TW202307139A - Photosensitive colored resin composition, cured product, color filter and display device - Google Patents

Abstract

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

Description

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

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, and tablet PCs) is also increasing, and the market for liquid crystal displays is expanding day by day. An organic light-emitting display device such as an organic EL (Electroluminescence, electroluminescence) display with high visibility due to self-luminescence is also attracting attention as a next-generation image display device. These liquid crystal display devices or organic light emitting display devices use color filters. For example, the formation of a color image of a liquid crystal display device is that the light passing through the color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. As a light source at this time, besides the conventional cold-cathode tube, there are cases where an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light is used. In organic light emitting display devices, color filters are used for color adjustment and the like.

Here, a color filter generally includes: a substrate; a colored layer formed on the substrate and including colored patterns of three primary colors of red, green, and blue; and a light shielding portion formed on the substrate to divide each colored pattern. As a method of forming a colored layer in a color filter, for example, a binder resin, a photopolymerizable compound, and a photoinitiator are added to a color material dispersion obtained by dispersing a color material with a dispersant or the like. The colored resin composition is coated on a glass substrate and dried, then exposed and developed using a photomask to form a colored pattern, and then heated to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.

In recent years, the requirements for higher brightness of color filters have become higher and higher, and it is difficult to achieve the current higher brightness requirements by color filters using pigments. Therefore, in recent years, the use of dyes with higher transmittance than pigments or lake color materials made of dyes insoluble by precipitating agents has been studied as color materials for color filters. However, compared with pigments currently used as color materials for color filters, dyes or lake color materials have the following problems: heat resistance is poor, and the colored layer is easily damaged when heated at a high temperature in the color filter manufacturing process. fade.

On the other hand, in Patent Document 1, it is a colored resin for color filters that uses a lake pigment, suppresses fading of the colored layer due to high-temperature heating in the color filter manufacturing process, and can form a high-brightness colored layer. composition, and discloses a colored resin composition for color filters, which contains a lake pigment, a dispersant, a hindered phenolic antioxidant, a binder component, and a solvent. The dispersant is at least a part of the nitrogen site and A specific polymer formed by the formation of salts of acidic organophosphorus compounds.

On the other hand, as a photosensitive coloring composition containing an ultraviolet absorber, Patent Document 2 discloses a coloring resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin. A resin composition characterized by further comprising (D) an antioxidant and (E) an ultraviolet absorber. The subject of Patent Document 2 is to provide a contact hole capable of forming a desired diameter while maintaining and improving the luminance and heat resistance of the obtained pixel. In addition, Patent Document 3 discloses a photosensitive coloring composition characterized by comprising a colorant (A), a resin (B), a photopolymerizable monomer (C), an acyl phosphine oxide-based organic compound or an oxime A photopolymerization initiator (D) of an ester-based organic compound, and at least one selected from the group consisting of a benzotriazole-based organic compound, a triazole-based organic compound, and a benzophenone-based organic compound The ultraviolet absorber (E), and the resin (B) includes a photosensitive resin (B-1) obtained by copolymerizing the following (b1), (b2) and (b3) (b6), the obtained copolymer (b6) is reacted with the unsaturated monobasic acid (b4) to obtain the copolymer (b7), and then the obtained copolymer (b7) is reacted with the polybasic acid anhydride (b5) to obtain Winners: (b1): Compounds with alicyclic skeleton and ethylenically unsaturated bonds in one molecule; (b2): Compounds with epoxy groups and ethylenically unsaturated bonds in one molecule; (b3): Except ( Compounds having ethylenically unsaturated bonds other than a1) and (a2). In Patent Document 3, the problem is to obtain a photosensitive coloring composition with high resolution that can cope with high image quality and low power consumption, especially even if it is thick like the COA (Color Filter on Array) method. The film is also a photosensitive coloring composition with high resolution and excellent adhesion without pattern peeling. Prior Art Documents Patent Documents

Patent Document 1: Japanese Patent Laid-Open No. 2014-153569 Patent Document 2: Japanese Patent Laid-Open No. 2015-98537 Patent Document 3: Japanese Patent No. 5664299

[Problem to be solved by the invention]

With the high-definition of 4K/8K displays, the size of the pixel becomes smaller, corresponding to the reduction of the aperture ratio (aperture ratio) of the pixel, a resist with higher brightness is required, and it is required to be able to form a pattern with a thinner line width A photosensitive colored resin composition. However, when the dye is dissolved and used as in Patent Document 2, especially the heat resistance is poor, and the brightness of the pixel is not improved enough, and in the technique of using a pigment as in Patent Document 3, the brightness of the pixel is not improved enough. As a coloring material effective for high brightness of pixels, a lake coloring material of a triarylmethane dye can be exemplified. However, compared with previously used pigments (such as C.I. Pigment Blue 15:6, C.I. Pigment Violet 23), the color lake material of triarylmethane dyes has a higher transmittance in the UV wavelength region. When a photoinitiator is prepared, the line width of the pattern tends to become thicker. If the photoinitiator dose is reduced, or antioxidants are added as in Patent Document 1, or the amount of antioxidants is increased in order to make the line width of the pattern conform to the specified value, the photocurability of the pattern part will be insufficient, and the photocurability of the pattern part will be insufficient, and the time between before and after development will be reduced. The variation of film thickness increases, and the residual film rate of development decreases. It is difficult to achieve a thinner line width design and a higher rate of residual film at the same time. Although Patent Document 1 records the color lake material of triarylmethane dyes, there is no suggestion on the subject of simultaneously achieving a thinner line width design and a higher rate of remaining film after developing. 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, it is easy to inhibit the hardening of the photocurable component. If the photoinitiator is formulated in the same way as the pigment, the photocurability will be insufficient and the line width will easily change. If it is thinner than the design, the residual film rate of developing is easy to reduce. Therefore, in the photosensitive colored resin composition containing the dye, in order to set the required thinner line width, it is necessary to increase the photoinitiator or use a photoinitiator with higher sensitivity, so the residual film rate of development will decrease. Raise naturally. Therefore, in the photosensitive colored resin composition containing dyes, there is no problem that it is difficult to simultaneously realize a thinner line width design and a higher residual film rate after development. In addition, Patent Document 3 uses pigments, so there is no problem that it is difficult to simultaneously realize a thinner line width design and a higher residual film rate after development. As mentioned above, in the case of using triarylmethane-based dye lake color materials, it is difficult to simultaneously achieve a thinner line width design and a higher residual film rate of development, unlike the case of using pigments or dyes. of the topic.

The present invention is made in view of the above-mentioned actual situation, and its object is to provide a kind of photosensitive coloring resin composition, this photosensitive coloring resin composition contains the color lake color material of triarylmethane series dye, can form and improve brightness and by finer The line width of the coloring layer suppresses the change in film thickness before and after development. Moreover, the object of this invention is to provide the color filter and display apparatus formed using this photosensitive colored resin composition. [Technical means to solve the problem]

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, The above-mentioned color material contains a lake color material of a triarylmethane dye.

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

The display device of the present invention has the above-mentioned color filter of the present invention. [Effect of Invention]

According to the present invention, it is possible to provide a photosensitive colored resin composition that contains a triarylmethane-based dye lake coloring material and can form a colored layer that improves brightness and suppresses changes in film thickness before and after development due to thinner line widths. Also, according to the present invention, a color filter and a display device formed using the photosensitive colored resin composition can be provided.

Hereinafter, the photosensitive colored resin composition, cured product, color filter, and display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves of wavelengths in the visible light and non-visible light regions, and further includes radiation. For example, radiation includes microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, (meth)acryl means each of acryl and methacryl, (meth)acryl means each of acryl and methacryl, (meth)acrylate Represents each of acrylate and methacrylate. In addition, in this specification, "-" which shows a numerical range is used in the meaning which includes the numerical value described before and after it as a lower limit and an upper limit.

I. Photosensitive colored resin composition 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, The above-mentioned color material contains a lake color material of a triarylmethane 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 above-mentioned coloring material is a triarylmethane-based dye lake coloring material, Therefore, it is possible to form a colored layer that improves luminance and suppresses changes in film thickness before and after development with thinner line widths. The function of exerting such an effect is not clear, but it is estimated as follows.

As mentioned above, the ultraviolet transmittance of the pigment is low, so in the photosensitive colored resin composition containing the pigment, it is relatively difficult to harden the photocurable component. Moreover, since a dye tends to suppress the curability of a photocurable component, in the photosensitive colored resin composition containing a dye, a photocurable component is relatively difficult to harden. In contrast, the color lake material of triarylmethane dyes has a higher transmittance of ultraviolet rays and does not inhibit the hardening of photocurable components, so the effect of insolubility in developing solutions after photocuring is higher than that of pigments or dye, so the pattern line width tends to become thicker. In the photosensitive coloring resin composition containing the lake material of a triarylmethane dye, it is necessary to effectively suppress the photocuring reaction in order to make the pattern line width a predetermined thinner line width. As a coloring material, a triarylmethane-based dye lake coloring material with high transmittance is used. It is believed that if the initial dose of light is reduced in order to make the pattern line width meet the specified value, the photoreaction will be reduced regardless of the film thickness direction. Free radicals are generated, so the photocurability of the pattern part is insufficient, the film thickness change from before to after development increases, and the residual film rate after development decreases. In addition, for the lake color material using triarylmethane dyes, it is considered that if an antioxidant is added or its amount is increased in order to make the pattern line width meet the specified value, the light passing through the photoinitiator will be blocked regardless of the film thickness direction. The free radicals generated by the reaction are deactivated, so the photocurability of the pattern part is insufficient, the film thickness change from before to after development is increased, and the residual film rate after development is reduced. On the other hand, in the present invention, an ultraviolet absorber is combined with the lake material of a triarylmethane dye. It is considered that the ultraviolet absorber will not attenuate the ultraviolet rays on the surface of the film, so the residual film will not be reduced, and it will attenuate the ultraviolet rays as it reaches the deep part of the film, reducing the generation of free radicals from the initiator. This works according to the depth of the film, so it can Suppresses reduction in film thickness of residual film after development and reduces line width. Furthermore, since the coloring material includes a lake coloring material of a triarylmethane dye, the transmittance of the coloring layer as a hardened product of the photosensitive colored resin composition of the present invention is high, and it is difficult to produce a coloring layer by ultraviolet irradiation or post-baking. Chromaticity changes caused by the steps are suppressed. Therefore, the photosensitive colored resin composition of the present invention can provide 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 ingredients. For example, the photosensitive colored resin composition of the present invention may further contain a dispersant in order to improve the dispersibility of the color material. Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail sequentially from the ultraviolet absorber first.

[ultraviolet absorber] The ultraviolet absorber in the present invention refers to a compound that has a maximum absorption wavelength below 400 nm and has no absorption under visible light with a wavelength exceeding 420 nm. The ultraviolet absorber used in the present invention may be a compound having no absorption wavelength under visible light with a wavelength exceeding 400 nm.

The structure of the ultraviolet absorber used in the present invention is not particularly limited. Examples of the ultraviolet absorber include: benzotriazole-based ultraviolet absorbers, trisulfone-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and benzoic acid-based ultraviolet absorbers. , Anthranilic acid-based UV absorbers, salicylic acid-based UV absorbers, cinnamic acid-based UV absorbers, etc.

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

(於通式(A)中，X ¹、X ²、及X ³分別獨立地表示氫原子、羥基、-OR ^a、或可具有取代基之碳原子數1～15之烴基，R ^a表示可具有取代基之碳原子數1～15之烴基，X ¹、X ²、及X ³之至少一者表示羥基、-OR ^a、或可具有取代基之碳原子數1～15之烴基。X ⁴表示氫原子或鹵素原子) [chemical 1]

(In the general formula (A), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a hydroxyl group, -OR ^a , or a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent, and R ^a represents an optional A hydrocarbon group having 1 to 15 carbon atoms having a substituent, at least one of X ¹ , X ² , and X ³ represents hydroxyl, -OR ^a , or a hydrocarbon group having 1 to 15 carbon atoms that may have a substituent. X ⁴ represents a hydrogen atom or a halogen atom)

In the general formula (A), the above-mentioned hydrocarbon groups having 1 to 15 carbon atoms in X ¹ , X ² , and X ³ , and R ^a can be straight-chain or branched aliphatic hydrocarbon groups and aromatic hydrocarbon groups, Examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, phenyl, naphthyl, biphenyl and the like. The number of carbon atoms in the above-mentioned hydrocarbon group may be 1-12, or may be 1-8. The above-mentioned hydrocarbon groups can be aliphatic hydrocarbon groups, also can be linear or branched chain alkyl groups, can also be methyl, tertiary butyl, tertiary pentyl, n-octyl, tertiary octyl (1,1,3 , 3-tetramethylbutyl), 2-ethylhexyl. As a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, or a group including a carbonyl group, an ester group, an ether group, an amido group, an imide group, etc., may be mentioned, and may be an acyl group, an acyloxy group, or an alkoxy group. group, aryloxy group, glycidyl group, etc. Furthermore, an alkyl group may be used as a substituent of an aromatic hydrocarbon group. Examples of hydrocarbon groups having substituents include -C ₂ H ₃ (OH)-CH ₂ -OC ₈ H ₁₇ , -C ₂ H ₃ (OH)-CH ₂ -OC ₁₂ H ₂₅ , -CH(CH ₃ ) -CO ₂ -C ₈ H ₁₇ , methacryloxyethyl, etc., and 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanobenzene 4-phenoxyphenyl, 4-glycidyloxyphenyl, 4-isocyanuratophenyl, etc. Each of the aforementioned -C ₈ H ₁₇ , -C ₁₂ H ₂₅ , etc. may be linear or branched. In the general formula (A), examples of the halogen atom include a chlorine atom, a fluorine atom, and a bromine atom.

Examples of benzotriazole-based ultraviolet absorbers include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 3-[3 -Mixture of tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propanoic acid 2-ethylhexyl ester, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5- Chlorobenzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzo Triazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2- base)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, etc.

For example, at least one ultraviolet absorber selected from the group consisting of trioxane-based ultraviolet absorbents represented by the following general formula (B) may be mentioned as the trioxane-based ultraviolet absorber.

(於通式(B)中，Y ¹、Y ²、Y ³、Y ⁴、Y ⁵、及Y ⁶分別獨立地表示氫原子、羥基、-OR ^b、或可具有取代基之碳原子數1～15之烴基，R ^b表示可具有取代基之碳原子數1～15之烴基，Y ¹、Y ²、Y ³、Y ⁴、Y ⁵、及Y ⁶之至少一者表示羥基、-OR ^b、或可具有取代基之碳原子數1～15之烴基) [Chem 2]

(In the general formula (B), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ each independently represent a hydrogen atom, a hydroxyl group, -OR ^b , or a carbon atom number 1 that may have a substituent A hydrocarbon group with ∼15 carbon atoms, R ^b represents a hydrocarbon group with 1 to 15 carbon atoms which may have a substituent, at least one of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ represents a hydroxyl group, -OR ^b , or a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent)

In Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , and Y ⁶ , and a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent in R ^b , it can be combined with the above-mentioned X ¹ , X ² , and X ³ , and the above-mentioned hydrocarbon group having 1 to 15 carbon atoms which may have a substituent in R ^a are the same. At least one of Y ² , Y ⁴ , and Y ⁶ may be a hydroxyl group, or may be a hydroxyphenyl trisulfone-based ultraviolet absorber.

Examples of trioxane-based ultraviolet absorbers include: 2-[4,6-bis(2,4-xylyl)-1,3,5-trizil-2-yl]-5-octyloxy Phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl]-5-[3-(dodecyloxy)-2 -Hydroxypropoxy]phenol, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-tributoxyphenyl wait.

For example, the benzophenone-based ultraviolet absorber may, for example, be a hydroxybenzophenone-based ultraviolet absorber, which may be selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbers represented by the following general formula (C). At least one ultraviolet absorber of the group formed.

(於通式(C)中，Z ¹表示羥基、-OR ^c、或可具有取代基之碳原子數1～15之烴基，Z ²表示氫原子、羥基、-OR ^c、或可具有取代基之碳原子數1～15之烴基，Z ³表示氫原子或羥基，R ^c表示可具有取代基之碳原子數1～15之烴基) [Chem 3]

(In the general formula (C), Z ¹ represents a hydroxyl group, -OR ^c , or a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent, and Z ² represents a hydrogen atom, a hydroxyl group, -OR ^c , or a hydrocarbon group that may have a substituent A hydrocarbon group with 1 to 15 carbon atoms, Z ³ represents a hydrogen atom or a hydroxyl group, R ^c represents a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent)

In the general formula (C), the hydrocarbon groups with 1 to 15 carbon atoms which may have substituents in Z ¹ , Z ² , and R ^c can be combined with the above-mentioned X ¹ , X ² , and X ³ , and R ^a The aforementioned hydrocarbon groups having 1 to 15 carbon atoms which may have substituents are the same.

Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-n-octyloxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, etc.

The weight average molecular weight of the ultraviolet absorber used in the present invention is usually 80 or more, preferably 150 or more, further preferably 300 or more, and usually 2000 or less, preferably 2000 or less, in terms of efficiently absorbing ultraviolet rays 1500 or less, more preferably 900 or less. In addition, the polymer of the ultraviolet absorber is preferably a non-polymer compound having no repeating unit because the ultraviolet absorbing ability is low.

The ultraviolet absorber used in the present invention is preferably an ultraviolet absorber with a transmittance of 45% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution. If, as mentioned above, the ultraviolet absorber with a lower transmittance at a wavelength of 365 nm is used in combination with the color lake material of triarylmethane dyes, it can effectively reduce the weak absorption of the triarylmethane color lake material and Ultra-high pressure mercury lamp has the highest irradiation intensity of ultraviolet rays. As a result, it is possible to add an initiator in an amount sufficient to ensure the hardening of the coating film surface to suppress the change in film thickness after developing residue, and effectively reduce the internal friction of the coating film. Photocurability is preferable in terms of being easy to adjust so that the amount of line width shift does not become too large.

The transmittance of the ultraviolet absorber at a wavelength of 365 nm can be prepared with a 0.002% by mass propylene glycol monomethyl ether acetate solution of the ultraviolet absorber, and measured using a UV-visible-near-infrared spectrophotometer (such as V-7100 of JASCO Co., Ltd.) This 0.002 mass % propylene glycol monomethyl ether acetate solution.

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

From the viewpoint of obtaining the effect of the present invention, the ultraviolet absorber used in the present invention is preferably one whose solubility in the solvent used for the photosensitive colored resin composition at 25° C. is 1% by mass or more. The ultraviolet absorber used in the present invention may have a solubility in propylene glycol monomethyl ether acetate at 25° C. of 1% by mass or more.

As the ultraviolet absorber used in the present invention, for example, the following compounds can be cited as suitable ones: 2-(2-hydroxyl-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxyl -5-tertiary octylphenyl)-2H-benzotriazole, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl] -4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethanone, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl) -4,6-bis(4-phenylphenyl)-1,3,5-trimethanone, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-benzene ethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-hydroxy-4-octyloxybenzophenone, 2-(2-hydroxy-5-methylbenzene base)-2H-benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-dihydroxy-4- Methoxybenzophenone, 2-(2-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, (2-hydroxy-3-dodecyl-5- Methylphenyl) benzotriazole, etc. As commercially available items, for example, TinuvinPS, Tinuvin329, Tinuvin405, Tinuvin477, Tinuvin479, Tinuvin571, Tinuvin928 (the above are manufactured by BASF), Kemisorb12, Kemisorb71, Kemisorb71D, Kemisorb73, Kemisorb111 (the above are manufactured by Chemipro Kasei), RUVA-93 (The above are manufactured by Otsuka Chemical), etc.

In the present invention, the ultraviolet absorbent may be used alone or in combination of two or more. In addition, even when selecting and using an ultraviolet absorber having a transmittance of 45% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution, two or more types may be used in combination. That is, even if the ultraviolet absorber used in the present invention has a transmittance of more than 45% at a wavelength of 365 nm in a 0.002 mass % propylene glycol monomethyl ether acetate solution alone, two or more types may be mixed to form a 0.002 mass % propylene glycol monomethyl ether acetate solution. If the transmittance at a wavelength of 365 nm in % propylene glycol monomethyl ether acetate solution is 45% or less, the ultraviolet absorber of the mixture can be used.

The content of the above-mentioned ultraviolet absorber is usually 0.2% by mass relative to the total solid content of the photosensitive colored resin composition for the purpose of obtaining the line width suppression effect and adjusting the photocurability so that the curing progresses favorably. It is within the range of ∼4.0% by mass, preferably within the range of 0.3% by mass to 3.0% by mass, more preferably within the range of 0.5% by mass to 2.0% by mass. In addition, the solid content refers to all components other than a solvent, and also includes a liquid photopolymerizable compound and the like.

In addition, for the purpose of obtaining the line width suppression effect and adjusting the photocurability in a manner to perform curing well, the ratio of the total mass of the ultraviolet absorber to the total mass of the photoinitiator and the ultraviolet absorber is preferably 2.0 It is in the range of mass % - 20.0 mass %, More preferably, it is in the range of 4.0 mass % - 18.0 mass %.

[color material] In order to form a photosensitive coloring layer that can suppress changes in chromaticity or decrease in brightness before and after the high-temperature heating step, improve the brightness of the finally obtained colored layer, and suppress changes in film thickness before and after development by thinner line widths The coloring resin composition, the coloring material in the present invention contains a lake coloring material of a triarylmethane dye. ＜Color material for triarylmethane-based dyes＞ The lake material of triarylmethane dyes is preferably a lake material of triarylmethane dyes and polyacids in terms of excellent heat resistance and light resistance, and high brightness of color filters. As the color material of the lake of triarylmethane dyes, preferably one or more selected from the color materials represented by the following general formula (1) and the color materials represented by the following general formula (2), In terms of forming a molecular aggregation state, exhibiting more excellent heat resistance, and being able to achieve high brightness, the color material represented by the following general formula (1) is preferable.

(通式(1)中，A為與N直接鍵結之碳原子不具有π鍵之a價之有機基，該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基、或具有該脂肪族烴基之芳香族基，碳鏈中可含有雜原子。B ^c-表示c價之多酸陰離子。R ⁱ～R ^v各自獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R ⁱⁱ與R ⁱⁱⁱ、R ^iv與R ^v可鍵結而形成環結構。R ^vi及R ^vii各自獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基。Ar ¹表示可具有取代基之二價芳香族基。存在複數個之R ⁱ～R ^vii及Ar ¹分別可相同亦可不同。 a及c表示2以上之整數，b及d表示1以上之整數。f及g表示0以上4以下之整數。存在複數個之f及g分別可相同亦可不同) [chemical 4]

(In general formula (1), A is an a-valent organic group that does not have a valence of a carbon atom directly bonded to N, and the organic group represents an aliphatic group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N. A hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, may contain heteroatoms in the carbon chain. B ^c- represents a c-valent polyacid anion. R ⁱ ~ R ^v each independently represent a hydrogen atom, an alkane that may have a substituent R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be bonded to form a ring structure. R ^vi and R ^vii each independently represent an alkyl group that may have a substituent, an alkyl group that may have a substituent An alkoxy group, a halogen atom or a cyano group. ^{Ar 1} represents a divalent aromatic group that may have a substituent. There are a plurality of R ⁱ ~ R ^vii and Ar ¹ may be the same or different. a and c represent 2 or more b and d represent integers of 1 or more. f and g represent integers of 0 to 4. Plural f and g may be the same or different)

(通式(2)中，R ^I～R ^VI各自獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R ^I與R ^II、R ^III與R ^IV、R ^V與R ^VI可鍵結而形成環結構。R ^VII及R ^VIII各自獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基。Ar ²表示可具有取代基之二價芳香族雜環基，存在複數個之R ^I～R ^VIII及Ar ²分別可相同亦可不同。E ^m-表示m價之多酸陰離子。 m表示2以上之整數。k及l表示0以上4以下之整數。存在複數個之k及l分別可相同亦可不同) [chemical 5]

(In general formula (2), R ^I to R ^VI each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, R ^I and R ^II , R ^III and R ^IV , R ^V May be bonded with R ^VI to form a ring structure. R ^VII and R ^VIII each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom or a cyano group. Ar ² represents a group that may have a substituent For the divalent aromatic heterocyclic group, there are multiple R ^I ~ R ^VIII and Ar ² which can be the same or different. ^{E m-} represents an m-valent polyacid anion. m represents an integer of 2 or more. k and l represent Integers from 0 to 4. Plural k and l may be the same or different)

The color material represented by the above-mentioned general formula (1) contains anion with a divalent or higher valence and a cation with a divalent or higher valence. Therefore, in the aggregate of the color material, the anion and the cation are not simply ionically bonded by one molecule to one molecule. , and can form a molecular aggregate in which multiple molecules are aggregated through ionic bonds, so the apparent molecular weight is significantly increased compared with the molecular weight of the previous lake pigment. It is estimated that through the formation of such molecular aggregates, the cohesive force in the solid state is further improved, thermal movement is reduced, the dissociation of ion pairs or the decomposition of cationic parts can be suppressed, and it is less likely to fade than previous lake pigments.

A in the above-mentioned general formula (1) is an organic group having a valency of a valence not having a π bond to a carbon atom directly bonded to N (nitrogen atom). The aliphatic hydrocarbon group of the hydrocarbon group, or the aromatic group having the aliphatic hydrocarbon group, may contain heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. That is, the organic group means at least an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N and may contain heteroatoms such as O, S, N in the carbon chain, or having an aliphatic hydrocarbon group at the end directly bonded to N. An aromatic group that is an aromatic hydrocarbon group and can contain heteroatoms such as O, S, and N in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as hue or transmittance of the cationic color-developing part will not be affected by the linking group A or other color-developing parts, and can be maintained with a single Body the same color.

In A, regarding the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, as long as the carbon atom at the terminal directly bonded to N does not have a π bond, it may be straight chain, branched or cyclic In either shape, the carbon atoms other than the terminal may have unsaturated bonds or substituents, and the carbon chain may contain O, S, and N. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amido group, etc. may be included, and a hydrogen atom may be further substituted with a halogen atom, etc. Also, in A, the above-mentioned aromatic group having an aliphatic hydrocarbon group can be, for example, a monocyclic or polycyclic aromatic group containing an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, and may have a substitution The group can be a heterocycle containing O, S, N. Among them, in terms of the fastness of the skeleton, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group. Examples of the cyclic aliphatic hydrocarbon group include those containing cyclohexane, cyclopentane, nor-alkane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 ^2,6 ]decane, and adamantane. Base etc. Moreover, as an aromatic group, the group containing a benzene ring, a naphthalene ring, etc. are mentioned, for example. For example, when A is a divalent organic group, it can be substituted by two straight-chain, branched, or cyclic alkylene groups or xylylene groups having 1-20 carbon atoms. Aromatic groups of alkylene groups, etc.

In the present invention, in terms of both fastness and freedom of molecular movement, and improving heat resistance, it is preferable that A has two or more cyclic aliphatic hydrocarbon groups, and has a saturation at the end directly bonded to N Aliphatic hydrocarbon group, an aliphatic hydrocarbon group that may contain O, S, and N in the carbon chain. A is more preferably an aliphatic hydrocarbon group having two or more cycloalkylene groups, a saturated aliphatic hydrocarbon group at the end directly bonded to N, and an aliphatic hydrocarbon group that may contain O, S, and N in the carbon chain. A structure in which two or more cyclic aliphatic hydrocarbon groups are linked by linear or branched aliphatic hydrocarbon groups. The two or more cyclic aliphatic hydrocarbon groups may be the same or different, for example, the same ones as the above-mentioned cyclic aliphatic hydrocarbon groups, among which cyclohexane and cyclopentane are preferable.

In the present invention, the aforementioned A is preferably a substituent represented by the following general formula (1a) in terms of heat resistance.

(通式(1a)中，R ^xi表示可具有碳數1以上4以下之烷基、或碳數1以上4以下之烷氧基作為取代基之碳數1以上3以下之伸烷基，R ^xii及R ^xiii各自獨立地表示碳數1以上4以下之烷基、或碳數1以上4以下之烷氧基，p表示1以上3以下之整數，q及r各自獨立地表示0以上4以下之整數。於R ^xi、R ^xii、R ^xiii及r存在複數個之情形時，該存在複數個之R ^xi、R ^xii、R ^xiii及r互相可相同亦可不同) [chemical 6]

(In the general formula (1a), R ^xi represents an alkylene group with a carbon number of 1 to 4 and an alkyl group or an alkoxy group with a carbon number of 1 to 4 as a substituent, and R ^xii and R ^xiii each independently represent an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms, p represents an integer from 1 to 3, and q and r each independently represent 0 to 4 inclusive Integers. When Rxi, ^Rxii , ^Rxiii , and r exist in plural, the plural ^Rxi , ^Rxii , ^Rxiii , and r may be the same or different from each other ⁾

It is preferably an alkylene group having 1 or more and 3 or less carbon atoms in R ^xi in terms of excellent balance between fastness and thermal movement of the color-developing site and improved heat resistance. Such an alkylene group may, for example, be a methylene group, an ethylidene group or a propylidene group, among which a methylene group or an ethylidene group is preferable, and a methylene group is more preferable. The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, or a butyl group, which may be linear or branched. Moreover, examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched.

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

In the general formula (1a), in terms of heat resistance, the number of cyclohexane (cyclohexylene) is preferably 2 to 4, that is, p is 1 to 3, and p is 1 more preferably Above 2 and below. Also, the number of substitutions of the substituents R ^xii and R ^xiii of the cyclohexylene group is not particularly limited, but is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less 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.

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

[chemical 7]

The alkyl groups in R ⁱ to R ^v are not particularly limited. For example, straight chain, branched or cyclic alkyl groups with 1 to 20 carbons can be exemplified, among which straight chain or branched alkyls with 1 to 8 carbons can be exemplified. In terms of brightness and heat resistance On the other hand, it may be a linear or branched alkyl group having 1 to 5 carbon atoms, and the alkyl group in R ⁱ to R ^v may be ethyl or methyl. The substituent that the alkyl group may have is not particularly limited, for example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, etc., and the substituted alkyl group includes an aralkyl group such as a benzyl group, etc. . The aryl group in R ⁱ to R ^v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. As a substituent which an aryl group may have, an alkyl group, a halogen atom, an alkoxyl group, a hydroxyl group etc. are mentioned, for example. Among them, in terms of chemical stability, R ⁱ to R ^v are preferably each independently a hydrogen atom, an alkyl group having 1 to 5 carbons, or a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v is bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

In terms of heat resistance, at least one of R ⁱⁱ to R ^v is preferably a cycloalkyl group which may have a substituent or an aryl group which may have a substituent. It is considered that when at least one of R ⁱⁱ to R ^v has a cycloalkyl group or an aryl group, the intermolecular interaction due to steric hindrance is reduced, so that the effect of heat on the color-developing site can be suppressed, and thus the heat resistance is excellent.

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

(通式(1b)中，R ^xiv、R ^xv、及R ^xvi各自獨立地表示氫原子、可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基) [chemical 8]

(In general formula (1b), R ^xiv , R ^xv , and R ^xvi each independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 4 that may have a substituent, or an alkyl group with a carbon number of 1 to 4 that may have a substituent the following alkoxy)

(通式(1c)中，R ^xvii、R ^xviii、及R ^xix各自獨立地表示氫原子、可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基) [chemical 9]

(In general formula (1c), R ^xvii , R ^xviii , and R ^xix each independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 4 that may have a substituent, or an alkyl group with a carbon number of 1 to 4 that may have a substituent the following alkoxy)

Examples of alkyl groups having 1 to 4 carbon atoms in R ^xiv , R ^xv , R ^xvi , R ^xvii , R ^xviii , and R ^xix include methyl, ethyl, propyl, and butyl, which may be straight Chain, may also have branched chain. Moreover, examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched. As a substituent which the said alkyl group and alkoxy group may have, a halogen atom, a hydroxyl group, etc. are mentioned.

In the case of having a substituent represented by the above general formula (1b), in terms of heat resistance, at least one of R ^xiv , R ^xv , and R ^xvi is preferably 1 carbon number that may have a substituent The above-mentioned alkyl group of 4 or less, or an alkoxy group having a carbon number of 1 or more and 4 or less which may have a substituent, more preferably at least one of R ^xiv and R ^xv is an alkyl group having a carbon number of 1 or more and no more than 4 which may have a substituent group, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.

Also, when having a substituent represented by the above-mentioned general formula (1c), it is preferable that at least one of R ^xvii , R ^xviii , and R ^xix is a carbon that may have a substituent in terms of heat resistance. An alkyl group with a number of 1 to 4, or an alkoxy group with a carbon number of 1 to 4 that may have a substituent, more preferably at least one of R ^xvii and R ^xviii has a carbon number of 1 to 4 that may have a substituent an alkyl group, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.

