TW202340859A - Photosensitive colored resin composition, cured product, color filter and display device - Google Patents

Abstract

A photosensitive colored resin composition comprising a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, wherein the color material contains a lake color material of a triarylmethane-based dye, and wherein the alkali-soluble resin contains an alkali-soluble resin (U) having a weight average molecular weight of 3000 or more and containing a constitutional unit having a benzotriazole skeleton.

Description

Photosensitive colored resin composition, hardened material, 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 been increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs (Personal Computers)) is also increasing, and the market for liquid crystal displays is expanding day by day. Organic light-emitting display devices such as organic EL (Electroluminescence) displays that have high visibility due to self-luminescence are also attracting attention as next-generation image display devices. These liquid crystal display devices or organic light-emitting display devices use color filters. For example, regarding the formation of a color image in a liquid crystal display device, light after passing through a 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 the light source at this time, an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light may be used. In organic light-emitting display devices, color filters are used for color adjustment and the like.

Here, the color filter usually has: 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 the colored layer in the color filter, for example, a binder resin, a photopolymerizable compound, and a photoinitiator are added to a color material dispersion liquid in which the color material is dispersed using a dispersant or the like. The colored resin composition is coated on a glass substrate and dried, and then exposed using a photomask and developed to form a colored pattern, and the pattern is fixed by heating to form a colored layer. Repeat these steps for each color to form a color filter.

In recent years, the requirements for high brightness of color filters have increased, and it is difficult for color filters using pigments to meet the current requirements for further high brightness. Therefore, in recent years, the industry is studying the use of dyes that generally have a higher transmittance than pigments, or lake pigments that use precipitants to make dyes insoluble as pigments for color filters. However, dyes or lake colorants have the following problems: Compared with pigments that have been used as colorants for color filters so far, they have poor heat resistance. When heated at high temperatures in the color filter manufacturing process, the colored layer is easily fade.

In this regard, Patent Document 1 discloses a colored resin composition for a color filter that uses a lake pigment and is capable of suppressing fading of the colored layer caused by high-temperature heating in the color filter manufacturing process and forming a high-brightness A colored resin composition for color filters with a colored layer, which contains a lake pigment, a dispersant, a hindered phenol antioxidant, a binder component, and a solvent, and the dispersant is at least a part of the nitrogen site and an acidic organic phosphorus compound Specific polymers that form salts.

On the other hand, as a photosensitive colored composition containing an ultraviolet absorber, Patent Document 2 discloses a colored resin composition characterized in that it contains (A) a dye, (B) a solvent, and (C) a binder. agent resin, and further contains (D) antioxidant and (E) ultraviolet absorber. The object of Patent Document 2 is to provide a colored resin composition that can maintain and improve the brightness and heat resistance of the obtained pixel and further form a contact hole with a desired diameter. Furthermore, Patent Document 3 discloses a photosensitive coloring composition characterized by containing a colorant (A); a resin (B); a photopolymerizable monomer (C); and a photopolymerization initiator (D), which contains A phosphine oxide-based organic compound or an oxime ester-based organic compound; and an ultraviolet absorber (E) selected from benzotriazole-based organic compounds, tristriazole-based organic compounds, and benzophenone-based organic compounds. At least one of the group; and the resin (B) includes a photosensitive resin (B-1), and the photosensitive resin (B-1) is the following (b1), (b2) and (b3): (b1): A compound with an alicyclic skeleton and an ethylenically unsaturated bond in one molecule (b2): A compound having an epoxy group and an ethylenically unsaturated bond in one molecule (b3): Copolymerize compounds having ethylenically unsaturated bonds other than a1) and (a2) to obtain copolymer (b6), and react the obtained copolymer (b6) with unsaturated monobasic acid (b4) to obtain A copolymer (b7) is obtained, and the copolymer (b7) obtained is further reacted with a polybasic acid anhydride (b5). The subject of Patent Document 3 is to obtain a photosensitive coloring composition with high resolution that can cope with high image quality and low power consumption, especially for COA (Color Filter on Array). It is a photosensitive coloring composition with a thick film, high resolution, and excellent adhesion that does not cause pattern peeling.

Furthermore, Patent Document 4 discloses a coloring composition for color filters, which is characterized in that it contains a colorant (A), a resin (B), a photopolymerizable monomer (C), and a photopolymerization initiator. (D), and an ultraviolet absorber (E) obtained by polymerizing raw material monomers containing benzotriazole-based monomers and other monomer components, and the above-mentioned raw material monomers include benzotriazole-based monomers 10.0 to 90.0% by mass, and the above-mentioned ultraviolet absorber (E) is contained in 0.5 to 6.0% by weight in the solid content of the entire coloring composition for color filters. The coloring composition for color filters described in Patent Document 4 has excellent light resistance and good adhesion by containing the above-mentioned ultraviolet absorber (E). Prior technical literature patent documents

Patent document 1: Japanese Patent Application Publication No. 2014-153569 Patent Document 2: Japanese Patent Application Publication No. 2015-98537 Patent Document 3: Japanese Patent No. 5664299 Patent Document 4: Japanese Patent No. 6578775

[Problem to be solved by the invention]

With the advancement of high-definition displays such as 4K/8K, the pixel size continues to decrease. Corresponding to the decrease in the aperture ratio (aperture ratio) of the pixel, photoresists with higher brightness are required, and patterns with thinner line widths are required to be formed. Photosensitive colored resin composition. However, when the dye is dissolved and used as in Patent Document 2, the heat resistance is particularly poor and the brightness of the pixel is not sufficiently improved, and in the technology using pigments as in Patent Documents 3 and 4, the brightness of the pixel is not sufficiently improved. . Examples of colorants that are effective in increasing the brightness of pixels include lake colorants of triarylmethane-based dyes. However, since the transmittance of the lake material of the triarylmethane series dye in the UV (Ultra Violet, ultraviolet) wavelength region is higher than that of previously used pigments (such as C.I. Pigment Blue 15:6, C.I. Pigment Violet 23), if it is used with If the photoinitiator is prepared in the same way as before, the pattern line width will tend to become thicker. If the light starting dose is reduced in order to make the pattern line width meet a specific value, or an antioxidant is added as in Patent Document 1, or the amount of antioxidant is increased, the photohardenability of the pattern portion will be insufficient. The change in film thickness increases and the residual film rate after development decreases, making it difficult to balance the thinner line width design with the higher residual film rate after development. Patent Document 1 describes a lake color material using a triarylmethane-based dye, but does not suggest the issue of balancing a thinner line width design with a higher development residual film rate. Patent Document 2 describes a photosensitive colored resin composition containing a triarylmethane dye. However, since the dye is dispersed in the photosensitive colored resin composition at a molecular level, it is easy to hinder the curability of the photocurable component. If the photoinitiator is blended in the same manner as the pigment, the photocurability will be insufficient and the line width will tend to become thin. Due to the design, the residual film rate after development is easily reduced. Therefore, in the photosensitive colored resin composition containing dyes, in order to achieve the required thinner line width, it is necessary to increase the photoinitiator or use a photoinitiator with higher sensitivity, so the development residual film rate will be reduced. Improve naturally. Therefore, the problem that it is difficult for photosensitive colored resin compositions containing dyes to achieve both a thinner line width design and a higher development residual film rate does not originally exist. In addition, since Patent Documents 3 and 4 use pigments, there is no problem that it is difficult to achieve both a thinner line width design and a higher development residual film rate. As mentioned above, when using lake colorants of triarylmethane-based dyes, unlike when using pigments or using dyes, it is difficult to balance a thinner line width design with a higher development residual film rate. subject.

On the other hand, the photosensitive colored resin composition for color filters containing an ultraviolet absorber as described in Patent Documents 2 and 3 has the following problem: even if it contains an ultraviolet absorber, the coloring layer finally obtained cannot improve the durability. Ultraviolet (UV) resistance. The reason is considered to be that the low molecular weight ultraviolet absorber volatilizes during a high-temperature heating step such as 230°C, and no ultraviolet absorber remains in the colored layer finally obtained after the high-temperature heating step. Furthermore, the photosensitive colored resin composition for a color filter containing an ultraviolet absorber obtained by polymerizing a raw material monomer containing a benzotriazole monomer described in Patent Document 4 has the following problem: In the case of a UV absorber containing a polymer with a high molecular weight, it is likely to remain as a development residue. In the case of a UV absorber containing a polymer with a low molecular weight, it will evaporate during a high-temperature heating step such as 230°C, resulting in the final colored layer. Unable to improve ultraviolet (UV) resistance. If the ultraviolet (UV) resistance of the finally obtained colored layer cannot be improved, the following problems may occur, for example: after the colored layer is formed, pre-cleaning is performed by UV irradiation using a low-pressure mercury lamp in subsequent steps such as protective layer formation. After the step, the coloring layer will fade. In order to suppress chromaticity changes during UV irradiation in such manufacturing steps, it is also necessary to improve the UV resistance of the colored layer.

The present invention was made in view of the above-mentioned actual situation, and its object is to provide a lake color material containing a triarylmethane-based dye that can improve brightness and form a thin line width to suppress film thickness changes before and after development and development residue. , a photosensitive colored resin composition that provides a colored layer with excellent UV resistance. Furthermore, an object of the present invention is to provide a color filter and a display device formed using the photosensitive colored resin composition. [Technical means to solve problems]

The photosensitive colored resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned color material contains a lake color material of a triarylmethane-based dye, The alkali-soluble resin contains an alkali-soluble resin (U). The alkali-soluble resin (U) contains a structural unit having a benzotriazole skeleton and has a weight average molecular weight of 3,000 or more.

The color filter of the present invention includes at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers 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. [Effects of the invention]

According to the present invention, it is possible to provide a lake color material containing a triarylmethane-based dye that can improve brightness and form a colored layer that suppresses changes in film thickness and development residue before and after development with a thin line width and has excellent UV resistance. Photosensitive colored resin composition. Furthermore, according to the present invention, it is possible to provide a color filter and a display device formed using the photosensitive colored resin composition.

Hereinafter, the photosensitive colored resin composition, hardened material, color filter, and display device of this invention are demonstrated in detail in order. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and further radiation. The radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with wavelengths below 5 μm. In the present invention, (meth)acrylyl group represents acrylic acid group and methacrylic acid group respectively, (meth)acrylic acid represents acrylic acid and methacrylic acid respectively, and (meth)acrylate represents acrylate and methacrylate respectively. Acrylate. In addition, in this specification, "～" indicating a numerical range is used in a meaning that includes the numerical values described before and after it as the lower limit and the upper limit.

I. Photosensitive colored resin composition The photosensitive colored resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned color material contains a lake color material of a triarylmethane-based dye, The alkali-soluble resin contains an alkali-soluble resin (U). The alkali-soluble resin (U) contains a structural unit having a benzotriazole skeleton and has a weight average molecular weight of 3,000 or more.

The photosensitive colored resin composition of the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and the above-mentioned colorant is a lake colorant of a triarylmethane-based dye, and the above-mentioned alkali-soluble resin is The resin contains an alkali-soluble resin (U). The alkali-soluble resin (U) contains a structural unit with a benzotriazole skeleton and has a weight average molecular weight of more than 3,000. Therefore, it can improve brightness and form a thinner line width to suppress development. A colored layer that eliminates changes in film thickness and development residue before and after, and has excellent UV resistance. The role that exerts this effect has not yet been identified, but it is presumed as follows.

