLE 2

TABLE 3

In the table, the abbreviations are as follows.

Photoinitiator 1 (I1): irgacure 907, manufactured by BASF, alpha-aminoacetophenone photoinitiator

Photoinitiator 2 (I2): oxime-02, BASF, oxime ester photoinitiator having carbazole skeleton

Ultraviolet absorber (U1): kemisorb71, manufactured by Chemipro Kasei

Ultraviolet absorber (U2): kemisorb12, manufactured by Chemipro Kasei

Ultraviolet absorber (U3): kemisorb111, manufactured by Chemipro Kasei

Ultraviolet absorber (U4): kemisorb73, manufactured by Chemipro Kasei

Ultraviolet absorber (U5): tinuvinPS, BASF manufacture

Ultraviolet absorber (U6): tinuvin928 manufactured by BASF

Ultraviolet absorber (U7): tinuvin405 manufactured by BASF

Ultraviolet absorber (U8): tinuvin479 manufactured by BASF

Ultraviolet absorber (U9): tinuvin329 manufactured by BASF

Ultraviolet absorber (U10): tinuvin477 manufactured by BASF

Ultraviolet absorber (U11): RUVA-93, chemical manufacture of tsukamurella

Antioxidants (A1): IRGANOX1010 manufactured by BASF

Latent antioxidant (LA 1): synthesis example 5 potential antioxidant

Resin P1: alkali-soluble resin P1 of preparation example 1

M1: photopolymerizable compound, ARONIX M-403, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by east Asia synthesis

M2: photopolymerizable compound, ARONIX M-305, pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by east Asia Synthesis

M3: photopolymerizable compound, ARONIX M-460, diglycerol ethylene oxide modified acrylate, manufactured by east asia synthesis

M4: photopolymerizable compound, kayard DPEA-12, ethylene oxide-modified (12) dipentaerythritol hexaacrylate, manufactured by Japanese chemical Co., ltd

Thiol: karenz MT PE1 manufactured by Showa electrician

TABLE 4 Table 4

TABLE 5

The photoinitiator, the ultraviolet absorber, the antioxidant, and the thiol were each a solid content ratio.

L1 (lake 1): lake 1 of triarylmethane dye in Synthesis example 1

L2 (lake 2): lake 2 of triarylmethane dye in Synthesis example 2

And (3) pigment: PB15:6 (C.I. pigment blue 15:6) and PV23 (C.I. pigment violet 23)

Dye: comparative Synthesis example 1 triarylmethane dye 1

[ summary of results ]

The photosensitive colored resin compositions of examples 1 to 28, in which the lake material of the triarylmethane dye and the ultraviolet absorber were combined, were able to form a colored layer having improved brightness, a fine line width, and suppressed film thickness variation before and after development.

In the examples, if a lake material of a triarylmethane dye is used in combination with an ultraviolet absorber, the line width shift amount can be adjusted to a target value of 5 μm or less by the initiator amount while maintaining the development residual film rate.

In the examples, when an ultraviolet absorber having a transmittance of 40% or less at 365nm in a 0.002 mass% propylene glycol monomethyl ether acetate solution is used, the line width shift is not likely to increase.

In addition, in the examples, when the photopolymerizable compound containing alkylene oxide is contained, it is easy to achieve both high development residual film ratio and fine line width.

In contrast, in the photosensitive colored resin composition of comparative example 1 containing no ultraviolet absorber, even if the antioxidant and the latent antioxidant are contained in the same manner as in example, the line width shift amount is large, the line width is large, and the colored layer cannot be formed with a desired fine line width.

The photosensitive colored resin compositions of comparative examples 2 and 3, which contained no ultraviolet absorber in the photosensitive colored resin composition of comparative example 1, reduced the photoinitiating agent amount in order to reduce the line width, had a slight decrease in the line width offset, but had a deterioration in the development residual film rate.

Among the photosensitive colored resin compositions of comparative example 1 containing no ultraviolet absorber, the photosensitive colored resin compositions of comparative examples 4 and 5, in which the antioxidant amount was increased to reduce the line width, had a reduced line width offset, but had a deteriorated development residual film rate.

On the other hand, in the photosensitive colored resin compositions of comparative examples 6 to 8 in which the pigment was used without using the lake material of the triarylmethane dye, a large amount of photoinitiating agent was required in order to obtain the same line width shift amount as in the example in which the lake material of the triarylmethane dye was used, and in this case, the development residual film rate was not a problem, but the brightness was low.

In addition, in the photosensitive colored resin compositions of comparative examples 9 to 11 in which the triarylmethane dye was used instead of the lake material using the triarylmethane dye, a large amount of photoinitiating amount was required to obtain the same line width shift amount as in the example in which the lake material using the triarylmethane dye was used, and in this case, the development residual film rate did not become a problem, but the color difference after heating increased and the brightness decreased.

Description of the reference numerals

1: substrate board

2: light shielding part

3: coloring layer

5: micropores

10: color filter

20: counter substrate

30: liquid crystal layer

40: liquid crystal display device having a light shielding layer

50: organic protective layer

60: inorganic oxide film

71: transparent anode

72: hole injection layer

73: hole transport layer

74: light-emitting layer

75: electron injection layer

76: cathode electrode

80: organic light-emitting body

100: an organic light emitting display device.

Claims

1. A photosensitive colored resin composition comprising a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent,

the colorant contains a lake of a triarylmethane-based dye.

2. The photosensitive colored resin composition according to claim 1, further comprising a dispersant.

3. The photosensitive colored resin composition according to claim 1 or 2, further comprising at least 1 of an antioxidant and a latent antioxidant.

4. The photosensitive colored resin composition according to any one of claims 1 to 3, further comprising a thiol compound.

5. The photosensitive colored resin composition according to any one of claims 1 to 4, wherein the lake material of the triarylmethane-based dye contains a coloring material represented by the following general formula (1),

general formula (1)

In the general formula (1), a is an organic group having a valence of a, which is not pi-bonded to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and a heteroatom is optionally contained in a carbon chain; b (B) ^c- A polyacid anion representing a valence of c; r is R ⁱ ～R ^v Each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, R ⁱⁱ And R is R ⁱⁱⁱ 、R ^iv And R is R ^v Optionally bonding to form a ring structure; r is R ^vi And R is ^vii Each independently represents an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano group; ar (Ar) ¹ Represents a divalent aromatic group optionally having a substituent; there are a plurality of R ⁱ ～R ^vii And Ar is a group ¹ Optionally the same or different, respectively;

a and c represent integers of 2 or more, and b and d represent integers of 1 or more; f and g represent integers of 0 to 4 inclusive; there are a plurality of f and g, optionally each identical or different.

6. 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 365nm in 0.002 mass% propylene glycol monomethyl ether acetate solution.

7. The photosensitive colored resin composition according to any one of claims 1 to 6, wherein the photopolymerizable compound contains a photopolymerizable compound containing an alkylene oxide.

8. A cured product of the photosensitive colored resin composition according to any one of claims 1 to 7.

9. 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.

10. A display device having the color filter of claim 9.