骨架內之共振結構之芳香環的任一部位，其中較佳為以-NR ⁱⁱR ⁱⁱⁱ或-NR ^ivR ^v所表示之胺基之取代位置為基準而取代於間位。 R ^vi and R ^vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. The alkyl group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkyl group with a carbon number of 1 to 8, and more preferably an alkane with a carbon number of 1 to 4. base. The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, or a butyl group, which may be linear or branched. It does not specifically limit as a substituent which an alkyl group may have, For example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned. Also, the alkoxy group in R ^vi and R ^vii is not particularly limited, but it is preferably a straight-chain or branched alkoxy group with a carbon number of 1 to 8, and more preferably a carbon number of 1 or more. Alkoxy groups of 4 or less. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched. It does not specifically limit as a substituent which an alkoxy group may have, For example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned. As a halogen atom in Rvi ^{and Rvii} , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The number of substitutions of R ^vi and R ^vii , that is, f and g each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1. Plural f and g may be the same or different. Also, R ^vi and R ^vii can be substituted with triarylmethane skeleton, or 𠮿

Any part of the aromatic ring of the resonance structure within the skeleton is preferably substituted at the meta position based on the substitution position of the amino group represented by -NR ⁱⁱ R ⁱⁱⁱ or -NR ^iv R ^v .

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in ^Ar1 may be a heterocyclic group in addition to an aromatic hydrocarbon group containing a carbocycle. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, it can be exemplified: condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fenene ring, anthracene ring, phenanthrene ring, etc.; Benzene, diphenylmethane, triphenylmethane, stilbene and other chain polycyclic hydrocarbons. In this chain polycyclic hydrocarbon, O, S, and N may be included in the chain skeleton like diphenyl ether or the like. On the other hand, examples of the heterocyclic ring in the heterocyclic group include five-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; pyran, pyrone, pyridine, and pyrone. , pyrimidine, pyrimidine, etc. 6-membered heterocycles; benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, and benzofuran , quinazoline, quinoline and other condensed polycyclic heterocycles. These aromatic groups may further have an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a phenyl group which may be substituted by these, etc. as a substituent.

Plural R ⁱ to R ^vii and Ar ¹ present in one molecule may be the same or different. Through the combination of R ⁱ ~ R ^vii and Ar ¹ , the required color can be adjusted.

The valency a in A is the number of color-forming cation sites constituting the cation, and a is an integer of 2 or more. In this lake coloring material, since the valence a of the cation is 2 or more, heat resistance is excellent, and 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, from the viewpoint of ease of manufacture.

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

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

As a polyacid anion formed by condensation of multiple oxyacids, it can be an isopolyacid anion (M _m O _n ) ^c- , or a heteropolyacid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a polyatom, X represents a heteroatom, m represents a composition ratio of a polyatom, and n represents a composition ratio of an oxygen atom. As polyatom M, Mo, W, V, Ti, Nb etc. are mentioned, for example. Moreover, as heteroatom X, Si, P, As, S, Fe, Co etc. are mentioned, for example. In addition, counter cations such as Na ⁺ or H ⁺ may be contained in a part. Among them, polyacids containing one or more elements selected from tungsten (W) and molybdenum (Mo) are preferable in terms of excellent heat resistance. As such polyacids, for example: tungstate ion [W ₁₀ O ₃₂ ] ^4- , molybdate ion [Mo ₆ O ₁₉ ] ^2- as isopolyacid; or phosphotungstate ion as heteropolyacid [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , silicotungstate ion [SiW ₁₂ O ₄₀ ] ^4- , phosphomolybdate ion [PMo ₁₂ O ₄₀ ] ^3- , silicomolybdate ion [SiMo ₁₂ O ₄₀ ] ^4- , Phosphotungstomolybdate ion [PW _12-s Mo _s O ₄₀ ] ^3- (s is an integer between 1 and 11), [P ₂ W _18-t Mo _t O ₆₂ ] ^{6 -} (t is an integer ranging from 1 to 17), silicon tungsten molybdate ion [SiW _12-u Mo _u O ₄₀ ] ^4- (u is an integer ranging from 1 to 11), etc. As the polyacid containing at least one of tungsten (W) and molybdenum (Mo), in terms of heat resistance and ease of raw material acquisition, among the above, a heteropolyacid is preferred, and it is more preferred to further contain Phosphorus (P) heteropolyacid. Furthermore, in terms of heat resistance, phosphotungstate molybdate ion [PW ₁₀ Mo ₂ O ₄₀ ] ^3- , [PW ₁₁ Mo ₁ O ₄₀ ] ^3- , phosphotungstate ion [PW ₁₂ O ₄₀ ] any of ^3- .

b in the general formula (1) represents the number of cations, d represents the number of anions in molecular aggregates, and b and d represent integers of 1 or more. When b is 2 or more, a plurality of cations present in a molecular aggregate may be a single type or a combination of two or more types. Moreover, when d is 2 or more, the anion which exists in plural in a molecular aggregate may be a single type, and may combine 2 or more types.

Furthermore, as the lake material represented by the general formula (1), for example, it can be prepared with reference to the specifications of International Publication No. 2012/144520 and International Publication No. 2018/003706.

On the other hand, in the general formula (2), R ^I to R ^VI each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, and R ^I and R ^II , R ^III and R ^IV , R ^V and R ^VI may be bonded to form a ring structure. R ^I to R ^VI may be the same as R ⁱ to R ^v of the above general formula (1), respectively. In the general formula (2), R ^VII and R ^VIII each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom or a cyano group, and these may also be the same as those described above R ^vi and R ^vii of the general formula (1) are the same. In the general formula (2), Ar ² represents a divalent aromatic heterocyclic group that may have a substituent, and the Ar ² may be the same as the aromatic heterocyclic group in Ar ¹ of the above-mentioned general formula (1) . Also, in the general formula (2), E ^m- represents an m-valent polyacid anion, and the m-valent polyacid anion may be the same as the c-valent polyacid anion of the above-mentioned 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. A plurality of cations present in the general formula (2) may be alone or in combination of two or more. Moreover, an anion may be independent of 1 type, and may combine 2 or more types. Also, k and l in the general formula (2) may be the same as f and g in the above-mentioned general formula (1). Furthermore, as the lake material represented by the general formula (2), for example, it can be prepared with reference to JP-A-2017-16099.

Also, as the lake color material of the triarylmethane dye used in the photosensitive colored resin composition of the present invention, it is not limited to the color material represented by the above general formula (1) and the color material represented by the above general formula (2). One or more of the color materials can be selected and used appropriately. For example, the cations of the triarylmethane dyes described in JP-A-2015-96947, JP-A-2016-27149, and JP-A-2017-16099 and the above-mentioned various Lake color material of polyacid anion; or the triarylmethane series dyes and poly Acid lake color material.

In the photosensitive colored resin composition of the present invention, the lake color material of the above-mentioned triarylmethane dye may be used alone or in combination of two or more.

＜Other color materials＞ The coloring material used in the present invention contains a triarylmethane-based dye lake coloring material as an essential component, and other coloring materials may be used in combination to adjust the color tone within the range that does not impair the effect of the present invention. As other coloring materials, known pigments, dyes, lake coloring materials, etc. can be used alone, or two or more of them can be used in combination.

染料及𠮿

系染料之色澱色材等。 As other color materials, among them, other blue color materials, purple color materials, and red color materials can be suitably used, but are not limited to these. As other blue color materials, there are known organic blue pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6. As the purple color material, there are known organic purple pigments such as CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, and 38. Examples of red or purple color materials include those described in International Publication No. 2020/071041, Japanese Patent Application Publication No. 2018-100323, and International Publication No. 2014/123125.

Dyes and 𠮿

It is a dye lake color material, etc.

＜Containing ratio of color material＞ In the photosensitive colored resin composition of the present invention, within the range that does not impair the effect of the present invention, other color materials other than triarylmethane-based dye lake color materials may be contained in the color material, triarylmethane The content ratio of the dye-based lake color material to the total color material is preferably from 70% by mass to 100% by mass, more preferably from 80% by mass to 100% by mass, and still more preferably at least 90% by mass 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less.

The average primary particle size of the color material used in the present invention is not particularly limited as long as the required color development can be achieved when the coloring layer of the color filter is made, depending on the color material used Depending on the type, it is preferably in the range of 10-100 nm, more preferably 15-60 nm. When the average primary particle diameter of a coloring material is the said range, the display device equipped with the color filter manufactured using the photosensitive colored resin composition of this invention can be made into a high-contrast and high-quality one.

Also, the average dispersed particle size of the color material in the photosensitive coloring resin composition varies depending on the type of color material used, and is preferably in the range of 10-100 nm, more preferably in the range of 15-60 nm. The average dispersed particle size of the color material in the photosensitive colored resin composition is the dispersed particle size of the color material particles dispersed in the dispersion medium containing at least a solvent, which can be measured by a laser light scattering particle size distribution meter. As the measurement of particle size using a laser light scattering particle size distribution meter, the photosensitive coloring resin composition can be appropriately diluted (for example, 1000 times, etc.) with the solvent used in the photosensitive coloring resin composition so that the laser light scattering particle size distribution can be used The concentration measured by the meter is measured at 23° C. by the dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average particle size distribution here is the volume average particle size.

The color material used in the present invention can be produced by known methods such as recrystallization method and solvent salt milling method. Moreover, a commercially available color material can also be used by subjecting it to miniaturization treatment.

In the photosensitive colored resin composition of the present invention, the content of the color material is not particularly limited. The content of the coloring material is usually in the range of 3% by mass to 65% by mass, preferably 4% by mass, relative to the total solid content of the photosensitive colored resin composition in terms of dispersibility and dispersion stability It is in the range of ∼60% by mass, more preferably in the range of 15% by mass to 60% by mass. When it is more than the said lower limit, the colored layer when apply|coating the photosensitive colored resin composition to predetermined film thickness (normally 1.0 micrometer - 5.0 micrometer) has sufficient color density. Moreover, if it is below the said upper limit, the colored layer which is excellent in storage stability and has sufficient hardness or the adhesiveness with a board|substrate can be obtained. Especially when forming a colored layer with a high concentration of coloring materials, the total content of coloring materials is preferably in the range of 20% by mass to 65% by mass relative to the total solid content of the photosensitive colored resin composition. More preferably, it exists in the range of 30 mass % - 60 mass %.

[Alkali-soluble resin] The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that function as a binder resin and are soluble in an alkaline developer used for pattern formation. In the present invention, the alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard. Preferred alkali-soluble resins in the present invention are resins having acid groups and usually carboxyl groups. Specifically, for example, acrylic acid-based copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups may be mentioned. Resin, epoxy (meth)acrylate resin with carboxyl group, etc.

Among them, those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are more preferable. In the case where a photopolymerizable functional group is contained, photopolymerizable compounds such as the alkali-soluble resins or the alkali-soluble resin and a polyfunctional monomer can be formed during the hardening step of the resin composition when producing a color filter. Crosslinks. The film strength of the cured film is further improved, the development resistance is improved, and the heat shrinkage of the cured film is suppressed, and the adhesiveness with the substrate becomes excellent. The method for introducing an ethylenically unsaturated bond into the alkali-soluble resin may be appropriately selected from previously known methods. For example, a method such as adding a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule to the carboxyl group of an alkali-soluble resin, such as glycidyl (meth)acrylate, etc., and introducing a side chain Ethylenically unsaturated bonds; or introduce structural units with hydroxyl groups into the copolymer in advance, add compounds with isocyanate groups and ethylenically unsaturated bonds in the molecule, and introduce ethylenically unsaturated bonds into the side chains. Hereinafter, a monomer containing a group having an ethylenically unsaturated bond (ethylenically unsaturated group-containing monomer) may be simply referred to as an ethylenically unsaturated monomer.

Moreover, it is preferable that an alkali-soluble resin further has a hydrocarbon ring from the point which is excellent in the adhesiveness of a colored layer. Since the alkali-soluble resin contains a hydrocarbon ring as a bulky group, the shrinkage during curing is suppressed, the peeling between the substrate and the substrate is eased, and the substrate adhesion is improved. Such hydrocarbon rings include, for example, aliphatic hydrocarbon rings which may have substituents, aromatic hydrocarbon rings which may have substituents, and combinations thereof. The hydrocarbon rings may have alkyl groups, carbonyl groups, carboxyl groups, oxycarbonyl groups, Amide group, hydroxyl group, nitro group, amino group, halogen atom and other substituents. The hydrocarbon ring may be contained as a monovalent group, or may be contained as a divalent or higher group.

Specific examples of hydrocarbon rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, nor-alkane, iso-alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclo[5.2.1.0(2,6)]decane, Cyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, stilbene and other aromatic hydrocarbon rings; biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene and other chain poly A ring, or a Cardo structure (9,9-diaryl oxane); a group in which a part of these groups is substituted by a substituent, etc. As said substituent, an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom, etc. are mentioned.

When an aliphatic hydrocarbon ring is contained as a hydrocarbon ring, it is preferable in terms of improving the heat resistance or adhesiveness of the colored layer and improving the brightness of the obtained colored layer. In addition, when the above-mentioned Cardo structure is included, the curability of the colored layer is improved, the fading of the color material is suppressed, and the solvent resistance (NMP (N-methylpyrrolidone, N-methylpyrrolidone) swelling suppression) is improved. Yan Youjia.

Acrylic resins such as an acrylic copolymer containing a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group are obtained by, for example, copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and, if necessary, by a known method. A (co)polymer obtained by (co)polymerizing other monomers. Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, and crotonic acid. , cinnamic acid, acrylic acid dimer, etc. Also, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω -Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as carboxyl group precursors. Among them, (meth)acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin in the present invention is preferably an acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and a copolymer containing a carboxyl group such as a styrene-acrylic copolymer, and more preferably a copolymer containing a carboxyl group. Carboxyl group-containing copolymers such as structural units, structural units having hydrocarbon rings and structural units having ethylenically unsaturated bonds, acrylic copolymers, and styrene-acrylic copolymers.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include: cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid Isophthalate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., are more effective in maintaining the cross-sectional shape of the colored layer after development even during heat treatment. It is preferred to use at least one of cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene 1 species.

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

The carboxyl-containing copolymer can be prepared into an alkali-soluble resin with required properties by properly adjusting the addition amount of each structural unit. The amount of the carboxyl group-containing ethylenically unsaturated monomer added is preferably at least 5% by mass, more preferably at least 10% by mass, based on the total amount of monomers, from the viewpoint of obtaining a good pattern. On the other hand, in terms of suppressing film roughness on the surface of the pattern after development, the amount of ethylenically unsaturated carboxyl group-containing monomer added is preferably 50% by mass or less, more preferably 40% by mass or less.

In addition, in carboxyl-containing copolymers such as acrylic copolymers containing structural units having ethylenically unsaturated bonds and styrene-acrylic copolymers that can be used more preferably as alkali-soluble resins, epoxy group The amount of the compound having an ethylenically unsaturated bond relative to the carboxyl group-containing ethylenically unsaturated monomer is preferably from 10% by mass to 95% by mass, more preferably from 15% by mass to 90% by mass.

The preferred mass average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When it is 1,000 or more, the adhesive function after hardening improves, and when it is 50,000 or less, pattern formation will become favorable at the time of image development with an alkaline developing solution.

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and an epoxy (meth)acrylate resin obtained by reacting an epoxy compound with a monocarboxylic acid containing an unsaturated group with an acid anhydride is suitable. ) acrylate compounds. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. As the epoxy (meth)acrylate resin having a carboxyl group, it is also preferable to have the above-mentioned hydrocarbon ring in the molecule. Among them, the curability of the colored layer is improved, the fading of the colored material is suppressed, and the residual film rate of the colored layer is improved. On the other hand, those containing a Cardo structure are preferable. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, and may use 2 or more types together.

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

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferable in terms of obtaining effects such as increased film strength of the cured film, improved development resistance, and excellent adhesion to the substrate. It is in the range of 100-2000, more preferably in the range of 140-1500. When the ethylenically unsaturated bond equivalent is 2000 or less, it will be excellent in image development resistance and adhesiveness. Moreover, if it is 100 or more, since the ratio of other structural units, such as the structural unit which has the said carboxyl group, or the structural unit which has a hydrocarbon ring, can be relatively increased, it is excellent in developability and heat resistance. Here, the ethylenically unsaturated bond equivalent is the mass average molecular weight with respect to 1 mol of ethylenically unsaturated bond in the said alkali-soluble resin, and is represented by following numerical formula (1).

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

The above-mentioned ethylenically unsaturated bond equivalent can also be calculated by measuring the number of ethylenically unsaturated bonds contained in 1 g of alkali-soluble resin according to the test method of iodine value described in JIS K 0070:1992, for example.