As mentioned above, since the ultraviolet transmittance of the pigment is low, in the photosensitive colored resin composition containing the pigment, the photocurable component is relatively difficult to harden. In addition, dyes easily hinder the curing properties of the photocurable component, so in the photosensitive colored resin composition containing the dye, the photocurable component is relatively difficult to harden. In contrast, since the lake material of triarylmethane dyes has a high transmittance of ultraviolet rays and does not hinder the curing properties of the photocurable component, the effect of being insoluble in the developer after photocuring is higher than that of pigments or Dye, so the pattern line width tends to become thicker. Regarding the photosensitive colored resin composition containing a lake color material of a triarylmethane-based dye, in order to set the pattern line width to a specific thin line width, it is necessary to effectively suppress the photocuring reaction. If a lake color material of a triarylmethane-based dye with a high transmittance is used as the color material, and the light starting dose is reduced in order to make the pattern line width meet a specific value, the light reaction caused by the light reaction will be reduced regardless of the film thickness direction. Since free radicals are generated, it is considered that the photohardenability of the pattern portion is insufficient, the change in film thickness from before development to after development increases, and the development residual film rate decreases. In addition, if a lake color material of a triarylmethane-based dye is used and an antioxidant is added or the amount is increased in order to make the pattern line width meet a specific value, the photoinitiator will be generated by the photoreaction regardless of the film thickness direction. Because of the deactivation of free radicals, it is considered that the photohardenability of the pattern part is insufficient, the change in film thickness from before development to after development increases, and the residual film rate after development decreases. On the other hand, in the present invention, an alkali-soluble resin (U) containing a structural unit having a benzotriazole skeleton and having a weight average molecular weight of 3,000 or more is combined with a lake material of a triarylmethane-based dye. The alkali-soluble resin (U) is easily and uniformly dispersed in the coating film. The benzotriazole skeleton contained in the alkali-soluble resin (U) has ultraviolet absorption function. It will not attenuate ultraviolet rays and harden on the film surface. Therefore, the residual film rate after development will not be reduced, and the ultraviolet rays will be absorbed deep into the film. Attenuation, a method of reducing the generation of free radicals from photoinitiators, works according to the depth of the film. Therefore, it is considered that by containing the alkali-soluble resin (U), the photosensitive colored resin composition of the present invention can suppress a decrease in the film thickness of the residual film after development and reduce the line width. Furthermore, since the coloring material contains a lake coloring material of a triarylmethane-based dye, the colored layer that is a cured product of the photosensitive colored resin composition of the present invention has a high transmittance and is produced by ultraviolet irradiation or post-baking. Colorimetric changes caused by time steps are suppressed. In addition, since the alkali-soluble resin (U) with a weight average molecular weight of 3,000 or more has an ultraviolet absorbing function and is alkali-soluble, it is developed during development and is less likely to become a development residue. Furthermore, the alkali-soluble resin (U) with a weight average molecular weight of 3000 or more is not easy to volatilize in a high-temperature heating step such as 230°C, so the UV resistance of the finally obtained colored layer can also be improved.

The photosensitive colored resin composition of the present invention contains at least a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. For example, in order to improve the dispersibility of the colorant, the photosensitive colored resin composition of the present invention may further contain a dispersant. Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail in order from the alkali-soluble resin.

[Alkali-soluble resin] The alkali-soluble resin in the present invention has an acidic group, can function as a binder resin, and is soluble in an alkaline developer used during pattern formation, and is appropriately selected and used. 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 an acidic group and usually a carboxyl group. Specifically, examples thereof include (meth)acrylic copolymers having a carboxyl group and styrene-(methyl) having a carboxyl group. ) (meth)acrylic resins such as acrylic copolymers, epoxy (meth)acrylate resins having carboxyl groups, etc.

(Alkali-soluble resin (U)) The alkali-soluble resin of the present invention contains an alkali-soluble resin (U). The alkali-soluble resin (U) contains a structural unit having a benzotriazole skeleton and has a weight average molecular weight of 3,000 or more. The alkali-soluble resin (U) used in the present invention has an acid value as described above, contains a structural unit having a benzotriazole skeleton, and has a weight average molecular weight of 3,000 or more. The structure of the alkali-soluble resin (U) is not particularly limited as long as it contains a structural unit having a benzotriazole skeleton. It may be a (meth)acrylic copolymer containing a structural unit having a carboxyl group, or styrene having a carboxyl group. -(meth)acrylic resins such as (meth)acrylic copolymers. The (meth)acrylic resin is, for example, a copolymer obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, other monomers that can be copolymerized by a known method. From the viewpoint of simple manufacturing steps and easy control of molecular weight, the alkali-soluble resin (U) is preferably a random copolymer.

The alkali-soluble resin (U) may be a (meth)acrylic copolymer or a styrene-(meth)acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a benzotriazole skeleton. A (meth)acrylic copolymer or styrene-(meth)acrylic acid having a structural unit derived from an ethylenically unsaturated monomer containing a carboxyl group and a structural unit derived from an ethylenically unsaturated monomer containing a benzotriazole skeleton System copolymer. Examples of the benzotriazole skeleton-containing ethylenically unsaturated monomer include a monomer having a benzotriazole skeleton represented by the following general formula (A).

[Chemical 1] General formula (A) (In the general formula (A), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group or an oxyalkylene group, and R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or a hydrocarbon group having 1 to 15 carbon atoms. Alkoxy group, R ⁴ represents a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 8 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a cyano group, or a nitro group)

The alkylene group of R ² may be an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include ethylene, propylene, butylene, hexylene, octyl, and decylene. The alkylene group may be a linear alkylene group such as methylene, ethylene, trimethylene, or tetramethylene, or may be a propylene, 2-methyltrimethylene, or 2-methyl group. Branched alkylene groups such as tetramethylene. The oxyalkylene group (-OR ^a -, here, R ^a is an alkylene group) of R ² may be an oxyalkylene group having 1 to 10 carbon atoms, or may be an oxyalkylene group having 1 to 5 carbon atoms. . Examples include oxyethyl, oxypropyl, oxytrimethylene, oxytetramethylene, and the like.

Examples of the hydrocarbon group having 1 to 15 carbon atoms in R ³ include linear, branched or cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. Specifically, examples of the hydrocarbon group having 1 to 15 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl. Linear or branched aliphatic hydrocarbon groups such as base, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; cyclopropyl, cyclopentyl, Cyclic aliphatic hydrocarbon groups (cycloalkyl) such as cyclohexyl, cycloheptyl and cyclooctyl; aromatic hydrocarbon groups such as phenyl, naphthyl and biphenyl; benzyl, phenylethyl, 1-methyl-1 - Combination bases such as phenylethyl and the like. The hydrocarbon group in R ³ can be an aliphatic hydrocarbon group, a straight-chain or branched alkyl group, and can be methyl, tert-butyl, tert-pentyl, n-octyl or tert-octyl. Examples of the alkoxy group having 1 to 15 carbon atoms in R ³ include: methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, and tert-butoxy group , pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, ten Pentaalkoxy etc.

Among them, R ³ can be a hydrogen atom, or a hydrocarbon group with 1 to 15 carbon atoms, a hydrogen atom, or a hydrocarbon group with 1 to 8 carbon atoms, or a hydrogen atom or a linear or branched alkyl group with 1 to 8 carbon atoms. , can be a hydrogen atom, methyl, tert-butyl, tert-pentyl, n-octyl, or tert-octyl.

Examples of the halogen atom of R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Examples of the hydrocarbon group having 1 to 8 carbon atoms in R ⁴ include the same hydrocarbon groups as those having 1 to 8 carbon atoms in the hydrocarbon group in R ³ described above. Examples of the alkoxy group having 1 to 6 carbon atoms in R ⁴ include the same alkoxy groups having 1 to 6 carbon atoms in the alkoxy group as R ³ .

R ⁴ may be a hydrocarbon group having 1 to 4 carbon atoms such as a hydrogen atom, a halogen atom, a nitro group, a cyano group, a methoxy group, or a tert-butyl group.

The monomer having a benzotriazole skeleton represented by the general formula (A) is not particularly limited. Specific examples include: 2-[2-hydroxy-5-(methacryloxymethyl) )phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(acrylyloxymethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-( Methacryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(acryloxyethyl)phenyl]-2H-benzotriazole, 2-[ 2-Hydroxy-5-(methacryloxypropyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloxypropyl)phenyl]-2H-benzene Triazole, 2-[2-hydroxy-5-(methacryloyloxybutyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(acrylyloxybutyl) Phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloxyhexyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(propene hydroxyhexyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(methacryloyloxyethyl)phenyl]-2H-benzotriazole Azole, 2-[2-hydroxy-3-tert-butyl-5-(acryloxyethyl)phenyl]-2H-benzotriazole, 2-[2-hydroxy-5-(methacrylamide) acyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2-hydroxy-5-(propenyloxyethyl)phenyl]-5-chloro-2H-benzotriazole Azole, 2-[2-hydroxy-5-(methacryloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(acryloxyethyl) [ethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloyloxyethyl)phenyl]-5-cyano-2H- Benzotriazole, 2-[2-hydroxy-5-(acryloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2-hydroxy-5-(methyl Acryloxyethyl)phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2-hydroxy-5-(acryloxyethyl)phenyl]-5-tert-butyl Base-2H-benzotriazole, 2-[2-hydroxy-5-(methacryloxyethyl)phenyl]-5-nitro-2H-benzotriazole, 2-[2-hydroxy- 5-(Acrylyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, methacrylic acid 2-[2-(2-hydroxy-4-octyloxyphenyl)-2H- 1,2,3-benzotriazole-5-oxy]ethyl ester, etc.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include: (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, and Conic acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction of a monomer having a hydroxyl group such as 2-(meth)acrylic acid hydroxyethyl ester and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride can also be utilized. substance, ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, as the carboxyl precursor, acid anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

Among the alkali-soluble resins, 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 particularly preferred. In the case where a photopolymerizable functional group is contained, the alkali-soluble resins may form with each other, or with a photopolymerizable compound such as a polyfunctional monomer, during the hardening step of the resin composition during the production of the color filter. Cross-linking bonds. The film strength of the cured film is further improved and the development resistance is improved. In addition, the thermal 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 conventionally known methods. For example, a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of the alkali-soluble resin, and ethylidene is introduced into the side chain. The method of unsaturated bonds; or the method of introducing structural units with hydroxyl groups into the copolymer in advance, adding compounds with isocyanato groups and ethylenically unsaturated bonds in the molecules, and introducing ethylenically unsaturated bonds into the side chains. wait.

Moreover, from the viewpoint of excellent adhesion of the colored layer, the alkali-soluble resin preferably further has a hydrocarbon ring. Since the alkali-soluble resin has a hydrocarbon ring as a bulky base, shrinkage during hardening is suppressed, peeling between substrates is relaxed, and substrate adhesion is improved. Examples of such a hydrocarbon ring include an aliphatic hydrocarbon ring that may have a substituent, an aromatic hydrocarbon ring that may have a substituent, and combinations thereof. The hydrocarbon ring may have an alkyl group, a carbonyl group, a carboxyl group, or an oxycarbonyl group. , amide group, hydroxyl group, nitro group, amine group, halogen atom and other substituents. The hydrocarbon ring may be included as a monovalent group or as a bivalent or higher group.

Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbisane, isobornane, tricyclo[5.2.1.0(2,6)]decane (di Aliphatic hydrocarbon rings such as cyclopentane) and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorine; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene, etc. Or Cardo structure (9,9-diaryl fluoride); a group in which part of these groups is substituted by a substituent, etc. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom, and the like.

When an aliphatic hydrocarbon ring is included as a hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance or adhesion of the colored layer and improving the brightness of the obtained colored layer. In addition, when the above-mentioned Cardo structure is included, the hardenability of the colored layer is improved, the fading of the color material is suppressed, and the solvent resistance (NMP (N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone) It is especially good to consider the improvement of swelling inhibition).

The alkali-soluble resin (U) in the present invention is preferably a (meth)acrylic copolymer containing a structural unit having a carboxyl group, a structural unit having a benzotriazole skeleton, and a structural unit having a hydrocarbon ring, and a styrene- At least one carboxyl group-containing copolymer among the (meth)acrylic copolymers, more preferably, a structural unit having a carboxyl group, a structural unit having a benzotriazole skeleton, a structural unit having a hydrocarbon ring, and a side chain having ethylene. At least one carboxyl group-containing copolymer among (meth)acrylic copolymers and styrene-(meth)acrylic copolymers with structural units of sexually unsaturated bonds.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include: (meth)cyclohexyl acrylate, (meth)acrylic acid dicyclopentyl, (meth)acrylic acid adamantyl ester, (methyl) Isoacrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., from the perspective of improving the strength or heat resistance of the coating film, it is preferred to use those selected from the group consisting of (methyl) (meth)acrylate, benzyl (meth)acrylate, and styrene.

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

The (meth)acrylic copolymer can be made into an alkali-soluble resin with required properties by appropriately adjusting the added amount of each structural unit. From the viewpoint of easily and favorably obtaining the effects of the present invention, the added amount of the benzotriazole skeleton-containing ethylenically unsaturated monomer is preferably 1 mass % or more, and may be 2 mass % or more relative to the total amount of monomers. On the other hand, the benzotriazole skeleton contains phenolic hydroxyl groups, so although it has developability, it is weakly acidic compared to carboxylic acid, so the developability is weak. On the other hand, due to its large-volume structure, it is subject to In view of the risk of lowering the developability when introduced in a large amount, the added amount of the ethylenically unsaturated monomer containing a benzotriazole skeleton is preferably 10% by mass or less based on the total amount of monomers, but may not be used. Up to 10 mass%, may be 8 mass% or less. That is, the structural unit having a benzotriazole skeleton is preferably included in an amount of 1% by mass or more and 10% by mass or less based on all the structural units of the alkali-soluble resin (U). The lower limit may be 2% by mass or more and the upper limit may be 2% by mass or more. The value may be less than 10% by mass and may be 8% by mass or less.

From the perspective of obtaining a good pattern, the added amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5 mass% or more, more preferably 10 mass% or more relative to the total amount of monomers. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, etc., the added amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50 mass % or less, more preferably 40 mass %, based on the total amount of the monomers. %the following.

Furthermore, at least one of a (meth)acrylic copolymer containing a structural unit having an ethylenically unsaturated bond and a styrene-(meth)acrylic copolymer that can be more preferably used as an alkali-soluble resin contains a carboxyl group In the copolymer, the amount of the compound having both an epoxy group and an ethylenically unsaturated bond relative to the carboxyl group-containing ethylenically unsaturated monomer is preferably 5 mass% or more and 95 mass% or less, more preferably 10 Mass% or more and 90 mass% or less.

From the viewpoint of improving the UV resistance of the finally obtained colored layer, the preferred weight average molecular weight (Mw) of the alkali-soluble resin (U) is 3,000 or more. The lower limit value may be above 4000 or above 5000. On the other hand, if the weight average molecular weight (Mw) is too large, the developability of the alkaline developer decreases, and residues may remain on the substrate. Therefore, the upper limit is preferably 20,000 or less, may be 18,000 or less, or may be 15,000 or less.

From the aspects of developability (solubility) in the alkaline aqueous solution used in the developer and the adhesion to the substrate, the acid value of the alkali-soluble resin (U) is preferably 40 mgKOH/g or more and 300 mgKOH/g or less. The lower limit value may be 50 mgKOH/g or more, 60 mgKOH/g or more, or 70 mgKOH/g or more. On the other hand, if the polarity is high, the upper limit may be 150 mgKOH/g or less, 130 mgKOH/g or less, or 110 mgKOH/g or less from the viewpoint of reduced solubility in a solvent.

Ethylenically unsaturated when the side chain of the alkali-soluble resin (U) has an ethylenically unsaturated group, in order to obtain effects such as improved film strength of the cured film, improved development resistance, and excellent adhesion to the substrate. The bond equivalent is preferably in the range of 100 to 2000, particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance and adhesion will be excellent. In addition, if it is 100 or more, the ratio of other structural units such as the above-mentioned structural unit having a carboxyl group or a structural unit having a hydrocarbon ring can be relatively increased, so the developability or heat resistance is excellent. Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bonds in the alkali-soluble resin, and is represented by the following mathematical formula (1).

Equation (1) Ethylenically unsaturated bond equivalent (g/mol)=W(g)/M(mol) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the mole 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, for example, by measuring the number of ethylenically unsaturated bonds contained per 1 g of the alkali-soluble resin according to the iodine value test method described in JIS K 0070:1992.

The alkali-soluble resin used in the photosensitive colored resin composition of the present invention includes the above-mentioned specific alkali-soluble resin (U), but may further include an alkali-soluble resin that does not meet the above-mentioned specific alkali-soluble resin (U). As long as the effects of the present invention can be obtained, the content ratio of the specific alkali-soluble resin (U) in the alkali-soluble resin used in the photosensitive colored resin composition of the present invention is not particularly limited. The content ratio of the specific alkali-soluble resin (U) may be 10% by mass or more, 20% by mass or more, 35% by mass or more, 50% by mass or more, relative to the total amount of the alkali-soluble resin. 70% by mass or more, or 100% by mass.

In the present invention, the alkali-soluble resin that does not meet the above-mentioned specific alkali-soluble resin (U) is not particularly limited, and a previously known alkali-soluble resin can be appropriately selected and used. For example, in the description of the specific alkali-soluble resin (U) mentioned above, an alkali-soluble resin similar to the above-mentioned alkali-soluble resin (U) except that it does not contain a structural unit having a benzotriazole skeleton can be cited. Examples of the alkali-soluble resin that does not meet the above-mentioned specific alkali-soluble resin (U) include a (meth)acrylic copolymer containing the above-mentioned structural unit having a carboxyl group and the above-mentioned structural unit having a hydrocarbon ring, and styrene-( At least one carboxyl group-containing copolymer among the meth)acrylic copolymers may also be one containing the above-mentioned structural unit having a carboxyl group, the above-mentioned structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond in the side chain. At least one carboxyl group-containing copolymer among methacrylic copolymers and styrene-(meth)acrylic copolymers.

In addition, the epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but an epoxy (meth)acrylate resin obtained by reacting an epoxy compound with an unsaturated group-containing monocarboxylic acid reactant and an acid anhydride is suitable. ) acrylate compound. 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 hardenability of the colored layer is improved, the fading of the color material is suppressed, and the residual film rate of the colored layer is increased. Considering this aspect, it is better to include the Cardo structure. As the alkali-soluble resin that does not meet the above-mentioned specific alkali-soluble resin (U), one type may be used alone, or two or more types may be used in combination.

As long as the alkali-soluble resin used in the photosensitive colored resin composition contains at least the above-mentioned specific alkali-soluble resin (U), one type can be used alone or two or more types can be used in combination. The content is not particularly limited. The alkali-soluble resin (U) is preferably in the range of 3 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less, based on the total solid content of the photosensitive colored resin composition. Within the range, more preferably within the range of 8 mass % or more and 40 mass % or less. If the content of the alkali-soluble resin (U) is more than the above lower limit, sufficient alkaline developability and ultraviolet absorption function can be obtained, a sufficient line width offset reduction effect can be obtained, and UV resistance can be improved, and , if the content of the alkali-soluble resin (U) is below the above upper limit, film roughness or pattern defects can be suppressed during development. The alkali-soluble resin is preferably in the range of 5 mass % or more and 60 mass % or less, and more preferably in the range of 8 mass % or more and 40 mass % or less relative to the total solid content of the photosensitive colored resin composition. . If the content of the alkali-soluble resin is more than the above-mentioned lower limit, sufficient alkaline developability can be obtained, and if the content of the alkali-soluble resin is less than the above-mentioned upper limit, film roughness or pattern defects can be suppressed during development. .

[Color] In order to produce photosensitive coloring that can suppress changes in chromaticity or decrease in brightness before and after the high-temperature heating step, improve the brightness of the coloring layer finally obtained, and form a coloring layer that suppresses changes in film thickness before and after development with a thin line width In the resin composition of the present invention, the colorant contains a lake colorant of a triarylmethane-based dye. ＜Triarylmethane dye lake material＞ From the perspective of excellent heat resistance and light resistance and achieving high brightness of the color filter, the lake color material of the triarylmethane-based dye is preferably a lake material of a triarylmethane-based dye and a polyacid. The lake color material of the triarylmethane-based dye is preferably at least one selected from the color material represented by the following general formula (1) and the color material represented by the following general formula (2), Since it forms a molecular association state, exhibits more excellent heat resistance, and can achieve high brightness, a colorant represented by the following general formula (1) is preferred.

[Chemical 2] General formula (1) (In the general formula (1), A is an a-valent organic group with no π bond on the carbon atom directly bonded to N. The organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the end directly bonded to N. , or an aromatic group having the aliphatic hydrocarbon group, which may contain heteroatoms in the carbon chain. ^{B c-} represents a c-valent polyacid anion. R ⁱ to R ^v each independently represent a hydrogen atom and an alkyl group that may have a substituent. Or an aryl group which 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 which may have a substituent, or an alkyl group which may have a substituent. Alkoxy group, halogen atom or cyano group. ^{Ar 1} represents a divalent aromatic group which may have a substituent. There are a plurality of R ⁱ to R ^vii and Ar ¹ which may be the same or different respectively. a and c represent 2 or more Integers, b and d represent integers above 1. f and g represent integers above 0 and below 4. There are a plurality of f and g which may be the same or different respectively.)

[Chemical 3] General formula (2) (In the general formula (2), R ^I to R ^VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ^I and R ^II , R ^III and R ^IV , and R ^V It can be bonded to R ^VI to form a ring structure. R ^VII and R ^VIII 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. Ar ² represents an optional substituent. For the divalent aromatic heterocyclic group, there are a plurality of R ^I to R ^VIII and Ar ² which may be the same or different respectively. ^{E m-} represents an m-valent polyacid anion. m represents an integer of 2 or more. k and l represent 0 An integer above and below 4. There are a plurality of k and l, which may be the same or different.)

The color material represented by the above general formula (1) contains anions with a valence of more than two valences and cations with a valence of more than two valences. Therefore, in the aggregate of the color material, the anions and the cations are not ionically bonded only one molecule to one molecule. Molecular aggregates in which multiple molecules are associated through ionic bonds can be formed, so the apparent molecular weight is significantly increased compared to the molecular weight of previous lake pigments. It is speculated that by forming such molecular aggregates, the cohesion force in the solid state is further improved, the thermal movement is reduced, and the dissociation of ion pairs or the decomposition of the cationic part is suppressed, making it less likely to fade than previous lake pigments.

A in the above general formula (1) is an a-valent organic group whose carbon atom is directly bonded to N (nitrogen atom) and does not have a π bond, and the organic group is a saturated aliphatic group at least at the end directly bonded to N. The hydrocarbon group is an aliphatic hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, and may contain heteroatoms such as O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in the carbon chain. That is, the organic group represents an aliphatic hydrocarbon group that has a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, and may contain heteroatoms such as O, S, N, etc. in the carbon chain; or an aliphatic hydrocarbon group at the terminal directly bonded to N An aromatic group that has an aliphatic hydrocarbon group and may contain heteroatoms such as O, S, N, etc. 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 remain consistent with the monomer. Same color.