The alkali-soluble resin used in the photosensitive colored resin composition may be used alone or in combination of two or more, and its content is not particularly limited. With respect to the total solid content of the photosensitive colored resin composition, the alkali The soluble resin is preferably within the range of 5% by mass to 60% by mass, and more preferably within the range of 8% by mass to 40% by mass. If the content of the alkali-soluble resin is more than the above lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is below the above upper limit, film roughness or pattern defects can be suppressed during 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 usually a compound having two or more ethylenically unsaturated bonds can be suitably used, especially A polyfunctional (meth)acrylate having two or more acryl groups or methacryl groups is preferable. As such a polyfunctional (meth)acrylate, what is necessary is just to select suitably from well-known thing beforehand, and to use it. As a specific example, what is described in Unexamined-Japanese-Patent No. 2013-029832, etc. are mentioned, for example.

These polyfunctional (meth)acrylates may be used alone or in combination of two or more. Also, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional (meth)acrylate preferably has three or more (trifunctional) vinylic resins capable of polymerizing. Those with unsaturated bonds are preferably poly(meth)acrylates of polyhydric alcohols with a valence of more than three or their modified dicarboxylic acids, specifically, trimethylolpropane tri(methyl)propane base) acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

The photopolymerizable compound used in the present invention preferably contains a photopolymerizable compound containing an alkylene oxide in terms of achieving both a high residual film rate after image development and a thin line width. As a photopolymerizable compound containing an alkylene oxide, Preferably, the photopolymerizable compound containing ethylene oxide and/or propylene oxide is mentioned. When the photopolymerizable compound containing the above-mentioned alkylene oxide is contained, active radicals are regenerated from peroxyl radicals which have lost their polymerization activity due to oxygen inhibition, so that curability is improved. Examples of the photopolymerizable compound containing alkylene oxide include: alkylene oxide-modified pentaerythritol tri(meth)acrylate, alkylene oxide-modified pentaerythritol tetra(meth)acrylate, alkylene oxide-modified di 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 glycerin di(meth)acrylate, etc., More specifically, 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, etc. Among them, it is more preferable to include ethylene oxide-modified diglycerin tetra(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate.

A photopolymerizable compound may be used individually by 1 type, or may mix and use 2 or more types. As a photopolymerizable compound, the photopolymerizable compound which contains an alkylene oxide, and the photopolymerizable compound which does not contain an alkylene oxide can be mixed and used. When the photopolymerizable compound containing alkylene oxide is contained, the content is preferably in the range of 3% by mass to 50% by mass, more preferably in the range of 5% by mass to 30% by mass, based on the total amount of the photopolymerizable compound Inside.

The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but it is preferably in the range of 5% by mass to 60% by mass relative to the total solid content of the photosensitive colored resin composition. More preferably, it exists in the range of 10 mass % - 40 mass %. If the content of the photopolymerizable compound is more than the above-mentioned lower limit value, then the photocuring will proceed sufficiently, the elution during development of the exposed part can be suppressed, the deviation of the line width is suppressed, and the solvent resistance becomes good. In addition, if the photopolymerizable compound Alkali developability is sufficient if the content is below the above upper limit.

等9-氧硫𠮿

類。 其中，本發明所使用之光起始劑就感度優異之方面而言，較佳為包含選自肟酯類及α-胺基酮類中之至少1種，就圖案形成時之線寬調整與顯影耐性之觀點而言，較佳為α-胺基酮類。由於具有三級胺結構之α-胺基酮類於分子內具有作為氧抑止劑之三級胺結構，故而自起始劑產生之自由基不易因氧而失活，能夠提高感度，因此較佳。 又，作為光起始劑，就抑制水斑、且提高感度之方面而言，亦較佳為將肟酯類與α-胺基酮類組合使用。再者，水斑係指若使用提高鹼性顯影性之成分，則鹼性顯影後，於利用純水沖洗後產生如水浸染之痕跡之情況。此種水斑於後烘烤後會消失，因此製品並無問題，但於顯影後圖案化面之外觀檢查中，會作為斑點異常被檢測出，產生正常品與異常品不加區別之問題。因此，於外觀檢查中，若降低檢查裝置之檢查感度，則結果會引起最終之彩色濾光片製品之良率降低而成為問題。 又，作為光起始劑，就調整感度、抑制水斑、顯影耐性提高之方面而言，較佳為將選自肟酯類及α-胺基酮類中之至少1種與9-氧硫𠮿

類加以組合。 [Photoinitiator] The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and may be used in combination of 1 or 2 or more types of previously known various initiators. As the photoinitiator, for example, benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (for example, Hicure ABP, Kawaguchi Pharmaceutical Co., Ltd. Manufacturing), 4-methoxy-4'-dimethylaminobenzophenone and other aromatic ketones; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; 2-(o-chlorophenyl)- 4,5-phenylimidazole dimer and other biimidazoles; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyl oxadiazoles Compounds; 2-(4-butoxy-naphthalene-1-yl)-4,6-bis-trichloromethyl-S-trichloromethyl-S-three sulfones and other methyl-S-three sulfides; 1,2-octanyl Ketone-1-[4-(phenylthio)-, 2-(o-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-,1-(o-acetyloxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010-527339 , Japanese Patent Publication No. 2010-527338, Japanese Patent Application Publication No. 2013-041153, etc. oxime esters such as oxime ester-based photoinitiators; 2-methyl-1-(4-methylthiobenzene base)-2-morpholinopropan-1-one (such as Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1 -butanone (for example, Irgacure 369, manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene α-amino ketones such as base]-1-butanone (Irgacure 379EG, manufactured by BASF Corporation); diethyl-9-oxothiophenone

9-oxosulfur

kind. Among them, the photoinitiator used in the present invention preferably contains at least one selected from the group consisting of oxime esters and α-amino ketones in terms of excellent sensitivity. From the viewpoint of development resistance, α-aminoketones are preferred. Since the α-aminoketones with a tertiary amine structure have a tertiary amine structure as an oxygen inhibitor in the molecule, the free radicals generated from the initiator are not easily inactivated by oxygen, and the sensitivity can be improved, so it is better . Also, as a photoinitiator, it is also preferable to use oxime esters and α-amino ketones in combination in terms of suppressing water spots and improving sensitivity. Furthermore, the water spot refers to the situation that if a component that improves the alkali developability is used, after the alkali development is rinsed with pure water, there will be traces such as water staining. This kind of water spots will disappear after post-baking, so there is no problem with the product, but in the visual inspection of the patterned surface after development, it will be detected as abnormal spots, causing the problem that normal products and abnormal products cannot be distinguished. Therefore, in the visual inspection, if the inspection sensitivity of the inspection device is lowered, the yield rate of the final color filter product will decrease as a result, which becomes a problem. In addition, as a photoinitiator, it is preferable to combine at least one selected from oxime esters and α-amino ketones with 9-oxysulfur in terms of adjusting sensitivity, suppressing water spots, and improving development resistance. 𠮿

Classes are combined.

The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as it does not impair the effect of the present invention. Preferably, it exists in the range of 0.1 mass % - 12.0 mass %, More preferably, it exists in the range of 1.0 mass % - 8.0 mass %. If the content is not less than the above-mentioned lower limit, the photocuring will proceed sufficiently, the elution of the exposed portion during development will be suppressed, and the solvent resistance will become good. On the other hand, if it is not more than the above-mentioned upper limit, the obtained coloring can be suppressed. The reduction of the brightness of the layer due to yellowing. In addition, the content ratio of the above-mentioned photopolymerizable compound and the above-mentioned photoinitiator used in the photosensitive coloring resin composition can suppress line width deviation and improve solvent resistance, and further improve the effect of suppressing development residue. On the other hand, relative to 100 parts by mass of the above-mentioned photopolymerizable compound, the total content ratio of the above-mentioned photoinitiator 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, it is 30 mass parts or less. Also, the ratio of the total mass of the above-mentioned photoinitiator to the total mass of the above-mentioned photoinitiator and the above-mentioned ultraviolet absorber is preferably in the range of 80% by mass to 98% by mass, more preferably 82% by mass to 96% by mass % range. If the content is more than the above lower limit, sufficient photocurability can be ensured even in the presence of an ultraviolet absorber. On the other hand, if it is below the above upper limit, the effect of adjusting the line width of the ultraviolet absorber can be 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 each component in the photosensitive colored resin composition and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types. As specific examples of solvents, for example, alcohol-based solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; Carbitol-based solvents such as oxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate Esters, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate and other ester solvents; acetone , methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketone solvents; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3 acetic acid - Glycol ether acetate-based solvents such as methyl-1-butyl ester, 3-methoxybutyl acetate, and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethyl acetate Carbitol acetate solvents such as ethyl ethyl ester and butyl carbitol acetate (BCA); diacetate esters such as propylene glycol diacetate and 1,3-butanediol diacetate; Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether Glycol ether solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other aprotic amide solvents; γ-butyrolactone, etc. Lactone solvents; tetrahydrofuran and other cyclic ether solvents; benzene, toluene, xylene, naphthalene and other unsaturated hydrocarbon solvents; N-heptane, N-hexane, N-octane and other saturated hydrocarbon solvents; toluene, Organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used from the point of solubility of other components. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetic acid in terms of solubility of other components or coating suitability. 1 of the group consisting of ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate more than one species.

In the photosensitive colored resin composition of this invention, content of a solvent should just be set suitably within the range which can form a colored layer with high precision. It can exist in the range of 55 mass % - 95 mass % normally with respect to the whole quantity of the photosensitive coloring resin composition containing this solvent, Preferably it can exist in the range of 65 mass % - 88 mass %. When content of the said solvent exists in the said range, it can become excellent in applicability.

[Dispersant] In the photosensitive colored resin composition of the present invention, the above-mentioned color material can be used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine can be used. Among the surfactants, polymer dispersants are preferred in terms of being able to disperse uniformly and finely.

Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; ) ammonium salts or (partial) alkylamine salts; (co)polymers of hydroxyl-containing polyacrylates and other unsaturated carboxylic acid esters containing hydroxyl groups or their modified products; polyurethanes; Saturated polyamides; Polysiloxanes; Long-chain polyaminoamide phosphates; Polyethyleneimine derivatives (by poly(lower alkyleneimine) and polyesters containing free carboxyl groups Amides or bases thereof obtained by the reaction); polyallylamine derivatives (cocondensation of polyallylamine with polyesters, polyamides or esters and amides selected from the group having free carboxyl groups) A reaction product obtained by reacting one or more of the three compounds of the compound (polyesteramide), etc. When the polymer dispersant is a copolymer, it can be any of block copolymer, graft copolymer or random copolymer. From the viewpoint of dispersibility, block copolymer and graft copolymer are preferred. copolymer.

The dispersing agent can be appropriately selected according to the type of color material, and the one with good dispersibility is not particularly limited. When dispersing the color material of the above-mentioned triarylmethane dye lake, as a dispersant, it is preferable to use an acidic color material. Acidic dispersant of polymer dispersant. As the acidic dispersant used for the dispersion of the color lake color material, for example, one selected from the polymers with structural units represented by the general formula (I) described below and the block copolymers containing carboxyl groups can be suitably used. At least 1 species. When further using a pigment as a color material and dispersing it, at least one selected from the group consisting of acidic or alkaline polymer dispersants and urethane-based dispersants can be used depending on the type of pigment. Acidic or alkaline polymer dispersants can be used. In the case of dispersing an alkaline-treated pigment, it is preferable to use an acidic dispersant as an acidic polymer dispersant, and in the case of dispersing an acid-treated pigment, it is preferable to use an alkaline high Alkaline dispersant of molecular dispersant. As the basic dispersant, for example, a polymer selected from repeating units having a tertiary amine, and at least a part of the amine groups in a polymer containing a repeating unit having a tertiary amine formed with an organic acid compound can be suitably used. At least one of the group consisting of salt-type polymers formed from salts. The urethane-based dispersant is a compound having one or more urethane bonds (-NH-COO-) in one molecule. As the urethane-based dispersant, for example, a reaction product of a polyisocyanate having two or more isocyanate groups in one molecule and a polyester having a hydroxyl group at one or both ends can be suitably used.

<Polymer having a structural unit represented by the general formula (I)> A polymer having a structural unit represented by the following general formula (I) can be preferably used as a coloring material for the above-mentioned triarylmethane-based dye lake Dispersant. If a polymer having a structural unit represented by the following general formula (I) is used as an acidic dispersant, the dispersibility and heat resistance of the color lake material of the above-mentioned triarylmethane dyes can be improved, and the color lake after heating can be suppressed. Chroma change of color material. Also, when using a color lake material and a pigment together as a color material, by using a polymer having a structural unit represented by the following general formula (I) as a dispersant, it is possible to form an improved pigment dispersibility and storage stability. Colored layer with improved performance, substrate adhesion and uniformity of coating film. Since the polymer having the structural unit represented by the following general formula (I) is a polymer of an ethylenically unsaturated monomer, it is estimated that the heat resistance of the skeleton is higher than that of a polyether or polyester polymer. And there are multiple acidic phosphorus compound groups (-P(=O)(-R ¹² )(OH)) and their salts (-P(=O)(-R ¹² )(O ^- X ⁺ )) Strong adsorption to the surface of the micronized color material. In addition, it is estimated that if the surface of the color material is covered with at least one of the acidic phosphorus compound group and its salt, the attack (hydrogen abstraction or replacement reaction) of active oxygen such as peroxyl radicals on the pigment skeleton of the color lake material can be suppressed. etc.) to suppress the deterioration of the lake material (oxidative deterioration).

(通式(I)中，L ¹¹為直接鍵或二價連結基，R ¹¹為氫原子或甲基，R ¹²為羥基、烴基、-[CH(R ¹³)-CH(R ¹⁴)-O] _x1-R ¹⁵、-[(CH ₂) _y1-O] _z1-R ¹⁵、或-O-R ¹⁶所表示之一價基，R ¹⁶為烴基、-[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、或-CH ₂-C(R ²¹)(R ²²)-CH ₂-OH所表示之一價基。 R ¹³及R ¹⁴分別獨立為氫原子或甲基，R ¹⁵為氫原子、烴基、-CHO、-CH ₂CHO、-CO-CH=CH ₂、-CO-C(CH ₃)=CH ₂或-CH ₂COOR ²³所表示之一價基，R ²³為氫原子或碳數為1個以上5個以下之烷基。R ¹⁷、R ¹⁸、R ¹⁹、R ²⁰、R ²¹及R ²²分別獨立為氫原子、烴基、或具有選自醚鍵及酯鍵中之1種以上之烴基，R ¹⁷及R ¹⁹可互相鍵結而形成環結構。於形成上述環狀結構之情形時，該環狀結構可進而具有取代基R ²⁴，R ²⁴為烴基、或具有選自醚鍵及酯鍵中之1種以上之烴基。上述烴基可具有取代基。X表示氫原子或有機陽離子。x1表示1以上18以下之整數，y1表示1以上5以下之整數，z1表示1以上18以下之整數) [chemical 10]

(In general formula (I), L ¹¹ is a direct bond or a divalent linking group, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydroxyl group, a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ )-O ] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , or a valent group represented by -OR ¹⁶ , where R ¹⁶ is a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ ) -O] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , -C(R ¹⁷ )(R ¹⁸ )-C(R ¹⁹ )(R ²⁰ )-OH, or -CH ₂ A valent group represented by -C(R ²¹ )(R ²² )-CH ₂ -OH. R ¹³ and R ¹⁴ are independently a hydrogen atom or a methyl group, and R ¹⁵ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ A valence group represented by CHO, -CO-CH=CH ₂ , -CO-C(CH ₃ )=CH ₂ or -CH ₂ COOR ²³ , R ²³ is a hydrogen atom or a carbon number of 1 to 5 Alkyl. R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, and R ¹⁷ and R ¹⁹ Can be bonded to each other to form a ring structure. In the case of forming the above-mentioned ring structure, the ring structure can further have a substituent R ²⁴ , R ²⁴ is a hydrocarbon group, or has more than one selected from ether bonds and ester bonds 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 being a direct bond means that a phosphorus atom is directly bonded to a carbon atom of the main chain skeleton without a linking group. The divalent linking group in L ¹¹ is not particularly limited as long as it can link a carbon atom of the main chain skeleton with a phosphorus atom. As the divalent linking group in ^L11 , for example, it can be exemplified: a linear, branched or cyclic alkylene group; a linear, branched or cyclic alkylene group having a hydroxyl group; an arylylene group, -CONH - group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof. Furthermore, in the present invention, the orientation of the bond of the divalent linking group is arbitrary. That is, when the divalent linking group includes -CONH-, -CO may be the carbon atom side of the main chain and -NH may be the phosphorus atom side of the side chain, or conversely, -NH may be the carbon atom side of the main chain side and -CO is the phosphorus atom side of the side chain.