In A, the aliphatic hydrocarbon group with at least a saturated aliphatic hydrocarbon group at the terminal directly bonded to N can be straight chain, branched or cyclic as long as the carbon atom at the terminal directly bonded to N does not have a π bond. In any of them, the carbon atoms other than the terminal ones may have unsaturated bonds, may have substituents, and may include O, S, and N in the carbon chain. For example, it may include a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc., and the hydrogen atom may be further substituted by a halogen atom or the like. In addition, the aromatic group having an aliphatic hydrocarbon group in A can be exemplified by a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and may have a substituent. , it can also be a heterocyclic ring containing O, S, and N. Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of the rigidity of the skeleton. Examples of the cyclic aliphatic hydrocarbon group include groups including cyclohexane, cyclopentane, nordecane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 ^2,6 ]decane, and adamantane. . Examples of the aromatic group include groups containing a benzene ring and a naphthalene ring. For example, when A is a divalent organic group, examples include a linear, branched, or cyclic alkylene group with 1 to 20 carbon atoms, or a xylylene group substituted with 2 carbon atoms from 1 to 20 carbon atoms. 20 alkylene group, aromatic group, etc.

In the present invention, from the perspective of balancing the robustness and freedom of molecular motion and improving heat resistance, A preferably has two or more cyclic aliphatic hydrocarbon groups, and has a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. Hydrocarbon group, and 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 cycloalkyl 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. Among them, A is more preferably It is a structure with two or more cyclic aliphatic hydrocarbon groups connected by linear or branched aliphatic hydrocarbon groups. The presence of two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples thereof include the same ones as the above-mentioned cyclic aliphatic hydrocarbon groups. Among them, cyclohexane and cyclopentane are preferred.

In the present invention, from the viewpoint of heat resistance, the above-mentioned A is preferably a substituent represented by the following general formula (1a).

[Chemical 4] General formula (1a) (In the general formula (1a), R ^xi represents an alkane having 1 to 3 carbon atoms which may have an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms as a substituent. group, R ^xii and R ^xiii each independently represent an alkyl group with a carbon number of 1 to 4 or less, or an alkoxy group with a carbon number of 1 to 4, p represents an integer of 1 to 3, q and r each independently represent represents an integer from 0 to 4. When there are a plurality of R ^xi , R ^xii , R ^xiii and r, the plurality of R ^xi , R ^xii , R ^xiii and r may be the same or different from each other)

An alkylene group having a carbon number of 1 or more and 3 or less in R ^xi is preferred from the viewpoint of excellent balance between robustness and thermal movement of the color-developing site and improvement of heat resistance. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, and the like. Among these, a methylene group or an ethylene group is preferred, and a methylene group is more preferred. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl, and may be linear or branched. Moreover, examples of the alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched.

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

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

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

[Chemistry 5]

The alkyl group in R ⁱ to R ^v is not particularly limited. For example, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms may be cited. Among them, linear or branched alkyl groups having 1 to 8 carbon atoms may be cited. From the viewpoint of brightness and heat resistance, From this perspective, examples include linear or branched chain alkyl groups having 1 to 5 carbon atoms, and examples include the case where the alkyl group in R ⁱ to R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like. Examples of the substituted alkyl group include an aralkyl group such as a benzyl group. wait. The aryl group in R ⁱ to R ^v is not particularly limited. For example, phenyl group, naphthyl group, etc. can be mentioned. Examples of substituents that the aryl group may have include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group, and the like. Among them, from the viewpoint of chemical stability, R ⁱ to R ^v are preferably each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , or R ^iv and R ^v bonds to form a pyrrolidine ring, a piperidine ring, and a morpholine ring.

From the viewpoint of heat resistance, it is preferred that at least one of R ⁱⁱ to R ^v be a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. It is considered that since at least one of R ⁱⁱ to R ^v has a cycloalkyl group or an aryl group, intermolecular interaction due to steric hindrance is reduced, and therefore the influence of heat on the color developing site can be suppressed, resulting in excellent heat resistance.

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

[Chemical 6] General formula (1b) (In the general formula ( ^{1b ) ,} R and less than 4 alkoxy groups)

[Chemical 7] General formula (1c) (In the general formula (1c), R ^xvii , R ^xviii , and R ^xix each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms that may have a substituent, or an alkyl group having 1 or more carbon atoms that may have a substituent. and less than 4 alkoxy groups)

Examples of the alkyl group having 1 to 4 carbon atoms in R ^xiv , R ^xv , R ^xvi , R ^xvii , R ^xviii , and R ^xix include methyl, ethyl, propyl, and butyl, and may be It is straight chain, and may also have branched chains. Moreover, examples of the alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched. Examples of substituents that the alkyl group and alkoxy group may have include a halogen atom, a hydroxyl group, and the like.

When having a substituent represented by the above general formula (1b), from the viewpoint of heat resistance, it is preferred that at least one of R ^xiv , R ^xv , and R ^xvi have a carbon number of 1 or more that may have a substituent. And an alkyl group of 4 or less, or an alkoxy group with a carbon number of 1 to 4 that may have a substituent, more preferably at least one of R ^xiv and R ^xv 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.

In addition, when having a substituent represented by the above general formula (1c), from the viewpoint of heat resistance, it is preferred that at least one of R ^xvii , R ^xviii , and R ^xix have a carbon number that may have a substituent. An alkyl group of 1 to 4 carbon atoms, or an alkoxy group having a carbon number of 1 to 4 or less that may have a substituent, more preferably at least one of R ^xvii and R ^xviii having a carbon number of 1 or more and that may have a substituent. an alkyl group having 4 or less carbon atoms, or an alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms which may have a substituent.

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 or more and 8 or less, and more preferably a carbon number of 1 or more and 4 or less. The alkyl group. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl, and may be linear or branched. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like. In addition, the alkoxy group in R ^vi and R ^vii is not particularly limited, but it is preferably a linear or branched alkoxy group with a carbon number of 1 or more and 8 or less, and more preferably an alkoxy group with a carbon number of 1 or more and 8 or more. 4 or less alkoxy groups. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched. The substituent that the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like. Examples of the halogen atom in R ^vi and R ^vii include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The substitution numbers of R ^vi and R ^vii , that is, f and g respectively independently represent an integer of 0 or more and 4 or less. Among them, 0 or more and 2 or less are preferred, and 0 or more and 1 or less are more preferred. There are plural f and g, which may be the same or different. In addition, R ^vi and R ^vii can be in the triarylmethane skeleton, or 𠮿 Any position of the aromatic ring having a resonance structure in the skeleton is substituted, and among them, it is preferable that the position between the substitution positions of the amino group represented by -NR ⁱⁱ R ⁱⁱⁱ or -NR ^iv R ^v is substituted.

The divalent aromatic group in Ar ¹ is not particularly limited. In addition to the aromatic hydrocarbon group containing a carbocyclic ring, the aromatic group in Ar ¹ may also be a heterocyclic group. Examples of the aromatic hydrocarbons in the aromatic hydrocarbon group include, in addition to the benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralan ring, indene ring, fentanyl ring, anthracene ring, phenanthrene ring, etc.; biphenyl, biphenyl, biphenyl, etc. Chain polycyclic hydrocarbons such as triphenyl, diphenylmethane, triphenylmethane, and stilbene. This chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton like diphenyl ether. On the other hand, examples of the heterocyclic ring in the heterocyclic group include: 5-membered heterocyclic rings such as furan, thiophene, pyrrole, ozole, thiazole, imidazole, and pyrazole; pyran, pyranone, pyridine, and pyranone 6-membered heterocycles such as , pyrimidine, and pyridine; benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyranone, quinoline, isoquinoline, acridine, phthalate , quinazoline, quinoline and other condensed polycyclic heterocycles. These aromatic groups may further have alkyl groups, alkoxy groups, hydroxyl groups, halogen atoms, and phenyl groups that may be substituted by these as substituents.

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

The valence a in A refers to the number of color-developing cationic sites constituting the cation, and a is an integer of 2 or more. In this lake color material, since the valence a of the cation is 2 or more, the heat resistance is excellent. However, the valence a of the cation may be 3 or more. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, a is preferably 4 or less, more preferably 3 or less.

The molecular weight of the cation in the color material represented by general formula (1) is preferably 1,200 or more, and more preferably 1,300 or more, in view of excellent heat resistance and easy suppression of color change during heating.

In the colorant represented by the general formula (1), the anionic part (B ^c- ) is a c-valent polyacid anion, and is an anion having a valence of more than or equal to two valences from the viewpoint of high brightness and excellent heat resistance.

The polyacid anion formed by the condensation of a plurality of oxygen-containing acids can be a homopolyacid 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 the composition ratio of polyatoms, and n represents the composition ratio of oxygen atoms. Examples of the polyatomic M include Mo, W, V, Ti, Nb, and the like. Examples of the hetero atom X include Si, P, As, S, Fe, Co, and the like. In addition, a part of it may contain counter cations such as Na ⁺ or H ⁺ . Among them, from the viewpoint of excellent heat resistance, a polyacid containing one or more elements selected from tungsten (W) and molybdenum (Mo) is preferred. Examples of such polyacid include tungstate ion [W ₁₀ O ₃₂ ] ^4- which is a homopoly acid, molybdate ion [Mo ₆ O ₁₉ ] ^2- , or phosphotungstate ion which is a heteropoly acid. [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 from 1 to 11), [P ₂ W _{182 - t} Mo _t O ₆₂ ] ^6- (t is an integer from 1 to 17), silicotungstomolybdate ion [SiW _{12 - u} Mo _u O ₄₀ ] ^4- (u is an integer from 1 to 11), etc. As the polyacid containing at least one of tungsten (W) and molybdenum (Mo), from the viewpoint of heat resistance and ease of acquisition of raw materials, a heteropoly acid containing phosphorus is more preferred among the above. (P) heteropoly acid. Furthermore, from the viewpoint of heat resistance, phosphotungstate ions [PW ₁₀ Mo ₂ O ₄₀ ] ^3- , [PW ₁₁ Mo ₁ O ₄₀ ] ^3- , and phosphotungstomolybdate ions [PW ₁₂ O ₄₀ ] are more preferred. ^3- any one.

In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent integers above 1. When b is 2 or more, a plurality of cations present in the molecular aggregate may be a single type or a combination of two or more types. Furthermore, when d is 2 or more, a plurality of anions present in the molecular aggregate may be a single type or a combination of two or more types.

In addition, the lake color material represented by the general formula (1) can be prepared by referring to the specifications of International Publication No. 2012/144520 and International Publication No. 2018/003706, for example.

On the other hand, in the general formula (2), R ^I to R ^VI each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ^I and R ^II , R ^III and R ^IV , ^RV and R ^VI can bond to form a ring structure. Each of R ^I to R ^VI may be the same as R ⁱ to R ^v of the above general formula (1). In the general formula (2), R ^VII and R ^VIII 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, which may also be combined with the above general formula (1) R ^vi and R ^vii are the same. In the general formula (2), Ar ² represents a divalent aromatic heterocyclic group which may have a substituent, and this Ar ² may be the same as the aromatic heterocyclic group in Ar ¹ of the general formula (1). Moreover, in the general formula (2), E ^m- represents an m-valent polyacid anion, and the m-valent polyacid anion can 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. The plural cations present in the general formula (2) may be a single type, or two or more types may be combined. In addition, the anion may be a single type or a combination of two or more types. In addition, k and l in the general formula (2) may be the same as f and g in the above-mentioned general formula (1). In addition, the lake color material represented by formula (2) can be prepared by referring to Japanese Patent Application Laid-Open No. 2017-16099, for example.