Among them, in terms of dispersibility, L ¹¹ in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group. For example, when L ¹¹ is a divalent linking group including a -COO- group, it is preferable that L ¹¹ is a -COO-L ^11' -group (here, L ^11' is a carbon number that may have a hydroxyl group and is 1 More than 8 alkylene groups, -[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 ^L13 are independently a hydrogen atom, a methyl group, or a hydroxyl group. x represents an integer ranging from 1 to 18, and y represents an integer ranging from 1 to 5 Integer, z represents an integer ranging from 1 to 18, and w represents an integer ranging from 1 to 18).

The alkylene group with 1 to 8 carbons in L ^11' can be linear, branched, or cyclic, such as methylene, ethylene, trimethylene, alkene In propyl groups, various butyl groups, various pentylene groups, various hexylene groups, various octylene groups, etc., a part of hydrogen may be substituted by hydroxyl groups. x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably for 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 an integer of 1 to 4.

As a suitable specific example of L ¹¹ in the general formula (I), for example, -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-, etc., but not limited thereto.

As the hydrocarbon group in ^R12 , for example, 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 may be mentioned. The above-mentioned alkyl group having 1 to 18 carbons may be linear, branched, or cyclic, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl Base, cyclopentyl, cyclohexyl, ??, iso??, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc. The above-mentioned alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited, but the double bond is preferably located at the end of the alkenyl group in terms of the reactivity of the obtained polymer. As an aryl group, a phenyl group, a biphenylyl group, a naphthyl group, a tolyl group, a xylyl group etc. are mentioned, It may further have a substituent. The carbon number of the aryl group is preferably from 6 to 24, and more preferably from 6 to 12. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group etc. are mentioned, It may further have a substituent. The number of carbon atoms in the aralkyl group is preferably from 7 to 20, and more preferably from 7 to 14. The above-mentioned alkyl group or alkenyl group may have a substituent, and the substituent may, for example, be a halogen atom such as F, Cl or Br, or a nitro group. In addition, as the substituent of the aromatic ring such as the above-mentioned aryl group or aralkyl group, in addition to straight-chain or branched-chain alkyl groups having 1 to 4 carbon atoms, alkenyl groups, nitro groups, etc. , halogen atoms, etc. Furthermore, the carbon number of the substituent is not included in the above preferred carbon number. In the above-mentioned ^R12 , x1 is the same as the above-mentioned x, y1 is the same as the above-mentioned y, and z1 is the same as the above-mentioned z. Examples of the hydrocarbon group in R ¹⁵ to R ²² include the same ones as those in R ¹² described above.

R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² have at least one hydrocarbon group selected from ether bonds and ester bonds as -R'-OR", -R'-(C=O )-OR", or -R'-O-(C=O)-R"(R' and R" are hydrocarbon groups, or groups that are bonded to hydrocarbon groups through at least one of ether bonds and ester bonds) foundation. One group may have two or more ether bonds and ester bonds. When the hydrocarbon group is monovalent, examples include alkyl, alkenyl, aralkyl, and aryl groups. When the hydrocarbon group is divalent, examples include alkylene, alkenylene, arylylene, and the combined basis of such.

When R ¹⁷ and R ¹⁹ are bonded to form a ring structure, the number of carbons forming the ring structure is preferably 5 or more and 8 or less, more preferably 6, that is, a 6-membered ring, preferably cyclohexane ring. The hydrocarbon group in the substituent R ²⁴ , or the hydrocarbon group having one or more types selected from ether linkages and ester linkages may be the same as those of the aforementioned R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² .

In terms of excellent dispersibility and dispersion stability of the dispersed particles, the above-mentioned R ¹² is preferably a hydroxyl group, a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , - [(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , or a valent group represented by -OR ¹⁶ , more preferably hydroxyl, methyl, ethyl, vinyl, aryl or aralkyl that may have substituents , vinyl, allyl, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , or -OR ¹⁶ One valent group and R ¹³ and R ¹⁴ are independently a hydrogen atom or a methyl group, R ¹⁵ is -CO-CH=CH ₂ or -CO-C(CH ₃ )=CH ₂ , wherein, R ¹² is more preferably Aryl group, vinyl group, methyl group and hydroxyl group which may have a substituent.

Also, in terms of improving alkali resistance, R ¹² is preferably a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , or -[(CH ₂ ) _y1 -O ] _z1 -R ¹⁵ represents a valence group. In the case of having a structure in which carbon atoms are directly bonded to phosphorus atoms, it is presumed that since hydrolysis is difficult, a resin layer excellent in alkali resistance can be formed. Among them, ^R12 is preferably a methyl group, an ethyl group, an aryl group or an aralkyl group that may have a substituent, vinyl group, allyl group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , or -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ represents a valent group and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is -CO-CH=CH ₂ or -CO-C(CH ₃ )=CH ₂ . Among them, in terms of dispersibility, R ¹² is more preferably an aryl group which may have a substituent.

Also, in the general formula (I), X represents a hydrogen atom or an organic cation. Organic cations refer to those in which the cation portion contains carbon atoms. Examples of organic cations include ammonium cations such as imidazolium cations, pyridinium cations, amidinium cations, piperidinium cations, pyrrolidinium cations, tetraalkylammonium cations, and trialkylammonium cations, and trialkylammonium cations. cations such as cerium cations, phosphonium cations such as tetraalkylphosphonium cations, and the like. Among them, protonated nitrogen-containing organic cations are preferred in terms of dispersibility and alkali developability. Among them, when the organic cation has an ethylenically unsaturated bond, it is preferable in terms of being able to impart curability.

The structural unit represented by general formula (I) may be contained in a polymer individually by 1 type, and may contain 2 or more types.

In the polymer, the structural unit represented by the general formula (I) may contain two structural units in which X is a hydrogen atom and X is a structural unit of an organic cation. In the case of including the two structural units, as long as good dispersibility and dispersion stability can be exerted, there is no special limitation, and X is the ratio of the number of structural units of organic cations to that represented by the general formula (I). The total number of structural units of the structural units is preferably from 0 to 50 mol%.

The synthesis method of the polymer having the structural unit represented by the general formula (I) is not particularly limited. For example, a polymer having the structural unit represented by the general formula (I) can be synthesized with reference to Japanese Patent Application Laid-Open No. 2017-2191. The polymer having the structural unit represented by the general formula (I) is preferably the reaction product of a polymer having at least one of epoxy group and cyclic ether group in the side chain and an acidic phosphorus compound, and is a compound of the acidic phosphorus compound group. At least a portion of the polymer is capable of forming a salt.

In an embodiment of the present invention, it is preferable that the polymer having the structural unit represented by the general formula (I) further has a solvent-affinity site from the viewpoint of dispersibility. Such a polymer preferably has a structural unit represented by the above-mentioned general formula (I) and A graft copolymer of 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).

(通式(II)中，L ²¹表示直接鍵或二價連結基，R ²⁵表示氫原子或甲基，Polymer表示具有下述通式(IV)所表示之結構單元之聚合物鏈。 通式(III)中，R ²⁶為氫原子或甲基，R ²⁷為烴基、-[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'或-O-CO-R ^30"所表示之一價基，R ²⁸及R ²⁹分別獨立為氫原子或甲基，R ³⁰為氫原子、烴基、-CHO、-CH ₂CHO或-CH ₂COOR ³¹所表示之一價基，R ^30'為烴基、-[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所表示之一價基，R ^30"為碳數為1個以上18個以下之烷基，R ³¹為氫原子或碳數為1個以上5個以下之烷基。上述烴基可具有取代基。 x2及x2'表示1以上18以下之整數，y2及y2'表示1以上5以下之整數，z2及z2'表示1以上18以下之整數) [chemical 11]

(In the general formula (II), ^L21 represents a direct bond or a divalent linking group, ^R25 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 (III), R ²⁶ is a hydrogen atom or a methyl group, R ²⁷ is a hydrocarbon group, -[CH(R ²⁸ )-CH(R ²⁹ )-O] _x2 -R ³⁰ , -[(CH ₂ ) _y2 -O] _z2 -R ³⁰ , -[CO-(CH ₂ ) _y2 -O] _z2 -R ³⁰ , -CO-OR ^30' or -O-CO-R ^30" , R ²⁸ and R ²⁹ respectively is independently a hydrogen atom or a methyl group, R ³⁰ is a valent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³¹ , 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 Represents a valent group, R ^30" is an alkyl group with 1 to 18 carbons, R ³¹ is a hydrogen atom or an alkyl group with 1 to 5 carbons. The above hydrocarbon groups may have substituents. x2 and x2' represent integers ranging from 1 to 18, y2 and y2' represent integers ranging from 1 to 5, z2 and z2' represent integers ranging from 1 to 18)

(通式(IV)中，R ³²為氫原子或甲基，R ³³為烴基、-[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或-O-CO-R ³⁸所表示之一價基，R ³⁴及R ³⁵分別獨立為氫原子或甲基，R ³⁶為氫原子、烴基、-CHO、-CH ₂CHO或-CH ₂COOR ³⁹所表示之一價基，R ³⁷為烴基、-[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所表示之一價基，R ³⁸為碳數為1個以上18個以下之烷基，R ³⁹為氫原子或碳數為1個以上5個以下之烷基，上述烴基可具有取代基。 n表示5以上200以下之整數。x3及x4表示1以上18以下之整數，y3及y4表示1以上5以下之整數，z3及z4表示1以上18以下之整數) [chemical 12]

(In general formula (IV), R ³² is a hydrogen atom or a methyl group, R ³³ is a hydrocarbon group, -[CH(R ³⁴ )-CH(R ³⁵ )-O] _x3 -R ³⁶ , -[(CH ₂ ) _y3 -O] _z3 -R ³⁶ , -[CO-(CH ₂ ) _y3 -O] _z3 -R ³⁶ , -CO-OR ³⁷ or -O-CO-R ³⁸ represents a valent group, R ³⁴ and R ³⁵ are independently a hydrogen atom or a methyl group, R ³⁶ is a valent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ , R ³⁷ is a hydrocarbon group, -[CH(R ³⁴ )- One of the valent groups represented by CH(R ³⁵ )-O] _x4 -R ³⁶ , -[(CH ₂ ) _y4 -O] _z4 -R ³⁶ , -[CO-(CH ₂ ) _y4 -O] _z4 -R ³⁶ , R ³⁸ is an alkyl group with 1 to 18 carbons, R ³⁹ is a hydrogen atom or an alkyl group with 1 to 5 carbons, and the above hydrocarbon groups may have substituents. n represents 5 to 200 Integer. x3 and x4 represent integers ranging from 1 to 18, y3 and y4 represent integers ranging from 1 to 5, z3 and z4 represent integers ranging from 1 to 18)

(Graft Copolymer) A graft copolymer preferably used as an acidic dispersant includes, for example, a graft copolymer 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. The divalent linking group in ^L21 is not particularly limited as long as it can link a carbon atom derived from an ethylenically unsaturated bond to a polymer chain. As the divalent linking group in ^L21 , for example, the same ones as the divalent linking group in ^L11 above can be mentioned.

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), the hydrocarbon group in ^R33 is preferably an alkyl group with 1 to 18 carbons, an alkenyl group with 2 to 18 carbons, an aralkyl group, or an aryl group. base. These are, for example, the same ones as those described above for ^R12 .

R ³⁶ is preferably a hydrogen atom, or an alkyl group, aralkyl group, aryl group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ with a carbon number of 1 to 18. ³⁷ is preferably an alkyl group, an aralkyl group, an aryl 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 represents a valent group. R ³⁸ is an alkyl group with 1 to 18 carbons, and R ³⁹ represents a hydrogen atom or an alkyl group with 1 to 5 carbons. Examples of the alkyl, aralkyl, and aryl groups having 1 to 18 carbon atoms in R ³⁶ and R ³⁷ above are the same as those for R ¹² above. The alkyl group in R ³⁸ and R ³⁹ above can be exemplified by the same ones as R ¹² above. When the aforementioned R ³⁶ , R ³⁷ and R ³⁹ are groups having an aromatic ring, the aromatic ring may further have a substituent. Examples of such substituents include linear, branched, and cyclic alkyl groups having 1 to 5 carbon atoms, halogen atoms such as alkenyl groups, nitro groups, F, Cl, and Br, etc. wait. Furthermore, the carbon number of the substituent is not included in the above preferred carbon number. In the above-mentioned ^R33 and ^R37 , x3 and x4 are the same as the above-mentioned x, y3 and y4 are the same as the above-mentioned y, and z3 and z4 are the same as the above-mentioned z.

Furthermore, the above-mentioned R ³³ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ may be further modified by an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, etc. within the range that does not hinder the dispersion performance of the above-mentioned graft copolymer. , isocyanate group, hydrogen bond forming group and other substituents. Moreover, after synthesizing the graft copolymer which has these substituents, it can react with the compound which has the functional group which reacts with this substituent, and a polymeric group, and can add a polymeric group. For example, a graft copolymer having a carboxyl group can be reacted with glycidyl (meth)acrylate, or a graft copolymer having an isocyanate group can be reacted with hydroxyethyl (meth)acrylate, and the addition polymeric base.

Among the above-mentioned structural units, the polymer chain having a structural unit represented by general formula (IV) preferably has a structural unit derived from the following substances: methyl (meth)acrylate, ethyl (meth)acrylate , Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-Ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, iso-(meth)acrylate, (meth)acrylate base) dicyclopentyl acrylate, adamantyl (meth)acrylate, styrene, α-methylstyrene, vinylcyclohexane, etc. However, it is not limited to these.

In the embodiment of the present invention, as the above-mentioned R ³³ and R ³⁷ , 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 color material dispersion. Specifically, for example, when the above-mentioned organic solvent is used as an organic solvent such as ether alcohol acetate, ether, and ester, which are generally used as organic solvents for color material dispersions, methyl, ethyl, Isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc. Here, the reason for setting the above-mentioned ^R33 and ^R37 in the above-mentioned manner is that: the structural unit including the above-mentioned ^R33 and ^R37 has solubility in the above-mentioned organic solvent, and the acidic phosphorus compound group of the above-mentioned monomer and the position of the salt thereof are color-sensitive. Particles such as color materials have high adsorption, so that the dispersibility and stability of particles such as color materials can be particularly excellent.

The weight average molecular weight of the polymer chains in the polymer is preferably in the range of 500 to 15,000, more preferably in the range of 1,000 to 8,000. By being in the above-mentioned range, sufficient steric repulsion effect as a dispersant can be maintained, and an increase in the time required for dispersion by particles such as a color material having a steric effect can also be suppressed.

Also, as a standard, it is preferable that the polymer chain in the polymer has a solubility of 50 (g/100 g solvent) or more at 23° C. with respect to the organic solvent used in combination.

The aforementioned polymer chains may be homopolymers or copolymers. In addition, the polymer chains contained in the structural unit represented by the general formula (II) may be one type alone or two or more types may be mixed in the graft copolymer.

The structural unit represented by the above-mentioned general formula (I) is preferably contained in a ratio of 3% by mass to 80% by mass in total, more preferably 10% by mass to 70% by mass, relative to all the structural units of the above-mentioned graft copolymer. % by mass or less, more preferably not less than 20% by mass and not more than 60% by mass. If the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity sites to the particles in the graft copolymer becomes appropriate, and the reaction to the organic solvent can be suppressed. The solubility of the product is reduced, so the adsorption of particles such as color materials becomes better, and excellent dispersibility and dispersion stability can be obtained. In addition, the acidic phosphorus compound group of the above-mentioned graft copolymer can stably exist locally around the color material, so a color filter excellent in heat resistance or contrast can be obtained. On the other hand, the structural unit represented by the above-mentioned general formula (II) is preferably contained in a ratio of 20% by mass to 97% by mass, more preferably 25% by mass or more, with respect to all the structural units of the above-mentioned graft copolymer 95% by mass or less, more preferably 40% by mass or more and 90% by mass or less. In addition, in this invention, the content ratio of each structural unit in a copolymer is calculated from the addition amount at the time of synthesizing a copolymer.

In addition, the weight average molecular weight of the graft copolymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 400,000, and still more preferably in the range of 5,000 to 300,000. Particles, such as a coloring material, can be uniformly disperse|distributed by being the said range.

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 that can be copolymerized with an ethylenically unsaturated monomer derived from the structural unit represented by the general formula (I) can be appropriately selected and copolymerized to introduce another structural unit.