Furthermore, the lake color material of the triarylmethane-based dye used in the photosensitive colored resin composition of the present invention is not limited to the color material selected from the color material represented by the above-mentioned general formula (1) and the above-mentioned general formula (2). One or more of the indicated colors can be appropriately selected and used. For example, cations of triarylmethane-based dyes described in Japanese Patent Laid-Open No. 2015-96947, Japanese Patent Laid-Open No. 2016-27149, and Japanese Patent Laid-Open No. 2017-16099 and the above various types can be used. A polyacid anionic lake color material; or a triarylmethane dye described in Japanese Patent Laid-Open No. 2015-96947, Japanese Patent Laid-Open No. 2016-27149, and Japanese Patent Laid-Open No. 2017-16099; A multi-acid lake color.

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

＜Other colors＞ The coloring material used in the present invention contains a lake coloring material of a triarylmethane-based dye as an essential component, but it can also be used in combination with other coloring materials in order to adjust the color tone within the scope 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 in a mixture of two or more types.

As other color materials, other blue color materials, purple color materials, and red color materials can be preferably used, but they are not limited to these. As other blue colorants, well-known organic blue pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are used. As the purple colorant, CI Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 and other well-known organic purple pigments are used. As the red or purple colorant, for example, those described in International Publication No. 2020/071041, Japanese Patent Application Publication No. 2018-100323, International Publication No. 2014/123125, etc. Dyes and 𠮿 It is a kind of lake color material of dye.

＜Color content ratio＞ In the photosensitive colored resin composition of the present invention, other color materials other than the lake color material of the triarylmethane-based dye may be further included in the color material within the range that does not impair the effect of the present invention. In total, the content ratio of the lake color material of the triarylmethane-based dye is preferably 70 mass % or more and 100 mass % or less, more preferably 80 mass % or more and 100 mass % or less, and still more preferably 90 mass % More than 100 mass % and less, More preferably, it is 95 mass % or more and 100 mass % or less.

The average primary particle diameter of the colorant used in the present invention is not particularly limited as long as it can achieve the required color development when forming the colored layer of the color filter, and it will be determined according to the The type of colorant used varies, but it is preferably in the range of 10 to 100 nm, and more preferably 15 to 60 nm. When the average primary particle diameter of the color material is in the above range, a display device including a color filter produced using the photosensitive colored resin composition of the present invention can be made high-contrast and high-quality.

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

The colorant used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. In addition, commercially available coloring materials may be finely processed and used.

In the photosensitive colored resin composition of the present invention, the content of the colorant is not particularly limited. From the aspects of dispersion and dispersion stability, the content of the colorant is usually in the range of 3% to 65% by mass, preferably 4% to 4% by mass relative to the total solid content of the photosensitive colored resin composition. Within the range of 60% by mass, more preferably within the range of 15% by mass to 60% by mass. If it is more than the said lower limit, the colored layer when the photosensitive colored resin composition is apply|coated to a specific film thickness (usually 1.0 micrometer - 5.0 micrometer) will have sufficient color density. Moreover, if it is below the said upper limit, the storage stability will be excellent, and the colored layer which will have sufficient hardness or adhesiveness with a board|substrate can be obtained. Especially when forming a colored layer with a high colorant concentration, the total content of the colorants is preferably in the range of 20 mass % to 65 mass % relative to the total solid content of the photosensitive colored resin composition. More preferably, it is in the range of 30 mass% to 60 mass%.

[Photopolymerizable compound] The photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized using a photoinitiator. Generally, a compound having two or more ethylenically unsaturated bonds can be suitably used. , particularly preferably a polyfunctional (meth)acrylate having two or more acrylic groups or methacrylic groups. As such a polyfunctional (meth)acrylate, any one appropriately selected from those known in the art can be used. Specific examples include those described in Japanese Patent Application Laid-Open No. 2013-029832.

One type of these polyfunctional (meth)acrylates may be used alone, or two or more types may be used in combination. Furthermore, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional (meth)acrylate is preferably polymerizable ethylene having three or more (trifunctional) The sexually unsaturated bond is preferably a poly(meth)acrylate of a trivalent or higher polyol or a dicarboxylic acid modified product thereof. Specifically, trimethylolpropane tri(meth)acrylate is preferred. acrylate, pentaerythritol tri(meth)acrylate, succinic acid modification of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, succinic acid modification of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

Among them, the photopolymerizable compound used in the present invention is preferably a photopolymerizable compound containing an alkylene oxide from the viewpoint of achieving both a high development residual film rate and a thin line width. Preferred examples of the photopolymerizable compound containing alkylene oxide include photopolymerizable compounds containing ethylene oxide and/or propylene oxide. It is presumed that when the above-mentioned photopolymerizable compound containing alkylene oxide is contained, peroxide radicals that have lost polymerization activity due to oxygen hindrance are regenerated into active radicals, so the 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, and alkylene oxide-modified dimethacrylate. Pentaerythritol tetra(meth)acrylate, alkylene oxide-modified dipentaerythritol penta(meth)acrylate, alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, alkylene oxide-modified trimethylolpropane triacrylate (meth)acrylate, ethylene oxide-modified glycerol 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 Meth)acrylate, etc. Among them, more preferred ones include ethylene oxide-modified diglycerol tetra(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate.

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

The content of the above-mentioned photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but 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 within the range of 10 mass% to 40 mass%. If the content of the photopolymerizable compound is more than the above lower limit, photohardening proceeds sufficiently, elution of the exposed part during development can be suppressed, line width shift can be suppressed, and solvent resistance becomes good. In addition, if the photopolymerizable compound When the content of the compound is below the above-mentioned upper limit, the alkaline developability is sufficient.

[Photoinitiator] The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and one type or a combination of two or more types of initiators may be used from among various previously known initiators. Examples of the photoinitiator include benzophenone, N,N-dimethylaminobenzophenone, and 4,4'-bisdiethylaminobenzophenone (such as Hicure ABP, Kawaguchi Pharmaceutical Co., Ltd.), 4-methoxy-4'-dimethylaminobenzophenone and other aromatic ketones; benzoin ethers such as benzoin methyl ether; ethyl benzoin and other benzoins; 2-(o-chlorobenzene methyl)-4,5-phenylimidazole dimer and other biimidazole; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-dioxadiazole and other halomethyl groups Oxadiazole compounds; 2-(4-butoxy-naphthyl-1-yl)-4,6-bis-trichloromethyl-S-trichloroethyl and other halomethyl-S-trixazoles; 1,2 -Octanedione-1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzyl) Aceto)-9H-carbazol-3-yl]-,1-(O-acetyl oxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010 - Oxime esters such as photoinitiators such as oxime esters described in Japanese Patent Publication No. 527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Publication No. 2013-041153, etc.; 2-methyl-1-(4 -Methylthienyl)-2-morpholinylpropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinylbenzene) base)-1-butanone (such as Irgacure369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-methyl) Phylyl)phenyl]-1-butanone (Irgacure379EG, manufactured by BASF) and other α-amino ketones; diethyl 9-oxosulfide𠮿 Etc. 9-oxysulfur𠮿 class. Among them, from the viewpoint of excellent sensitivity, the photoinitiator used in the present invention is preferably at least one selected from the group consisting of oxime esters and α-aminoketones. From the viewpoint of wide adjustment and development resistance, α-aminoketones are preferred. α-aminoketones with a tertiary amine structure are preferred because they have a tertiary amine structure as an oxygen quenching agent in the molecule, so the free radicals generated by the initiator are not easily deactivated by oxygen and can improve the sensitivity. . In addition, as the photoinitiator, it is also preferable to use a combination of oxime esters and α-aminoketones from the viewpoint of suppressing water spots and improving sensitivity. Furthermore, water spots refer to traces of water infiltration that may occur after rinsing with pure water after alkaline development using ingredients that enhance alkaline developability. This kind of water spots will disappear after post-baking, so there is no problem as a product. However, during the appearance inspection on the pattern surface after development, it will be detected as abnormal spots, causing the problem that normal products cannot be distinguished from abnormal products. Therefore, if the inspection sensitivity of the inspection device is reduced during appearance inspection, the yield of the final color filter product will be reduced, which becomes a problem. In addition, as the photoinitiator, from the viewpoint of adjusting sensitivity, suppressing water spots, and improving development resistance, it is preferable to combine at least one selected from the group consisting of oxime esters and α-aminoketones and 9 -oxygen sulfur𠮿 class combination.

As long as the effects of the present invention are not impaired, the total content of the photoinitiators used in the photosensitive colored resin composition of the present invention is not particularly limited. Preferably, it is in the range of 0.1 mass % - 12.0 mass %, More preferably, it is in the range of 1.0 mass % - 8.0 mass %. If the content is more than the above lower limit, photocuring proceeds sufficiently, and the exposed portion is inhibited from elution during development, and the solvent resistance becomes good. On the other hand, if it is less than the above upper limit, it is possible to inhibit the obtained The decrease in brightness caused by yellowing of the colored layer. In addition, regarding the content ratio of the above-mentioned photopolymerizable compound and the above-mentioned photoinitiator used in the photosensitive colored resin composition, from the viewpoint of suppressing line width deviation and improving solvent resistance, and further from the viewpoint of the development residue From the perspective of improving the inhibitory effect, 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 more preferably 40 parts by mass with respect to 100 parts by mass of the above-mentioned photopolymerizable compound. or less, more preferably 30 parts by mass or less.

[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 the components. The solvent can be used alone or in combination of two or more types. Specific examples of the solvent include alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, methoxyalcohol, and ethoxyalcohol; methoxyethoxyethanol, and ethoxyethoxyethanol. Other carbitol solvents; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethoxyethylpropionate, ethyl lactate, methyl hydroxypropionate, hydroxypropionate Ester solvents such as ethyl propionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate; acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketone solvents; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate Ester, 3-methoxybutyl acetate, ethoxyethyl acetate and other glycol ether acetate solvents; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butylcarboxylate Carbitol acetate solvents such as BCA, etc.; diacetate esters such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol Glycol ether solvents such as alcohol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; Aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; tetrahydrofuran, etc. cyclic ether solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; aromatic hydrocarbons such as toluene and xylene and other organic solvents. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used in view of the 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 acetate from the viewpoint of solubility of other components or coating suitability. One of the group consisting of ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethoxyethyl propionate, ethyl lactate, and 3-methoxybutyl acetate above.

In the photosensitive colored resin composition of the present invention, the content of the solvent may be appropriately set within the range in which the colored layer can be formed with high accuracy. Relative to the total amount of the photosensitive colored resin composition containing the solvent, it can usually be in the range of 55 mass % to 95 mass %, and preferably in the range of 65 mass % to 88 mass %. When the content of the above-mentioned solvent is within the above-mentioned range, the coating property can be excellent.

[Dispersant] In the photosensitive colored resin composition of the present invention, the above-mentioned color material can be dispersed in a solvent using a dispersant. In the present invention, the dispersant can be appropriately selected and used from previously known dispersants. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, polysiloxane, and fluorine-based surfactants can be used. Among surfactants, polymer dispersants are preferred because they can be dispersed uniformly and finely.