(block copolymer) A preferred block copolymer as an acidic dispersant includes, for example, one 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). block copolymers. In this block copolymer, in the block part containing the structural unit represented by the said general formula (I), it is preferable to contain 3 or more structural units represented by the said general formula (I) in total. Among them, in terms of improving dispersibility and improving heat resistance, it is preferable to include 3 or more and 200 or less, more preferably include 3 or more and 50 or less, and still more preferably include 3 or more and 30 or less. the following. The structural unit represented by the above-mentioned general formula (I) only needs to function as a color material affinity site, and may contain one type, or may contain two or more types of structural units. In the case of including two or more structural units, two or more structural units may be randomly arranged in the block portion containing the structural unit represented by the above general formula (I).

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

The above-mentioned block copolymer has a block part including the structural unit represented by the above-mentioned general formula (III), thereby making the solvent affinity become good, the dispersibility and dispersion stability of the color material are good, and the heat resistance is also good, Furthermore, the resistance to N-methylpyrrolidone (NMP) (NMP resistance) becomes 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-OR ^30' or -O-CO-R ^30" represents a valence group. The hydrocarbon group in R ²⁷ can be the same as the above The one represented by ^R12 is the same.

In addition, the above-mentioned R ³⁰ is a valent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³¹ , and R ^30' is a hydrocarbon group, -[CH(R ²⁸ )-CH(R ²⁹ ) -O] _x2' -R ³⁰ , -[(CH ₂ ) _y2' -O] _z2' -R ³⁰ , -[CO-(CH ₂ ) _y2' -O] _z2' -R ³⁰ represents one of the valence groups , R ^30" is an alkyl group with 1 to 18 carbons, R ³¹ is a hydrogen atom or an alkyl group with 1 to 5 carbons, and the above hydrocarbon group may have a substituent. The hydrocarbon group in the above R ³⁰ It can be set to be the same as that represented by the above-mentioned R ^12. In the above-mentioned R ²⁷ and R ^30' , x2 and x2' are the same as the above-mentioned x, y2 and y2' are the same as the above-mentioned y, and z2 and z2' are the same as the above-mentioned z. , R ²⁷ in the structural unit represented by the above general formula (III) may be the same as or different from each other.

Among them, R ²⁷ and R ^30' are preferably those having excellent solubility in the solvents described below, for example, the same ones as R ³³ and R ³⁷ above are mentioned. In addition, R ²⁷ , R ³⁰ , R ^30' , R ^30" and R ³¹ in the above-mentioned general formula (IV) may be modified by alkoxy, hydroxyl, Substituents such as carboxyl, amine, epoxy, isocyanate, and hydrogen bond forming groups can also be used to react with compounds having the above-mentioned substituents after synthesizing the above-mentioned block copolymers, and Add the above-mentioned substituents. Also, after synthesizing the block copolymer with these substituents, it can be reacted with a compound having a functional group and a polymerizable group that reacts with the substituent to add polymerizable For example, a block copolymer having a glycidyl group can be reacted with (meth)acrylic acid, or a block copolymer having an isocyanate group can be reacted with hydroxyethyl acrylate to add into a polymeric base.

The number of structural units constituting the block portion including the structural unit represented by the general formula (III) is not particularly limited, and the solvent-affinity site and the color material-affinity site effectively function to improve the dispersibility of the color material dispersion On the other hand, it is preferably from 10 to 200, more preferably from 20 to 100, and still more preferably from 30 to 80.

In the above-mentioned block copolymer, the content ratio 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, relative to all the structural units of the above-mentioned block copolymer. % to 90% by mass.

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 contain one type, or may contain two or more types Structural units. In an embodiment of the present invention, when the structural unit represented by the general formula (III) contains two or more structural units, in the block portion containing the structural unit represented by the above general formula (III), two or more Structural units can be randomly arranged.

In the block copolymer used as a dispersant, the number of units m of the structural unit of the block portion comprising the structural unit represented by the general formula (I) and the number of blocks comprising the structural unit represented by the general formula (III) The ratio m/n of the unit number n of the structural unit of the segment is preferably in the range of 0.01 to 1, and in terms of the dispersibility and dispersion stability of the color material, it is more preferably in the range of 0.1 to 0.7 Inside.

As the bonding order of the above-mentioned block copolymer, as long as it has a block part containing a structural unit represented by the above general formula (I) and a block part containing a structural unit represented by the general formula (III), and can make the color As long as the material is stably dispersed, it is not particularly limited. In terms of excellent interaction with the color material and the ability to effectively inhibit the aggregation of the dispersants, it is preferable to include the structural unit represented by the above general formula (I) The block part is bonded only to one end of the above-mentioned block copolymer.

The weight average molecular weight of the block copolymer is not particularly limited, but is preferably from 2,500 to 500,000, more preferably from 3,000 to 400,000, and still more preferably More than 6,000 and less than 300,000.

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

On the other hand, as the above-mentioned carboxyl group-containing block copolymer, a block copolymer containing a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid can be included. An A block and a B block comprising structural units derived from alkyl (meth)acrylates. In the block copolymer containing a carboxyl group, the B block comprising a structural unit derived from an alkyl (meth)acrylate can be combined with the block copolymer comprising a structural unit represented by the above-mentioned general formula (I) The block portion of the structural unit represented by the general formula (III) is the same.

The content ratio (mole %) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials added at the time of production, and can be measured using an analysis device such as NMR. Moreover, the structure of a dispersing agent can be measured using NMR, various mass spectrometry, etc. In addition, the dispersant may be decomposed by thermal decomposition or the like if necessary, and the obtained decomposed products are subjected to 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 spectroscopy) and TOF-SIMS (time of flight secondary ion mass spectrometry, time of flight secondary ion mass spectrometry) and so on.

In the present invention, the content of the dispersant may be appropriately selected according to the type of color material used, and furthermore, the solid content concentration in the photosensitive colored resin composition described below. The content of the dispersant is preferably within the range of 2% by mass to 30% by mass, more preferably within the range of 3% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. If it is more than the said lower limit, it will be excellent in the dispersibility and dispersion stability of a color material, and the storage stability of a photosensitive colored resin composition will be more excellent. Moreover, developability will become favorable as it is below the said upper limit.

[Antioxidants] It is preferable that the photosensitive colored resin composition of this invention further contains at least 1 sort(s) of antioxidant and latent antioxidant from the point which improves heat resistance and brightness|luminance. The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from previously known ones. Specific examples of antioxidants include, for example, hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Generally, it is preferable to use a hindered phenolic antioxidant in terms of the ability to form a thin line pattern and in terms of heat resistance. The latent antioxidant used in the present invention is a compound having a protecting group that can be detached by heating, and the compound exhibits an antioxidant function through the detachment of the protecting group. Among them, preferred are those from which the protecting group can be easily detached by heating at 150° C. or higher. As the latent antioxidant used in the present invention, for example, those described in International Publication No. 2014/021023 and International Publication No. 2017/170263 may be mentioned. Among them, a latent antioxidant in which the phenolic hydroxyl group of the hindered phenolic antioxidant is protected by a protecting group is suitable, and more specifically, a carbamic acid such as a tertiary butoxycarbonyl group can be exemplified. The structure in which the hydrogen of the phenolic hydroxyl group of the hindered phenolic antioxidant is substituted with an ester-based protecting group is suitable.

As hindered phenolic antioxidants, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF Corporation), iso 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) cyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy- 3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) ( Trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5- Diethyl di-t-butyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, BASF company manufacture).

The content of the antioxidant is preferably within a range of 0.1% by mass to 10.0% by mass, more preferably within a range of 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive colored resin composition. When it is more than the said lower limit, it is excellent in the point which improves heat resistance and improves brightness. On the other hand, the colored resin composition of this invention can be made into the highly sensitive photosensitive resin composition as it is below the said upper limit.

[thiol compound] It is preferable that the photosensitive colored resin composition of this invention further contains a thiol compound from the point which improves the suppression effect of the film thickness change before and after image development by a thinner line width. The thiol compound is not subject to polymerization inhibition by oxygen due to the enethiol reaction, so it has excellent surface hardening properties and increases the residual film rate of development. The thiol compound also has the effect of making the line width thicker, but by using the ultraviolet absorber in combination, it has a synergistic effect of taking into account the thinner line width and increasing the residual film after development. The thiol compound may, for example, be a monofunctional thiol compound having one thiol group or a polyfunctional thiol compound having two or more thiol groups. It is more preferable to use a multifunctional thiol from the point of view of enhancing the effect of suppressing the change in film thickness before and after development with a thinner line width. Examples of monofunctional thiol compounds 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 polyfunctional thiol compounds include: 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3 ,5-tris-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate), etc. As the thiol compound, it can be used alone or in combination of two or more. Among them, pentaerythritol tetrakis(3-mercaptobutyl) is preferred in terms of improving the effect of suppressing the change in film thickness before and after development due to the thinner line width. esters). As content of a thiol compound, it is 0.5 mass % - 10 mass % normally with respect to the solid content total amount of a photosensitive coloring resin composition, Preferably it exists in the range of 1 mass % - 5 mass %. When it is more than the said lower limit, the suppression effect of the film thickness change before and behind image development is excellent. On the other hand, it is easy to make the photocurable red resin composition of this invention favorable in developability as it is below the said upper limit, and line width shift is suppressed.

[other ingredients] The photosensitive colored resin composition of this invention may contain various additives as needed. As an additive, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an adhesion promoter, etc. are mentioned, for example. As a specific example of a surfactant and a plasticizer, what was described in Unexamined-Japanese-Patent No. 2013-029832 is mentioned, for example.

<Manufacturing method of photosensitive colored resin composition> The production method of the photosensitive colored resin composition of the present invention can be by using a known mixing method to mix a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, a solvent, and as required It is prepared by mixing the dispersant, etc. or various additives. As the preparation method of the resin composition, for example: (1) First, add a color material and a dispersant to a solvent to prepare a color material dispersion, and mix an alkali-soluble resin and a photopolymerizable compound in the dispersion , photoinitiator, ultraviolet absorber, and the method of adding various ingredients according to the needs; (3) Add alkali-soluble resin, photopolymerizable compound, photoinitiator, ultraviolet absorber, and A method of adding a color material to disperse after mixing the dispersant or various additional components; (4) adding a color material, a dispersant, and an alkali-soluble resin to a solvent to prepare a color material dispersion, and adding the color material to the dispersion liquid A method of further adding an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various additional components used as required and mixing them; etc. Among these methods, the above-mentioned methods (1) and (4) are preferable in terms of effectively preventing aggregation of coloring materials and uniformly dispersing them.

The method for preparing the color material dispersion can be appropriately selected from previously known dispersion methods. Examples of dispersing machines for dispersing treatment include roller mills such as two-roll mills and three-roll mills; ball mills such as ball mills and vibrating ball mills; paint conditioners, continuous disc bead mills, and continuous ring bead mills. machine and other bead mills. As a preferred dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

[use] The photosensitive colored resin composition of the present invention is a lake color material containing a triarylmethane dye and can form a colored layer that improves brightness and suppresses changes in film thickness before and after development with a thinner line width, so it 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 above-mentioned 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 above-mentioned photosensitive colored resin composition of the present invention, drying the coating film, and performing exposure and development. As the method of forming, exposing, and developing the coating film, for example, the same method as the method used for forming the colored layer included in the color filter of the present invention described below can be used. In addition, the hardened product of the present invention is a coloring layer containing a triarylmethane-based dye lake material that increases brightness and suppresses changes in film thickness before and after development with a thinner line width, and can be suitably used as a color filter The coloring layer.

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

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

[coloring layer] At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition of the present invention. The colored layer is usually formed in the opening of the light-shielding portion on the substrate described below, and usually includes colored patterns of three or more colors. In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type can be used. In addition, the width, area, etc. of the colored layer can be set arbitrarily. The thickness of the colored layer can be properly controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive colored resin composition, etc., and is usually preferably in the range of 1-5 μm.

This colored layer can be formed by the following method, for example. First, the above-mentioned photosensitive colored resin of the present invention is coated by spray coating, dip coating, rod coating, roll coating, spin coating, die coating and other coating methods. The compositions were coated on the substrates described below to form wet coating films. Among them, a spin coating method and a die coating method can be suitably used. Next, after drying the wet coating film using a hot plate or an oven, etc., it is exposed through a mask with a predetermined pattern, and the alkali-soluble resin and multifunctional monomer are photopolymerized to form a cured coating film. As a light source used for exposure, ultraviolet rays, such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, electron beam, etc. are mentioned, for example. The exposure amount can be adjusted appropriately according to the light source used or the thickness of the coating film. Moreover, after exposure, you may heat-process in order to accelerate a polymerization reaction. Heating conditions can be appropriately selected according to the compounding ratio of each component in the photosensitive colored resin composition used, the thickness of a coating film, etc.

Next, a developing treatment is performed using a developing solution to dissolve and remove unexposed parts, thereby forming a coating film in a desired pattern. As a developing solution, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. A suitable amount of surfactant or the like may also be added to the alkaline solution. In addition, as a developing method, a usual method can be used. After the development treatment, washing of the developing solution and drying of the cured coating film of the photosensitive colored resin composition are usually carried out to form a colored layer. In addition, heat processing may be performed in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited, and may be appropriately selected according to the application of the coating film.

[shading department] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate described below, and can be set to be the same as that used as the light-shielding portion in a normal color filter. It does not specifically limit as a pattern shape of this light shielding part, For example, shapes, such as a stripe shape and a matrix shape, are mentioned. The light-shielding portion may be a metal thin film of chromium or the like obtained by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, and heating a photosensitive resist. Method of transfer, etc.

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 set to about 0.5 to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.

[substrate] As the substrate, a transparent substrate described below, a silicon substrate, and a thin film of aluminum, silver, silver/copper/palladium alloy, etc. formed on a transparent substrate or a silicon substrate can be used. Other color filter layers, resin layers, TFT (thin-film transistor, thin-film transistor) and other transistors, circuits, etc. can be formed on these substrates. The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in ordinary color filters can be used. Specifically, examples include non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent resin films, optical resin plates, and flexible transparent soft materials such as flexible glass. . The thickness of the transparent substrate is not particularly limited, and depending on the use of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used. Furthermore, the color filter of the present invention may be, for example, an overcoat layer or a transparent electrode layer, and further formed with an alignment film or a columnar spacer, in addition to the above-mentioned substrate, light-shielding portion, and colored layer.

IV. Display device A display device of the present invention is characterized by comprising the above-mentioned color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from previously known display devices, for example, a liquid crystal display device or an organic light-emitting display device.

[Liquid crystal display device] As the liquid crystal display device of the present invention, for example, a liquid crystal having the above-mentioned color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate can be exemplified. display device. Such a liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As shown 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 a liquid crystal formed between the color filter 10 and the counter substrate 20. Layer 30. In addition, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2 , and may have a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be employed. As such a driving method, for example, a TN (Twisted Nematic) method, an IPS (In-Plane Switching, transverse electric field effect) method, an OCB (optically compensated bend) method, and an MVA ( Multi-Domain Vertical Alignment, multi-domain vertical alignment) method, etc. In the present invention, any of these modes can be suitably used. In addition, as a counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention, and the like. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention and the like.

As a method for forming a liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, for example, a vacuum injection method or a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal unit is slowly cooled to room temperature, thereby aligning the sealed liquid crystal.

[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-mentioned color filter of the present invention and an organic light-emitting body can be exemplified. The organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing an example of an organic light emitting display device of the present invention. As shown in FIG. 3 , the organic light emitting display device 100 of the present invention has a color filter 10 and an organic light emitting body 80 . An organic protection layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitting body 80 .

As a lamination method of the organic luminescent body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode are sequentially formed on the upper surface of a color filter. 76; or a method of attaching the organic luminescent body 80 formed on another substrate to the inorganic oxide film 60, etc. The transparent anode 71 , hole injection layer 72 , hole transport layer 73 , light emitting layer 74 , electron injection layer 75 , and cathode 76 in the organic luminescent body 80 and other components can appropriately use known ones. The organic light-emitting display device 100 manufactured in the above manner can be applied to, for example, an organic EL display of a passive driving method, and can also be applied to an organic EL display of an active driving method. Furthermore, the organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3 , and may be a structure generally known as an organic light emitting display device using a color filter. Example

Hereinafter, an Example is shown and this invention is demonstrated concretely. These descriptions do not limit the present invention. The mass-average molecular weight (Mw) of the copolymer before salt formation can be expressed as a standard polystyrene-equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention described above. Find out.