Examples of the polymer dispersant include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts and (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid. Ammonium salts or (partial) alkylamine salts; hydroxyl-containing polyacrylates and other hydroxyl-containing unsaturated carboxylate (co)polymers or their modified products; polyurethanes; unsaturated Polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethylene imine derivatives (produced by the reaction of poly(lower alkylene imine) and polyester containing free carboxyl groups Obtained amide or such alkali); polyallylamine derivatives (co-condensation products of polyallylamine and polyesters, polyamides or esters and amide selected from the group with free carboxyl groups (polyesteramides) Reaction products obtained by reacting more than one of these three compounds), etc. When the polymer dispersant is a copolymer, it may be any of a block copolymer, a graft copolymer, or a random copolymer. From the viewpoint of dispersion, block copolymers and graft copolymers are preferred. copolymer.

The dispersing agent can be appropriately selected and used according to the type of the colorant to have good dispersion properties, and is not particularly limited. When dispersing the lake material of the triarylmethane-based dye, an acidic dispersant that is an acidic polymer dispersant is preferably used as the dispersant. As the acidic dispersant used for dispersing the lake color material, for example, at least one selected from the group consisting of a polymer having a structural unit represented by the following general formula (I) and a carboxyl group-containing block copolymer can be suitably used. . When a pigment is further used as a colorant and dispersed, at least one selected from the group consisting of acidic or alkaline polymer dispersants and urethane dispersants may be used depending on the type of pigment. , and acidic or alkaline polymer dispersants can be used. When dispersing pigments that have undergone alkaline treatment, it is preferable to use an acidic dispersant as an acidic polymer dispersant. When dispersing pigments that have been acidified, it is preferable to use an alkaline polymer dispersant. alkaline dispersant. As the alkaline dispersant, for example, at least part of the amine groups selected from a polymer containing a repeating unit having a tertiary amine and a polymer containing a repeating unit having a tertiary amine, and an organic acid compound can be suitably used. At least one of the group consisting of salt-type polymers. The urethane dispersant is a compound having one or more urethane bonds (-NH-COO-) in one molecule. As the urethane dispersant, for example, the reaction product of a polyisocyanate having two or more isocyanate groups per molecule and a polyester having a hydroxyl group at one or both terminals 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 lake material for the above-mentioned triarylmethane dye. Dispersants. As the acidic dispersant, if a polymer having a structural unit represented by the following general formula (I) is used, the dispersibility and heat resistance of the lake color of the above-mentioned triarylmethane-based dye can be improved, and the color after heating can be suppressed. The color change of lake color material. Furthermore, when a lake colorant and a pigment are used together as a colorant, the dispersibility and storage stability of the pigment can be improved by using a polymer having a structural unit represented by the following general formula (I) as a dispersant. , forming a colored layer with improved substrate adhesion and coating film uniformity. It is presumed that since the polymer having the structural unit represented by the following general formula (I) is an ethylenically unsaturated monomer polymer, the skeleton has higher heat resistance than the polyether-based or polyester-based polymer, and There are multiple acidic phosphorus compound groups (-P(=O)(-R ¹² )(OH)) and their salts (-P(=O)(-R ¹² )(O ^- X ⁺ ) in the polymer ) has strong adsorption force on the surface of micronized colorants. Furthermore, it is speculated that if the surface of the color material is covered with at least one of acidic phosphorus compound groups and its salts, the pigment skeleton of the lake color material will be attacked (hydrogen abstraction or replacement) caused by active oxygen such as peroxide radicals. reactions, etc.) are suppressed, and the deterioration (oxidative deterioration) of the lake color material is suppressed.

[Chemical 8] (In the general formula (I), L ¹¹ is a direct bond or a bivalent linking group, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydroxyl group, a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ )-O ] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , or a monovalent group represented by -OR ¹⁶ , R ¹⁶ is a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ ) -O] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , -C(R ¹⁷ )(R ¹⁸ )-C(R ¹⁹ )(R ²⁰ )-OH, or -CH ₂ -C(R ²¹ )(R ²² )-CH ₂ -OH represents a monovalent group. R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH=CH ₂ , -CO-C(CH ₃ )=CH ₂ or -CH ₂ COOR ²³ represents a monovalent group, R ²³ is a hydrogen atom or the number of carbon atoms is 1 or more and 5 The following alkyl groups. R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrocarbon group having one or more selected from the group consisting of a hydrogen atom, a hydrocarbon group, or an ether bond and an ester bond. R ¹⁷ and R ¹⁹ can be bonded to each other to form a ring structure. In the case of forming the ^above -mentioned cyclic structure, the cyclic structure can further have a substituent R ²⁴ , which is a hydrocarbon group, or has one selected from the group consisting of ether bonds and ester bonds. The above hydrocarbon group. The above hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 represents an integer from 1 to 18, y1 represents an integer from 1 to 5, z1 represents an integer from 1 to 18)

In the general formula (I), L ^{1 1} is a direct bond or a bivalent linking group. Here, L ^{1 1} direct bonding means that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without intervening a connecting group. The bivalent linking group in L ^{1 1} is not particularly limited as long as it can connect the carbon atom and the phosphorus atom of the main chain skeleton. Examples of the divalent linking group in L ^{1 1} include: linear, branched or cyclic alkylene group, linear, branched or cyclic alkylene group having a hydroxyl group, aryl group, -CONH- group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof. Furthermore, in the present invention, the bonding direction of the bivalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the phosphorus atom side of the side chain. Conversely, -NH may be on the main chain side. The carbon atom side and -CO is on the phosphorus atom side of the side chain.

Among them, from the viewpoint of dispersibility, L ¹¹ in the general formula (I) is preferably a bivalent linking group containing a -CONH- group or a -COO- group. For example, when L ¹¹ is a bivalent linking group containing a -COO- group, L ¹¹ is preferably 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 each independently a hydrogen atom, a methyl group, or a hydroxyl group. x represents an integer from 1 to 18, and y represents 1 or more and An integer below 5, z represents an integer from 1 to 18, w represents an integer from 1 to 18).

The alkylene group with more than 1 and less than 8 carbon atoms in L ^{1 1'} can be linear, branched, or cyclic, such as methylene, ethylene, or trimethylene. base, propylene group, various butylene groups, various pentylene groups, various hexylene groups, various octylene groups, etc., part of the hydrogen can be substituted by hydroxyl group. x is an integer from 1 to 18, preferably 1 to 4, more preferably 1 to 2, y is an integer from 1 to 5, preferably 1 to 4 an integer, preferably 2 or 3. z is an integer from 1 to 18, preferably from 1 to 4, more preferably from 1 to 2. w is an integer from 1 to 18, preferably from 1 to 4.

Suitable specific examples of L ^{1 1} in the general formula (I) include -COO-CH ₂ CH(OH)CH ₂ -O-, -COO-CH ₂ CH ₂ -O-CH ₂ CH. (OH)CH ₂ -O-, -COO-CH ₂ C(CH ₂ CH ₃ )(CH ₂ OH)CH ₂ -O-, etc., but are not limited thereto.

Examples of the hydrocarbon group in R ^{1 2} include an alkyl group having from 1 to 18 carbon atoms, an alkenyl group from 2 to 18 carbon atoms, an aralkyl group, and an aryl group. The above-mentioned alkyl group having from 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, 𦯉yl, iso-𦯉yl, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc. The alkenyl group having 2 or more carbon atoms and 18 or less carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, and the like. The position of the double bond of the alkenyl group is not limited. From the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond exists at the end of the alkenyl group. Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, etc., and may further have a substituent. The number of carbon atoms in the aryl group is preferably from 6 to 24, more preferably from 6 to 12. Moreover, examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl, biphenylmethyl, etc., and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably from 7 to 20, more preferably from 7 to 14. The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, and nitro groups. In addition, as the substituent of the aromatic ring such as the above-mentioned aryl group or aralkyl group, in addition to a linear or branched alkyl group with a carbon number of 1 or more and 4 or less, alkenyl group and nitro group can be exemplified. , halogen atoms, etc. Furthermore, the above preferred carbon number does not include the carbon number of the substituent. In the above-mentioned R ^{1 2} , 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 ^{1 5} to R ²² include the same hydrocarbon groups as those in R ^{1 2} described above.

Among R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² , the hydrocarbon group having at least one selected from ether bond and ester bond is -R'-O-R'', -R'-(C =O)-O-R'', or -R'-O-(C=O)-R''(R' and R'' are hydrocarbon groups, or at least one of ether bond and ester bond is used to combine the hydrocarbon group The basis represented by the bonded basis). One group may have two or more ether bonds and ester bonds. When the hydrocarbon group is monovalent, there may be exemplified an alkyl group, an alkenyl group, an aralkyl group, and an aryl group. When the hydrocarbon group is divalent, there may be exemplified an alkylene group, an alkenylene group, an aryl group, and These combination bases.

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

From the viewpoint 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 monovalent group represented by -OR ¹⁶ , more preferably the following: R ¹² is a hydroxyl group, a methyl group, an ethyl group, a vinyl group, or an aromatic group which may have a substituent group or aralkyl group, vinyl group, allyl group, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , or -OR ¹⁶ represents a valent group, R ¹³ and R ¹⁴ are independently hydrogen atoms or methyl groups, R ¹⁵ is -CO-CH=CH ₂ or -CO-C(CH ₃ )=CH ₂ ; wherein, R ¹² is more preferably an aryl group, vinyl group, methyl group and hydroxyl group which may have a substituent.

In addition, from the viewpoint 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 base. It is speculated that if the structure has a structure in which carbon atoms are directly bonded to phosphorus atoms, it is less likely to be hydrolyzed, and therefore a resin layer with excellent alkali resistance can be formed. Among them, from the viewpoint of excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles, the following are preferred: R ¹² is a methyl group, an ethyl group, an optionally substituted aryl group, or an aralkyl group, vinyl, allyl, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , or -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ represents a valence group, R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ^{1 5} is -CO-CH=CH ₂ or -CO-C(CH ₃ )=CH ₂ . Among them, from the viewpoint of dispersibility, R ¹² is more preferably an aryl group which may have a substituent.

Moreover, in general formula (I), X represents a hydrogen atom or an organic cation. Organic cations are those containing carbon atoms in the cation portion. 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 trialkylsulfonium cations. Cations such as sulfonium cations, tetraalkylphosphonium cations and other phosphonium cations, etc. Among them, protonated nitrogen-containing organic cations are preferred from the viewpoint of dispersibility and alkaline developability. Among them, when the organic cation has an ethylenically unsaturated bond, it is preferable from the viewpoint of imparting curability.

The structural unit represented by the general formula (I) may be contained individually in one type or two or more types in the polymer.

The polymer may contain two structural units in which X is a hydrogen atom and a structural unit in which X is an organic cation among the structural units represented by the general formula (I). When these two structural units are included, it is not particularly limited as long as it exhibits good dispersibility and dispersion stability. X is the ratio of the number of structural units of the organic cation to that represented by the general formula (I) The total number of structural units of the structural units is preferably 0 or more and 50 mol% or less.

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

In the embodiment of the present invention, from the viewpoint of dispersibility, the polymer having the structural unit represented by the general formula (I) preferably further has a solvent affinity moiety. Among such polymers, those having the structural unit represented by the general formula (I) are preferred because they are excellent in dispersibility and storage stability and can form a high-contrast coating film even after long-term storage. , and a graft copolymer having a structural unit represented by the following general formula (II); or a block having a structural unit represented by the above general formula (I) and a structural unit represented by the following general formula (III) copolymer.