[Solubility test of UV absorber in PGMEA] The solubility test of ultraviolet absorbers in PGMEA measured 0.5 g of each ultraviolet absorber at 25° C., added to 9.5 g of PGMEA, stirred with a stirrer for 1 hour, and evaluated visually. 〇: No dissolved residue ×: Dissolution remains

[Measurement of the transmittance of ultraviolet absorbers at a wavelength of 365 nm] The transmittance of the ultraviolet absorber at a wavelength of 365 nm is prepared by preparing 0.002% by mass propylene glycol monomethyl ether acetate solution of each ultraviolet absorber, using a UV-visible-near-infrared spectrophotometer (such as V-7100 of JASCO Co., Ltd.) This 0.002 mass % propylene glycol monomethyl ether acetate solution was measured. Table 1 shows the measurement results of the transmittance of the ultraviolet absorber at a wavelength of 365 nm.

[Table 1] Table 1. UV absorber PGMEA solubility 365 nm transmittance UV absorber U1 〇 38.8% UV absorber U2 〇 77.9% UV absorber U3 〇 14.9% UV absorber U4 〇 16.0% UV absorber U5 〇 29.4% UV absorber U6 〇 34.5% UV absorber U7 〇 65.8% UV absorber U8 〇 46.9% UV absorber U9 〇 30.2% UV absorber U10 〇 16.5% UV absorber U11 〇 39.1% UV absorber (U1): Kemisorb71, manufactured by Chemipro Kasei UV absorber (U2): Kemisorb12, manufactured by Chemipro Kasei UV absorber (U3): Kemisorb111, manufactured by Chemipro Kasei UV absorber (U4): Kemisorb73, manufactured by Chemipro Kasei UV absorber UV absorber (U5): TinuvinPS, made by BASF UV absorber (U6): Tinuvin928, made by BASF UV absorber (U7): Tinuvin405, made by BASF UV absorber (U8): Tinuvin479, made by BASF UV absorber (U9): Tinuvin329 , Ultraviolet absorber (U10) made in BASF: Tinuvin477, ultraviolet absorber (U11) made in BASF: RUVA-93, made in Otsuka Chemical

(Synthesis Example 1: Synthesis of Lake Color Material 1) (1) Synthesis of Intermediate 1 With reference to the production method of intermediate A-2, intermediate B-1, and compound 1-3 described in Japanese Patent Application Laid-Open No. 2018-3013, intermediate 1 represented by the following chemical formula (a) was obtained (yield 87 %). From the analysis results described below, it was confirmed that the obtained compound was the target compound. ・MS(ESI) (m/z): 677(+), bivalent ・Elemental analysis value: CHN (Carbon-Hydrogen-Nitrogen, carbon hydrogen nitrogen) measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%, 7.36%, 5.90%)

[chemical 13]

(2) Synthesis of Lake Color Material 1 Heat and dissolve 2.59 g (0.76 mmol) of 12 tungstophosphoric acid-n-hydrate manufactured by Kanto Chemical in a mixture of 40 mL methanol and 40 mL water, and add 1.6 g (1.19 mmol) The above intermediate 1, and stirred for 1 hour. The precipitate was collected by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain a lake color material 1 represented by the following chemical formula (b) (yield: 95%). From the analysis results described below, it was confirmed that the obtained compound was the target compound.・31P NMR (d-dmso, ppm) δ-15.15 ・MS (MALDI) (m/z): 1355 (M ⁺ ), 2879 (MH ₂ ^- ) ・Elemental analysis value: CHN measured value (35.55%, 3.24% , 2.61%); theoretical value (35.61%, 3.20%, 2.57%) ・Fluorescence X-ray analysis: MoW measured ratio (0%, 100%); theoretical value (0%, 100%)

[chemical 14]

(Synthesis Example 2: Synthesis of Lake Color Material 2) (1) Preparation of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) NaWO ₄ ·2H ₂ O (manufactured by Wako Pure Chemical Industries) 44.0 g, Na ₂ MoO ₄ · 1.90 g of 2H ₂ O (manufactured by Kanto Chemical Industry) was dissolved in 230 g of purified water. 64.9 g of 85% phosphoric acid was added to this solution, stirring using the dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction liquid was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added while stirring. After further stirring for 1 hour, the precipitate was separated by filtration. The obtained solid was dried at 90°C, whereby 29.4 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was obtained. (2) Synthesis of Lake Coloring Material 2 5.30 g of CI basic blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into 350 ml of purified water, stirred and dissolved at 40° C., and a BB7 solution was prepared. Separately, 10.0 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) prepared in (1) above was dissolved in 40 ml of purified water. Add the K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution into the BB7 solution, and directly stir at 40° C. for 1 hour. Then, internal temperature was raised to 80 degreeC, and it stirred for 1 hour further, and it made into a lake. After cooling, filter and wash 3 times with 300 ml of purified water. The obtained solid was dried at 90° C., whereby 10.4 g of a lake color material having an average primary particle diameter of 40 nm as a triarylmethane-based dye and a polyacid was obtained as a dark blue solid. Material 2.

(Synthesis Example 3: Synthesis of Acidic Dispersant A1 (a polymer having at least one structural unit selected from the above-mentioned general formula (I))) (1) Synthesis of macromonomer MM-1 Add 80.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA for short) to a reactor equipped with a condenser tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and heat while stirring under a nitrogen stream. is 90°C. 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, α,α' were added dropwise over 1.5 hours - A mixed solution of 1.0 parts by mass of azobisisobutyronitrile (abbreviated as AIBN), further reacted for 3 hours. Next, the flow of nitrogen gas was stopped, the reaction solution was cooled to 80° C., and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added. , and stirred for 3 hours, thereby obtaining a 49.5% by mass solution of the macromonomer MM-1. As a result of GPC measurement of the obtained macromonomer MM-1, the mass average molecular weight (Mw) was 4010, the number average molecular weight (Mn) was 1910, and the molecular weight distribution (Mw/Mn) was 2.10.

(2) Synthesis of graft copolymer A1 Add 85.0 parts by mass of PGMEA to a reactor equipped with a condenser, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and heat the temperature to 90°C while stirring under a nitrogen stream. After 1.5 hours, 67.34 parts by mass of the above-mentioned macromonomer MM-1 solution (33.33 parts by mass of solid content), 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecyl mercaptan, A mixed solution of 25.0 parts by mass of PGMEA and 0.5 parts by mass of AIBN was heated and stirred for 3 hours, then a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour, thereby obtaining 25.0 mass % solution of branch copolymer A1. As a result of GPC measurement of the obtained graft copolymer A1, the mass average molecular weight (Mw) was 10570, the number average molecular weight (Mn) was 4370, and the molecular weight distribution (Mw/Mn) was 2.42.

(3) Manufacture of a polymer (acidic dispersant A1) having at least one structural unit selected from the above-mentioned general formula (I) on a device equipped with a condenser tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA", manufactured by Nissan Chemical) were added to the reactor of the thermometer, and the temperature was heated to 90°C while stirring under a nitrogen stream. 100.0 parts by mass of the above-mentioned graft copolymer A1 was added dropwise over 30 minutes, heated and stirred for 2 hours, thereby obtaining a polymer (acidic dispersant A1) Solution (solid content: 25.0% by mass). The progress of the esterification reaction of GMA and PPA of the obtained acidic dispersant A1 was confirmed by the acid value measurement and ¹ H-NMR measurement (it confirmed that the peak originating in an epoxy group disappeared). The acid value of the obtained acidic dispersant A1 was 98 mgKOH/g.

(Synthesis example 4:: Acidic dispersant A2 (contains A block comprising a structural unit derived from a carboxyl-containing ethylenically unsaturated monomer and a B block comprising a structural unit derived from an alkyl (meth)acrylate Synthesis of block copolymers) Referring to Example 1 described in International Publication No. 2016/132863, a block having 20 parts by mass of methyl methacrylate (MMA), 40 parts by mass of n-butyl methacrylate (BMA), and methacrylic acid (MAA) were synthesized. ) 20 mass parts, BMA 20 mass parts block, and MMA 20 mass parts, BMA 40 mass parts block triblock copolymer. 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 130 mgKOH/g.

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

[chemical 15]

(Comparative Synthesis Example 1: Synthesis of Triarylmethane Dye 1) Triarylmethane-based dye 1 was synthesized in the same manner as dye A described in Example 1 of JP-A-2011-133844. First, as described in Example 1 of Japanese Patent Application Laid-Open No. 2011-133844, triethylamine salt of (tosyl)trifluoromethanesulfoimidate was synthesized. Next, C.I. Basic Blue 7(N-[4-[[4-(diethylamino)phenyl][4-(ethylamino)-1-naphthyl]methylene]-2,5 -Cyclohexadiene-1-ylidene]-N-ethylethanolammonium-chloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 g was dissolved in methanol 30 mL, and (tosyl)trifluoromethane was added while stirring 3.93 g of triethylamine sulfonylimidate was stirred at room temperature for 1 hour. Concentrate the methanol in the solution with an evaporator, add 100 mL of water, filter the precipitate, and wash it with water. This filter cake was dried under reduced pressure to obtain a triarylmethane dye 1 .

(Preparation Example 1: Preparation of Alkali-soluble Resin P1) Add 300 parts by mass of PGMEA to the polymerization tank, and after raising the temperature to 100°C under a nitrogen atmosphere, continuously drop 67.6 parts by mass of benzyl methacrylate (BzMA), 67.6 parts by mass of MMA, and methacrylic acid (MAA) dropwise over 1.5 hours 36.4 parts by mass, 3 parts by mass of PERBUTYL O (manufactured by NOF), and 9 parts by mass of a chain transfer agent (n-dodecyl mercaptan). Thereafter, the reaction was continued while maintaining 100° C., and 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after completion of the dripping of the above-mentioned main chain forming mixture to stop the polymerization. Then, while blowing in air, 28.4 parts by mass of glycidyl methacrylate (GMA) was added as a compound containing an epoxy group. After raising the temperature to 110°C, 0.8 parts by mass of triethylamine was added, and an addition reaction was carried out at 110°C. After 15 hours, an alkali-soluble resin P1 solution (weight average molecular weight (Mw) 9000, acid value 75 mgKOH/g, solid content 40% by mass) was obtained. Furthermore, the above method for measuring the weight average molecular weight is to use polystyrene as a standard substance and THF (tetrahydrofuran, tetrahydrofuran) as an eluent to measure the weight average molecular weight by Shodex GPC System-21H (Shodex GPC System-21H). In addition, the measuring method of an acid value was measured based on JISK0070.

(Example 1: Manufacture of Photosensitive Colored Resin Composition 1) (1) Preparation of color material dispersion 1 In a 225 mL mayonnaise bottle, pack 61 mass parts of PGMEA, 5 mass parts of the alkali-soluble resin P1 solution (solid content 40 mass %) of Preparation Example 1, the acidic dispersant A1 solution (solid content 25.0 mass %) of Synthesis Example 3 %) 24 parts by mass and stirred. 10 parts by mass of triarylmethane-based color lake material 1 of Synthesis Example 1 and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm were placed therein, and shaken for 1 hour by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) Preliminary disintegration, and then changed to 200 parts of zirconia beads with a particle size of 0.1 mm, and dispersed for 4 hours by a paint shaker as the main disintegration, and the color material dispersion 1 was obtained.

(2) Preparation of photosensitive adhesive component B1 Add 26.5 parts by mass of the alkali-soluble resin P1 solution (solid content 40% by mass) obtained in Preparation Example 1, photopolymerizable compound (trade name ARONIX M-403, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, East Asia Synthetic manufacture) 17.7 parts by mass, photopolymerizable compound (trade name ARONIX M-305, pentaerythritol triacrylate and pentaerythritol tetraacrylate, Toagosei manufacture) 7.06 parts by mass, photoinitiator 1 (I1 ): Irgacure 907 (manufactured by BASF, α-aminoacetophenone-based photoinitiator) 1.96 parts by mass and photoinitiator 2 (I2): OXE-02 (manufactured by BASF, oxime ester-based photoinitiator having a carbazole skeleton) Initiator) 1.96 parts by mass, ultraviolet absorber (ultraviolet absorber 1 (U1): Kemisorb71, manufactured by Chemipro Kasei) 0.392 parts by mass, IRGANOX1010 (manufactured by BASF) as an antioxidant 0.392 parts by mass, PGMEA 44.1 parts by mass, to obtain Photosensitive adhesive component B1. (3) Preparation of Photosensitive Colored Resin Composition 1 3.44 parts by mass of the color material dispersion 1 obtained above, 3.50 parts by mass of the photosensitive adhesive component B1, and 3.06 parts by mass of PGMEA were mixed to prepare the photosensitive colored resin composition of Example 1.

(Examples 2-27: Production of Photosensitive Colored Resin Compositions 2-27) In Example 1, each photosensitive adhesive component B2 to B27 was prepared and used as shown in Table 2, instead of the photosensitive adhesive component B1. In the same manner, photosensitive colored resin compositions 2-27 were obtained.

(Example 28: Production of Photosensitive Colored Resin Composition 28) In Example 2, the color material in the color material dispersion 1 was changed from the triarylmethane-based color lake material 1 of Synthesis Example 1 to the triarylmethane-based color lake color material 2 of Synthesis Example 2. In addition, In the same manner as in Example 2, a photosensitive colored resin composition 28 was obtained.

(Comparative Examples 1-5: Production of Comparative Photosensitive Colored Resin Compositions 1-5) In Example 1, each photosensitive adhesive component CB1 to CB5 was prepared and used as shown in Table 3, instead of the photosensitive adhesive component B1. In the same manner, Comparative Photosensitive Colored Resin Compositions 1-5 were obtained.

(Comparative Examples 6-8: Production of Comparative Photosensitive Colored Resin Compositions 6-8) (1) Preparation of color material dispersion C1 In a 225 mL mayonnaise bottle, pack 65 mass parts of PGMEA, 15 mass parts of the alkali-soluble resin P1 solution (solid content 40 mass %) of Preparation Example 1, the PGMEA solution (solid content 40 mass %) of the acidic dispersant A2 of Synthesis Example 4 20.0 mass%) 10 parts by mass and stirred. 8.8 parts by mass of PB15:6, 1.2 parts by mass of PV23, and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm were placed therein, and vibrated for 1 hour by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-crushed solution. Then, it was changed to 200 parts of zirconia beads with a particle size of 0.1 mm, and dispersed for 4 hours with a paint shaker as the formal disintegration to obtain color material dispersion C1. (2) Comparative Preparation of Photosensitive Colored Resin Compositions 6-8 In Example 1, each photosensitive adhesive component CB6-CB8 was prepared as shown in Table 3 instead of the photosensitive adhesive component B1. 2.56 parts by mass of the color material dispersion C1, 3.58 parts by mass of the photosensitive adhesive component, and 3.85 parts by mass of PGMEA were mixed to obtain Comparative Photosensitive Colored Resin Compositions 6-8.

(Comparative Examples 9-11: Production of Comparative Photosensitive Colored Resin Compositions 9-11) In Example 1, each photosensitive adhesive component CB9-CB11 was prepared as shown in Table 3 instead of the photosensitive adhesive component B1. Comparative photosensitive colored resin compositions 9 to 11 were obtained by mixing 0.333 parts by mass of the dye (triarylmethane dye 1 of Comparative Synthesis Example 1), 4.17 parts by mass of the photosensitive binder component, and 5.50 parts by mass of PGME.

[Evaluation method] Using a spin coater, the photosensitive colored resin compositions of Examples and Comparative Examples were coated on glass substrates (NH TECHNO GLASS Manufacture, "NA35"), heat and dry at 80°C for 3 minutes using a hot plate. Afterwards, irradiate ultraviolet rays of 60 mJ/cm ² with an ultra-high pressure mercury lamp through a photomask forming a 40 μm line, and then use 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer to spray and develop for 60 seconds. Thereafter, it was post-baked in a clean oven at 230° C. for 30 minutes, thereby fabricating a pattern forming substrate in which a colored layer was formed on a glass substrate in a line pattern of 40 μm.

＜Inhibition of Line Width Increase in Colored Layer＞ Measure the width of the thin line pattern of the coloring layer in the chrome mask used for exposure with an optical microscope at a portion corresponding to an opening width of 40 μm, and evaluate the line width deviation based on the difference between the average line width and the target line width quantity. (Evaluation Criteria for Line Width Increase Suppression) AA: Relative to the target line width, the difference is within 5.0 μm; A: Relative to the target line width, the difference exceeds 5.0 μm and is within 7.0 μm; B: Relative to the target line width, the difference exceeds 7.0 μm and is within 10.0 μm; C: The difference exceeds 10.0 μm with respect to the target line width. If the evaluation result is A, the line width increase suppression is good, and if the evaluation result is AA, the line width increase suppression is excellent.

<Evaluation of developing residual film ratio> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on glass substrates with a thickness of 0.7 mm using a spin coater so that the film thickness after baking was 2.2 μm ( Made by NH TECHNO GLASS, "NA35"), heat and dry at 80°C for 3 minutes using a hot plate. Thereafter, without intervening a photomask, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 60 mJ/cm ² , and thereafter, a film thickness T1 of the resist coating film was measured using a film thickness gauge. Next, spray image development was performed for 60 seconds using 0.05 mass % potassium hydroxide aqueous solution as an alkaline developing solution, and the film thickness T2 after image development was measured. It is calculated in the form of developing residual film rate=T2/T1[%]. (Evaluation criteria for developing residual film rate) AA: Developing residual film rate is above 98%; A: Developing residual film rate is above 97% and less than 98%; B: Developing residual film rate is above 94% and less than 97% ; C: The rate of remaining film after development does not reach 94%. If the evaluation result is A, the residual image development rate is good, and if the evaluation result is AA, the residual image development rate is excellent.

<Evaluation of Brightness and Heat Resistance> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on glass substrates with a thickness of 0.7 mm ( Made by NH TECHNO GLASS, "NA35"). Afterwards, heat and dry on a heating plate at 80°C for 3 minutes, and use an ultra-high pressure mercury lamp to irradiate ultraviolet rays of 60 mJ/cm ² without intervening a light shield, and then bake in a clean oven at 230°C for 30 minutes, thereby A cured film (colored film) was obtained. The luminance (Y), L, a, b (L ₀ , a ₀ , b ₀ ) of the obtained colored substrate was measured using the "microspectrometry device OSP-SP200" manufactured by Olympus Corporation, and evaluated according to the following evaluation criteria . Then, after baking the substrate with the above-mentioned cured film in a clean oven at 230° C. for 30 minutes, let it cool for 30 minutes, repeat the above steps 3 times, and measure the L, a, and b of the obtained colored substrate ( L ₁ , a ₁ , b ₁ ). Based on the measured value, the color difference (ΔEab) before and after treatment was calculated according to the following formula. Color difference (ΔEab)＝{(L ₁ -L ₀ ) ² +(a ₁ -a ₀ ) ² +(b ₁ -b ₀ ) ² } ^1/2

(Brightness evaluation standard) AA: Brightness (Y) is above 10.6; A: Brightness (Y) is above 10.0 and less than 10.6; B: Brightness (Y) is above 9.5 and less than 10.0; C: Brightness (Y) is less than 9.5. If the evaluation result is A, the luminance is good, and if the evaluation result is AA, the luminance is excellent.

(Heat resistance evaluation standard) 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. When the evaluation result is A, the heat resistance is good, and when the evaluation result is AA, the heat resistance is excellent.

[Table 2] Table 2. Adhesive ingredients Photoinitiator UV absorber Antioxidants Resin P1 M1 M2 M3 M4 Thiol solvent I1 I2 U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 EO modification B1 1.96 1.96 0.392 0.392 26.5 17.7 7.06 44.1 B2 1.94 1.94 0.388 0.388 0.388 26.2 17.5 6.99 44.3 B3 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B4 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B5 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B6 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B7 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B8 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B9 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B10 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B11 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B12 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B13 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B14 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B15 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B16 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B17 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B18 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B19 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B20 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B21 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B22 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B23 1.92 1.92 0.769 0.385 0.385 26.0 17.3 6.92 44.4 B24 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B25 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B26 2.31 2.31 0.769 0.385 0.385 25.4 16.9 6.77 44.8 B27 1.91 1.91 0.762 0.381 0.381 25.7 17.1 6.86 0.381 44.6

[Table 3] Table 3. Adhesive ingredients Photoinitiator UV absorber Antioxidants Resin P1 M1 M2 M3 M4 Thiol solvent I1 I2 U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 EO modification CB1 1.96 1.96 0.392 0.392 26.5 17.7 7.06 44.1 CB2 1.57 1.57 0.392 0.392 27.1 18.0 7.22 43.8 CB3 1.18 1.18 0.392 0.392 27.7 18.4 7.37 43.4 CB4 1.96 1.96 0.784 26.5 17.7 7.06 44.1 CB5 1.92 1.92 1.538 26.0 17.3 6.92 44.4 CB6 2.00 2.00 27.0 18.0 7.20 43.8 CB7 3.60 3.60 24.6 16.4 6.56 45.2 CB8 3.53 3.53 0.784 24.1 16.1 6.43 45.5 CB9 1.98 1.98 0.396 26.4 17.8 7.13 44.3 CB10 3.96 3.96 0.396 23.8 15.8 6.34 45.7 CB11 3.92 3.92 0.392 0.392 23.5 15.7 6.27 45.9

In the table, the abbreviations are as follows. Photoinitiator 1 (I1): Irgacure 907, manufactured by BASF, α-aminoacetophenone-based photoinitiator Photoinitiator 2 (I2): OXE-02, manufactured by BASF, an oxime ester photoinitiator having a carbazole skeleton Ultraviolet absorber (U1): Kemisorb71, manufactured by Chemipro Kasei Ultraviolet absorber (U2): Kemisorb 12, manufactured by Chemipro Kasei Ultraviolet absorber (U3): Kemisorb 111, manufactured by Chemipro Kasei Ultraviolet absorber (U4): Kemisorb73, manufactured by Chemipro Kasei Ultraviolet absorber (U5): TinuvinPS, product made in BASF Ultraviolet absorber (U6): Tinuvin928, made by BASF Ultraviolet absorber (U7): Tinuvin405, made by BASF Ultraviolet absorber (U8): Tinuvin479, made by BASF Ultraviolet absorber (U9): Tinuvin329, made by BASF Ultraviolet absorber (U10): Tinuvin477, made by BASF Ultraviolet absorber (U11): RUVA-93, made by Otsuka Chemical Antioxidant (A1): IRGANOX1010, manufactured by BASF Potential antioxidant (LA1): potential antioxidant in Synthesis Example 5 Resin P1: Alkali-soluble resin P1 of Preparation Example 1 M1: Photopolymerizable compound, ARONIX M-403, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei M2: Photopolymerizable compound, ARONIX M-305, pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Toa Gosei M3: Photopolymerizable compound, ARONIX M-460, diglycerol ethylene oxide modified acrylate, manufactured by Toa Gosei M4: Photopolymerizable compound, Kayarad DPEA-12, ethylene oxide modified (12) dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Mercaptan: Karenz MT PE1, manufactured by Showa Denko

[Table 4] Table 4. Proportion in the binder composition [wt%] color material Adhesive ingredients Photoinitiator UV absorber Antioxidants EO modified/mercaptan Line Width Offset Developing residual film rate brightness Heat-resistant color difference ΔEab U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 determination determination determination determination Example 1 L1 B1 10 1 1 4.8 AAA 97.4 A 10.4 A 3.3 A Example 2 L1 B2 10 1 1 1 4.7 AAA 97.4 A 10.7 AAA 2.7 AAA Example 3 L1 B3 10 2 1 1 3.3 AAA 97.3 A 10.7 AAA 2.3 AAA Example 4 L1 B4 12 2 1 1 3.7 AAA 98.3 AAA 10.7 AAA 2.4 AAA Example 5 L1 B5 10 2 1 1 4.2 AAA 97.4 A 10.6 AAA 2.8 AAA Example 6 L1 B6 12 2 1 1 4.8 AAA 98.5 AAA 10.6 AAA 2.6 AAA Example 7 L1 B7 10 2 1 1 2.9 AAA 97.5 A 10.7 AAA 2.6 AAA Example 8 L1 B8 12 2 1 1 3.3 AAA 98.4 AAA 10.6 AAA 2.5 AAA Example 9 L1 B9 10 2 1 1 3.5 AAA 97.2 A 10.6 AAA 2.6 AAA Example 10 L1 B10 12 2 1 1 3.9 AAA 98.1 AAA 10.6 AAA 2.5 AAA Example 11 L1 B11 10 2 1 1 3.5 AAA 97.3 A 10.6 AAA 2.5 AAA Example 12 L1 B12 12 2 1 1 3.9 AAA 98.4 AAA 10.6 AAA 2.6 AAA Example 13 L1 B13 10 2 1 1 2.7 AAA 97.2 A 10.7 AAA 2.7 AAA Example 14 L1 B14 12 2 1 1 3.4 AAA 98.1 AAA 10.7 AAA 2.6. AAA Example 15 L1 B15 10 2 1 1 4.1 AAA 97.0 A 10.6 AAA 2.5 AAA Example 16 L1 B16 12 2 1 1 4.4 AAA 98.0 AAA 10.6 AAA 2.5 AAA Example 17 L1 B17 10 2 1 1 4.2 AAA 97.3 A 10.6 AAA 2.5 AAA Example 18 L1 B18 12 2 1 1 4.7 AAA 98.4 AAA 10.6 AAA 2.6 AAA Example 19 L1 B19 10 2 1 1 3.0 AAA 97.5 A 10.7 AAA 2.6 AAA Example 20 L1 B20 12 2 1 1 3.7 AAA 98.7 AAA 10.7 AAA 2.5 AAA Example 21 L1 B21 10 2 1 1 3.3 AAA 97.7 A 10.6 AAA 2.7 AAA Example 22 L1 B22 12 2 1 1 3.9 AAA 98.7 AAA 10.6 AAA 2.6 AAA Example 23 L1 B23 10 2 1 1 3.5 AAA 97.5 A 10.7 AAA 2.8 AAA Example 24 L1 B24 12 2 1 1 3.9 AAA 98.4 AAA 10.7 AAA 2.7 AAA Example 25 L1 B25 12 2 1 1 M3 2.4 AAA 98.0 AAA 10.6 AAA 2.7 AAA Example 26 L1 B26 12 2 1 1 M4 2.7 AAA 98.2 AAA 10.6 AAA 2.7 AAA Example 27 L1 B27 10 2 1 1 Thiol 4.1 AAA 98.1 AAA 10.7 AAA 2.5 AAA Example 28 L2 B2 10 1 1 1 5.4 A 97.3 A 10.2 A 3.2 A

[table 5] table 5. Proportion in the binder composition [wt%] color material Adhesive ingredients Photoinitiator UV absorber Antioxidants EO modified/mercaptan Line Width Offset Developing residual film rate brightness Heat-resistant color difference ΔEab U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 A1 LA1 determination determination determination determination Comparative example 1 L1 BC1 10 1 1 7.8 B 97.5 A 10.7 AAA 2.7 AAA Comparative example 2 L1 BC2 8 1 1 6.9 A 95.4 B 10.7 AAA 2.8 AAA Comparative example 3 L1 BC3 6 1 1 6.3 A 93.9 C 10.6 AAA 3.0 AAA Comparative example 4 L1 BC4 10 2 6.1 A 95.9 B 10.5 A 2.6 AAA Comparative Example 5 L1 BC5 10 4 5.4 A 93.1 C 10.5 A 2.7 AAA Comparative Example 6 pigment BC6 10 1.2 AAA 93.5 C 9.3 C 1.0 AAA Comparative Example 7 pigment BC7 18 4.8 AAA 99.5 AAA 9.2 C 0.5 AAA Comparative Example 8 pigment BC8 18 2 3.8 AAA 99.3 AAA 9.4 C 0.6 AAA Comparative Example 9 dye BC9 10 1 0.3 AAA 91.4 C 8.9 C 15.9 C Comparative Example 10 dye BC10 20 1 4.7 AAA 98.2 AAA 9.3 C 14.3 C Comparative Example 11 dye BC11 20 1 1 4.3 AAA 97.5 A 9.6 B 14.2 C

Furthermore, the numerical values of photoinitiator, ultraviolet absorber, antioxidant and mercaptan are solid content ratios. L1 (color lake material 1): the color lake material 1 of triarylmethane dyes in Synthesis Example 1 L2 (color lake material 2): color lake material 2 of triarylmethane dyes in Synthesis Example 2 Pigment: PB15:6 (C.I. Pigment Blue 15:6) and PV23 (C.I. Pigment Violet 23) Dye: Triarylmethane dye 1 in Comparative Synthesis Example 1

[Summary of results] The photosensitive coloring resin compositions of Examples 1 to 28 in which a triarylmethane-based dye lake coloring material is combined with an ultraviolet absorber can form coloring that improves brightness and suppresses changes in film thickness before and after development with thinner line widths layer. Also, in the embodiment, if the color lake material of the triarylmethane series dye is used together with the ultraviolet absorber, the line width deviation can be adjusted to 5 by using the starting dose while maintaining the residual film rate of development. The target value below μm. Also, in the examples, if an ultraviolet absorber having a transmittance of 40% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution is used, it is difficult to increase the amount of line width shift. Moreover, in an Example, when containing the photopolymerizable compound containing an alkylene oxide, it becomes easy to make both a high developing residual film rate and a narrow line width compatible. On the other hand, in the photosensitive colored resin composition of Comparative Example 1 that does not contain an ultraviolet absorber, even though antioxidants and latent antioxidants are included in the same manner as in Examples, the line width deviation is large, and the line width is also large. becomes thicker, and cannot form a colored layer with the required thinner line width. In the photosensitive colored resin composition of Comparative Example 1 that does not contain an ultraviolet absorber, in the photosensitive colored resin compositions of Comparative Examples 2 and 3 in which the amount of photoinitiator was reduced in order to make the line width thinner, although the line The amount of wide offset decreased somewhat, but the residual film rate deteriorated. In the photosensitive colored resin composition of Comparative Example 1 that did not contain an ultraviolet absorber, in the photosensitive colored resin compositions of Comparative Examples 4 and 5 in which the amount of antioxidant was increased to make the line width thinner, although the line width The amount of offset decreased, but the residual film rate deteriorated. On the other hand, in the photosensitive colored resin compositions of Comparative Examples 6 to 8 in which a pigment was used without using a triarylmethane-based dye lake material, in order to be compatible with the lake color material using a triarylmethane-based dye The same line width offset in the above embodiment requires a large amount of photoinitial dose. In this case, the residual film rate is not a problem, but the brightness is low. In addition, in the photosensitive colored resin compositions of Comparative Examples 9 to 11 in which a triarylmethane-based dye was used without using a triarylmethane-based dye lake color material, in order to set it as a color lake using a triarylmethane-based dye The same line width offset in the embodiment of the color material requires a large amount of photoinitiator dose. In this case, the residual film rate of development is not a problem, but the color difference after heating increases and the brightness decreases.

1: Substrate 2: shading part 3: coloring layer 5: tiny hole 10:Color filter 20: facing the substrate 30: Liquid crystal layer 40: Liquid crystal display device 50: organic protective layer 60: Inorganic oxide film 71: Transparent anode 72: Hole injection layer 73: Hole transport layer 74: luminous layer 75: Electron injection layer 76: Cathode 80: organic luminous body 100: Organic light-emitting display device

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

1: Substrate

2: shading part

3: coloring layer

10:Color filter

Claims (10)

A photosensitive colored resin composition, which contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, The above-mentioned color material contains a lake color material of a triarylmethane dye. The photosensitive colored resin composition according to claim 1, which further contains a dispersant. The photosensitive colored resin composition according to claim 1 or 2, further comprising at least one of antioxidant and latent antioxidant. The photosensitive colored resin composition according to claim 1 or 2, which further contains a thiol compound. The photosensitive colored resin composition as claimed in claim 1 or 2, wherein the lake color material of the above-mentioned triarylmethane series dye contains the color material represented by the following general formula (1), [Chem. 1]

(In the general formula (1), A is an a-valent organic group that does not have a valence of a carbon atom directly bonded to N, and the organic group represents an aliphatic group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N. A hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, may contain heteroatoms in the carbon chain; B ^c- represents a c-valent polyacid anion; R ⁱ ~ R ^v each independently represent a hydrogen atom, an alkane that may have a substituent R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be bonded to form a ring structure; R ^vi and R ^vii each independently represent an alkyl group that may have a substituent, and may have a substituent An alkoxy group, a halogen atom or a cyano group; Ar ¹ represents a divalent aromatic group that may have a substituent; there are multiple R ⁱ ~ R ^vii and Ar ¹ may be the same or different; a and c represent 2 or more b and d represent integers not less than 1; f and g represent integers not less than 0 and not more than 4; there are plural f and g which may be the same or different respectively). The photosensitive colored resin composition according to claim 1 or 2, wherein the transmittance of the ultraviolet absorber at a wavelength of 365 nm in a 0.002 mass % propylene glycol monomethyl ether acetate solution is 40% or less. The photosensitive colored resin composition according to claim 1 or 2, wherein the photopolymerizable compound contains a photopolymerizable compound containing alkylene oxide. A cured product, which is a cured product of the photosensitive colored resin composition according to any one of claims 1 to 7. A color filter comprising at least a substrate and a colored layer disposed on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition according to Claim 8. A display device having the color filter according to claim 9 above.

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