[Chemical 9] (In the general formula (II), L ²¹ represents a direct bond or a bivalent linking group, R ²⁵ represents a hydrogen atom or a methyl group, and Polymer represents a polymer chain having a structural unit represented by the following general formula (IV). General formula 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'' represents a valent base, R ²⁸ and R ²⁹ are each independently a hydrogen atom or a methyl group, R ³⁰ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or a monovalent group represented by -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 monovalent group, R ^30'' is an alkyl group with more than 1 and less than 18 carbon atoms, R ³¹ is a hydrogen atom or an alkyl group with more than 1 and less than 5 carbon atoms. The above-mentioned hydrocarbon group can Has a substituent. x2 and x2' represent an integer from 1 to 18, y2 and y2' represent an integer from 1 to 5, z2 and z2' represent an integer from 1 to 18)

[Chemical 10] (In the 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 each independently a hydrogen atom or a methyl group, R ³⁶ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ , R ³⁷ is a hydrocarbon group, -[CH(R ³⁴ ) -CH(R ³⁵ )-O] _x4 -R ³⁶ , -[(CH ₂ ) _y4 -O] _z4 -R ³⁶ , -[CO-(CH ₂ ) _y4 -O] _z4 -R ³⁶ represents a valence group, R ³⁸ is an alkyl group with 1 to 18 carbon atoms, R ³⁹ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and the above hydrocarbon group may have a substituent. n represents 5 or more and an integer below 200. x3 and x4 represent integers from 1 to 18, y3 and y4 represent integers from 1 to 5, z3 and z4 represent integers from 1 to 18)

(Graft copolymer) A preferred graft copolymer as an acidic dispersant is, for example, a graft copolymer having a structural unit represented by the above-mentioned general formula (I) and a structural unit represented by the above-mentioned general formula (II). things. In the above general formula (II), L ²¹ is a direct bond or a divalent linking group. The bivalent linking group in L ²¹ is not particularly limited as long as it can link a carbon atom derived from an ethylenically unsaturated bond to a polymer chain. Examples of the divalent coupling group in L ²¹ include the same bivalent coupling group as the above-described divalent coupling group in L ¹¹ .

In the above-mentioned general formula (II), Polymer represents a polymer chain having a structural unit represented by the above-mentioned general formula (IV). In the general formula (IV), the hydrocarbon group in R ³³ is preferably an alkyl group with 1 to 18 carbon atoms, an alkenyl group with 2 to 18 carbon atoms, an aralkyl group, or Aryl. Examples of these include the same ones as R ¹² described above.

R ³⁶ is preferably a hydrogen atom, or an alkyl group, an aralkyl group, an aryl group having 1 to 18 carbon atoms, or a monovalent group represented by -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ , R ³⁷ is preferably an alkyl group, aralkyl group, aryl group, -[CH(R ³⁴ )-CH(R ³⁵ )-O] _x4 -R ³⁶ , -[( CH ₂ ) _y4 -O] _z4 -R ³⁶ , a valent group represented by -[CO-(CH ₂ ) _y4 -O] _z4 -R ³⁶ . R ³⁸ represents an alkyl group having from 1 to 18 carbon atoms, and R ³⁹ represents a hydrogen atom or an alkyl group having from 1 to 5 carbon atoms. Examples of the alkyl group, aralkyl group and aryl group having 1 or more carbon atoms and 18 or less carbon atoms in R ³⁶ and R ³⁷ are the same as those for R ¹² above. Examples of the alkyl group in R ³⁸ and R ³⁹ are the same as those for R ¹² . When the above-mentioned R ³⁶ , R ³⁷ and R ³⁹ are groups having an aromatic ring, the aromatic ring may further have a substituent. Examples of the substituent include, in addition to linear, branched, and cyclic alkyl groups having 1 to 5 carbon atoms, alkenyl groups, nitro groups, halogens such as F, Cl, and Br. Atoms etc. Furthermore, the above preferred carbon number does not include the carbon number of the substituent. In the above-mentioned R ³³ and R ³⁷ , 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 can be set as follows: within the range that does not hinder the dispersion performance of the above-mentioned graft copolymer, etc., and further, through an alkoxy group, a hydroxyl group, a carboxyl group, an amine group, Substituted with substituents such as base, epoxy group, isocyanate group, and hydrogen bond forming group. Moreover, after synthesizing the graft copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group is reacted to add a polymerizable group. For example, glycidyl (meth)acrylate can be reacted with a graft copolymer having a carboxyl group, or hydroxyethyl (meth)acrylate can be reacted with a graft copolymer having an isocyanate group to add a polymerizable group. .

The polymer chain having a structural unit represented by the general formula (IV) is preferably one having among the above structural units derived from methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isopropyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth)acrylate Structural units of adamantyl acrylate, styrene, α-methylstyrene, vinylcyclohexane, etc. However, it is not limited to these.

In the embodiment of the present invention, among the above-mentioned R ³³ and R ³⁷ , those having excellent solubility in the following organic solvents are preferably used, and they may be appropriately selected according to the organic solvent used in the color dispersion liquid. Specifically, for example, when the above-mentioned organic solvent uses an organic solvent such as an ether alcohol acetate type, an ether type, an ester type, etc. that is commonly used as an organic solvent for color dispersion liquids, methyl, ethyl, isotopic, etc. are preferred. Butyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc. Here, the reason why the above-mentioned R ³³ and R ³⁷ are set in this way is because the structural unit including the above-mentioned R ³³ and R ³⁷ has solubility in the above-mentioned organic solvent, and the acidic phosphorus compound group of the above-mentioned monomer and the site of its salt correspond to the color. Particles such as pigments have high adsorption properties, which can make the dispersion and stability of particles such as pigments particularly excellent.

The weight average molecular weight of the polymer chain in the polymer is preferably in the range of 500 or more and 15,000 or less, and more preferably in the range of 1,000 or more and 8,000 or less. By keeping it within the above range, it is possible to maintain a sufficient steric repulsive effect as a dispersant, and also to suppress an increase in the time required for dispersion of particles such as colorants due to the steric effect.

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

The above-mentioned polymer chain may be a homopolymer or a copolymer. In addition, the polymer chain contained in the structural unit represented by the general formula (II) may be a single type in the graft copolymer, or two or more types may be mixed.

The structural units represented by the general formula (I) are preferably included in a ratio of a total of 3 mass % or more and 80 mass % or less, more preferably 10 mass %, relative to all the structural units of the graft copolymer. It is more than 70 mass % and less than 70 mass %, and it is more preferable that it is 20 mass % or more and 60 mass % or less. If the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity sites to the particles in the graft copolymer becomes appropriate, and the organic solvent can be suppressed. The solubility is reduced, so the adsorption of particles such as colorants becomes better, and excellent dispersion and dispersion stability can be obtained. In addition, since the acidic phosphorus compound group of the graft copolymer can stably exist locally around the color material, a color filter excellent in heat resistance and contrast can be obtained. On the other hand, the structural units represented by the general formula (II) are preferably included in a ratio of 20 mass % or more and 97 mass % or less, and more preferably 25 mass % with respect to all the structural units of the graft copolymer. It is more than 95 mass % and less than 95 mass %, and it is more preferable that it is 40 mass % or more and 90 mass % or less. Furthermore, in the present invention, the content ratio of each structural unit in the copolymer is calculated based on the amount added when synthesizing the copolymer.

Furthermore, the weight average molecular weight of the graft copolymer is preferably in the range of 1,000 or more and 500,000 or less, more preferably in the range of 3,000 or more and 400,000 or less, and still more preferably in the range of 5,000 or more and 300,000 or less. By being in the above range, particles such as colorants can be uniformly dispersed.

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

(block copolymer) Preferable block copolymers as acidic dispersants include, for example, block copolymers having a block portion including a structural unit represented by the above general formula (I), and a block portion including a structural unit represented by the above general formula (III). The block portion of the structural unit represented. In the block copolymer, in the block portion including the structural unit represented by the general formula (I), it is preferable that the total number of structural units represented by the general formula (I) is 3 or more. Among them, from the viewpoint of improving dispersibility and improving heat resistance, it is preferably 3 or more and 200 or less, more preferably 3 or more and 50 or less, still more preferably 3 or more and 50 or less. 30 or less. The structural unit represented by the above-mentioned general formula (I) only needs to function as a colorant affinity site, and may include one type or two or more types of structural units. When two or more structural units are included, two or more structural units may be randomly arranged in the block portion including 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 mass % or more and 80 mass % or less with respect to all the structural units of the above-mentioned block copolymer, and more preferably It is 10 mass % or more and 70 mass % or less, and it is more preferable that it is 20 mass % or more and 60 mass % or less. If it is within the above range, the ratio of the affinity sites for particles in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, so the adsorption property to particles such as colorants becomes good. Excellent dispersion and dispersion stability can be obtained. In addition, since the acidic phosphorus compound group of the block copolymer can stably exist around the color material, a color filter excellent in heat resistance and contrast can be obtained.

By having a block portion including a structural unit represented by the general formula (III), the block copolymer has good solvent affinity, good dispersibility and dispersion stability of the colorant, and good heat resistance, and further Those with excellent resistance to N-methylpyrrolidone (NMP) (NMP resistance).

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 valent base. The hydrocarbon group in R ²⁷ may be the same as that represented by R ¹² above.

In addition, the above-mentioned R ³⁰ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or a monovalent group represented by -CH ₂ COOR ³¹ , and R ^30' is a hydrocarbon group, -[CH(R ²⁸ )-CH(R ²⁹ ) -O] _x2' -R ³⁰ , -[(CH ₂ ) _y2' -O] _z2' -R ³⁰ , -[CO-(CH ₂ ) _y2' -O] _z2' -R ³⁰ represents a univalent base , R ^30'' is an alkyl group with 1 to 18 carbon atoms, R ³¹ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and the above hydrocarbon group may have a substituent. The hydrocarbon group in the above-mentioned R ³⁰ may be the same as that represented by the above-mentioned R ¹² . Among 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. In addition, R ²⁷ in the structural unit represented by the above-mentioned general formula (III) may be the same or different from each other.

As the above-mentioned R ²⁷ and R ^{30 ′} , it is preferable to use those having excellent solubility in the following solvents, and examples thereof include the same ones as the above-mentioned R ³³ and R ³⁷ . In addition, R ²⁷ , R ³⁰ , R ^30′ , R ^30″ and R ³¹ in the above general formula (IV) may be set to the following values within a range that does not hinder the dispersion performance of the above block copolymer, etc. Substituted with substituents such as alkoxy, hydroxyl, carboxyl, amine, epoxy, isocyanate, and hydrogen bond forming groups. Alternatively, after synthesizing the above block copolymer, it may be reacted with a compound having the above substituents. And add the above substituents. Moreover, after synthesizing the block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group is reacted to add a polymerizable group. For example, a polymerizable group can be added by reacting (meth)acrylic acid with a block copolymer having a glycidyl group, or by reacting hydroxyethyl (meth)acrylate with a block copolymer having an isocyanate group.

The number of structural units constituting the block portion including the structural unit represented by the general formula (III) is not particularly limited, but it effectively functions from the solvent affinity portion and the colorant affinity portion to improve the dispersibility of the colorant dispersion. From this aspect, it is preferably 10 or more and 200 or less, more preferably 20 or more and 100 or less, and still more preferably 30 or more and 80 or less.

In the above-mentioned block copolymer, the content ratio of the structural units represented by the general formula (III) is preferably 30 mass % or more and 95 mass % or less, more preferably 40 mass % with respect to all the structural units of the above-mentioned block copolymer. % or more and less than 90 mass%.

The block portion containing the structural unit represented by the general formula (III) may be selected so as to function as a solvent affinity site. The structural unit represented by the general formula (III) may include one type or two types. The above structural units. In the embodiment of the present invention, when the structural unit represented by the general formula (III) includes two or more structural units, the block portion including the structural unit represented by the general formula (III) may be randomly Arrange two or more structural units.

In the block copolymer used as a dispersant, the number of units m as the structural unit of the block portion containing the structural unit represented by the general formula (I), and the number m of the block containing 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 or more and 1 or less. From the perspective of the dispersion and dispersion stability of the color material, it is more preferably 0.1 or more and 0.7 or less. within the range.

As the bonding order of the above-mentioned block copolymer, as long as it has a block part containing the structural unit represented by the above-mentioned general formula (I) and a block part containing the structural unit represented by the general formula (III), the color material can be made It is not particularly limited as long as it can be stably dispersed. However, in terms of excellent interaction with the colorant and effective suppression of aggregation of dispersants, a mosaic containing the structural unit represented by the general formula (I) is preferred. The segment is only bonded to one end of the block copolymer.

The weight average molecular weight of the above-mentioned block copolymer is not particularly limited, but from the viewpoint of good dispersibility and excellent heat resistance, it is preferably 2,500 or more and 500,000 or less, more preferably 3,000 or more and 400,000 or less, and still more preferably It is above 6,000 and below 300,000.

From the aspects of dispersion and storage stability of the above-mentioned colorant, the acid value of the above-mentioned polymer having the structural unit represented by the general formula (I) is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more. , and more preferably 40 mgKOH/g or more. On the other hand, from the viewpoint of excellent developability, the acid value of the polymer having the structural unit represented by the general formula (I) is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and still more preferably Preferably, it is less than 100 mgKOH/g. 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, the above-mentioned carboxyl group-containing block copolymer may be a block copolymer containing an A block containing a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid. , and a B block containing structural units derived from alkyl (meth)acrylate. In the carboxyl group-containing block copolymer, the B block including the structural unit derived from the alkyl (meth)acrylate may be the same as the block copolymer having the structural unit represented by the above general formula (I).

The content ratio (mol%) of each structural unit in the copolymer in the dispersant can be determined based on the amount of raw materials added during production, and can be measured using an analysis device such as NMR (Nuclear Magnetic Resonance). . In addition, the structure of the dispersant can be measured using NMR, various mass spectrometry analyses, etc. In addition, if necessary, the dispersant can be decomposed by thermal decomposition, etc., and the obtained decomposition products can be 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/electron spectroscopy for chemical analysis) and TOF-SIMS (Time-Of-Flight Secondary Ion Mass Spectrometry, time-of-flight secondary ion mass spectrometry) are obtained.

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

[Antioxidants] From the viewpoint of improving heat resistance and brightness, the photosensitive colored resin composition of the present invention preferably further contains at least one of an antioxidant and a latent antioxidant. The antioxidant used in the present invention is not particularly limited, as long as it is appropriately selected from those known in the past. Specific examples of antioxidants include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc. Thin lines are formed by designing the mask line width. In terms of improving patterning ability and heat resistance, it is preferable to use a hindered phenol antioxidant. The latent antioxidant used in the present invention is a compound that has a protective group that can be detached by heating, and is a compound that exhibits an antioxidant function when the protective group is detached. Among these, those in which the protective group is easily released by heating at 150° C. or higher are preferred. Examples of the latent antioxidant used in the present invention include those described in International Publication No. 2014/021023 and International Publication No. 2017/170263. Among them, a suitable latent antioxidant in which the phenolic hydroxyl group of a hindered phenolic antioxidant is protected by a protecting group can be exemplified. More specifically, a potential antioxidant using a tert-butoxycarbonyl group or the like can be exemplified. The structure in which the ester protective group replaces the hydrogen of the phenolic hydroxyl group of the hindered phenolic antioxidant is suitable.

Examples of hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF), isopropyl 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) cyanurate (trade name: Irganox3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3) , 5-di-tert-butylbenzyl) mesitylene (trade name: Irganox1330, 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: Irganox1081, manufactured by BASF), 3,5-di-tertiary Butyl-4-hydroxybenzylphosphonate diethyl ester (trade name: Irgamod 195, manufactured by BASF), etc. Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferred ).

The content of the antioxidant is preferably in the range of 0.1 mass% to 10.0 mass%, more preferably in the range of 0.5 mass% to 5.0 mass% relative to the total solid content of the photosensitive colored resin composition. If it is more than the said lower limit, it will be excellent in improving heat resistance and brightness. On the other hand, if it is below the upper limit, the colored resin composition of the present invention can be turned into a highly sensitive photosensitive resin composition.

[thiol compound] The photosensitive colored resin composition of the present invention preferably further contains a thiol compound from the viewpoint of improving the effect of suppressing changes in film thickness before and after development with a thin line width. Regarding the thiol compound, since the enthiol reaction is not inhibited by polymerization caused by oxygen, it has excellent surface hardening properties and improves the development residual film rate. The thiol compound also has the effect of thickening the line width, but when used in combination with an ultraviolet absorber, it has a synergistic effect of both thinning the line width and improving the development residual film. Examples of the thiol compound include a monofunctional thiol compound having one thiol group and a polyfunctional thiol compound having two or more thiol groups. From the viewpoint of improving the effect of suppressing changes in film thickness before and after development with a thin line width, it is more preferable to use a polyfunctional thiol. Examples of the monofunctional thiol compound include: 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto -5-Methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, etc. Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyloxy)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. The thiol compound may be used alone or in combination of two or more. Among them, pentaerythritol tetrakis(3-mercaptobutyrate) is preferred from the viewpoint of improving the effect of suppressing changes in film thickness before and after development with a thinner line width. ). The content of the thiol compound is usually in the range of 0.5% to 10% by mass, and preferably in the range of 1% to 5% by mass relative to the total solid content of the photosensitive colored resin composition. If it is the above-mentioned lower limit value or more, the effect of suppressing the film thickness change before and after development will be excellent. On the other hand, if it is less than the above-mentioned upper limit, the photocurable red resin composition of the present invention can easily have good developability and can suppress line width deviation.

[Other ingredients] The photosensitive colored resin composition of the present invention may contain various additives as necessary. Examples of additives include polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoaming agents, silane coupling agents, adhesion accelerators, ultraviolet absorbers, and the like. Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Laid-Open No. 2013-029832.

<Production method of photosensitive colored resin composition> The photosensitive colored resin composition of the present invention can be produced by using a known mixing method to combine colorants, alkali-soluble resins, photopolymerizable compounds, photoinitiators, solvents, and if necessary, dispersants, etc., or various Prepare by adding ingredients and mixing. An example of a method for preparing the resin composition is: (1) First, add a colorant and a dispersant to a solvent to prepare a colorant dispersion, and mix an alkali-soluble resin and a photopolymerizable compound into the dispersion. Photo initiator, and the method of using various added ingredients as needed; (2) Put the colorant, alkali-soluble resin, photopolymerizable compound, photo initiator, and various added ingredients as needed into the solvent at the same time and Mixing method; (3) A method of adding alkali-soluble resin, photopolymerizable compound, photoinitiator, dispersant, etc. or various additional ingredients as needed to the solvent and mixing, and then adding colorants for dispersion; ( 4) Add a colorant, a dispersant, and an alkali-soluble resin to a solvent to prepare a colorant dispersion, and further add an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and other materials as needed to the dispersion. Various methods of adding ingredients and mixing, etc. Among these methods, the above-mentioned methods (1) and (4) are preferred from the viewpoint of being able to effectively prevent the aggregation of the colorant and disperse it uniformly. Furthermore, in the method (4), the alkali-soluble resin (U) used in the present invention may or may not be included in the alkali-soluble resin added to the color dispersion liquid.

The method for preparing the colorant dispersion liquid can be appropriately selected and used from previously known dispersion methods. Examples of dispersers used for dispersion include: roller mills such as two-roll mills and three-roll mills; ball mills such as ball mills and vibration ball mills; paint conditioners, continuous disc bead mills, and continuous ring bead mills. Mill and other bead mills. As the preferred dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

[use] The photosensitive colored resin composition of the present invention contains a lake material of a triarylmethane-based dye and can improve brightness and form a colored layer that suppresses changes in film thickness before and after development with a thinner line width, so it can be suitably used. Color filter uses.

[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 photosensitive colored resin composition of the present invention, drying the coating film, and then performing exposure and development. The formation, exposure, and development methods of the coating film may be, for example, the same methods as those used for forming the colored layer included in the color filter of the present invention described below. In addition, the hardened material of the present invention is a colored layer that contains a lake material of a triarylmethane-based dye to increase brightness and suppress changes in film thickness before and after development with a thin line width, and can be suitably used as a color filter. color layer.

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

The 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 , the color filter 10 of the present invention has a substrate 1 , a light-shielding portion 2 , and a colored layer 3 .

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

The colored layer can be formed by the following method, for example. First, the photosensitive colored resin composition of the present invention is coated using a coating method such as spray coating, dip coating, rod coating, roll coating, spin coating, or die coating. A wet coating film is formed on the following substrate. Among them, the spin coating method and the die coating method can be preferably used. Then, after drying the wet coating film using a hot plate or an oven, the wet coating film is exposed through a photomask with a specific pattern, so that the alkali-soluble resin, multifunctional monomer, etc. are photopolymerized to form a cured coating film. Examples of the light source used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The exposure amount is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, after exposure, heat treatment may be performed in order to promote the polymerization reaction. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition used, the thickness of the coating film, and the like.

Next, a developer is used for development to dissolve and remove the unexposed parts, thereby forming a coating film in the desired pattern. As a developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent can usually be used. An appropriate amount of surfactant, etc. may also be added to the alkaline solution. In addition, a common method can be used for the development method. After the development process, the developer is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. In addition, after the development process, in order to fully harden the coating film, heat treatment may also be performed. The heating conditions are not particularly limited and are appropriately selected according to the application of the coating film.

[Light shielding part] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate described below, and can be the same as the light-shielding portion used in a normal color filter. The pattern shape of the light shielding portion is not particularly limited, and examples thereof include striped shapes, matrix shapes, and the like. The light-shielding part may also be a metal film such as chromium formed by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding part may be a resin layer containing light-shielding particles such as carbon particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are methods of patterning using photosensitive photoresist through development, methods of patterning using inkjet ink containing light-shielding particles, and thermal transfer of photosensitive photoresist. methods, etc.

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

[Substrate] As the substrate, the following transparent substrates, silicon substrates, and those in which aluminum, silver, silver/copper/palladium alloy thin films are formed on the transparent substrate or silicon substrate, etc. can be used. Other color filter layers, resin layers, TFT (Thin Film Transistor, thin film transistor) and other transistors, circuits, etc. may also be formed on the 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. A transparent substrate commonly used in 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 flexible transparent materials such as transparent resin films, optical resin plates, and flexible glass. Flexible material. The thickness of the transparent substrate is not particularly limited, and can be, for example, about 100 μm to 1 mm according to the use of the color filter of the present invention. Furthermore, in addition to the above-mentioned substrate, light-shielding portion and colored layer, the color filter of the present invention may also be formed with a protective layer, a transparent electrode layer, an alignment film or a columnar spacer, for example.

IV.Display device The display device of the present invention is characterized by having the above-mentioned color filter of the present invention. In the present invention, the structure of the display device is not particularly limited and can be appropriately selected from previously known display devices, such as a liquid crystal display device or an organic light-emitting display device.

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

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method commonly used for devices can be used. Examples of such driving methods include: TN (Twisted nematic) method, IPS (In-Plane Switching) method, OCB (Optically Compensated Birefringence) method, and MVA (Optically Compensated Birefringence) method. Multi-Domain Vertical Alignment, multi-domain vertical alignment) method, etc. In the present invention, any of these methods can be used appropriately. In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method of forming the liquid crystal layer, a method commonly used for manufacturing a liquid crystal cell may be used, such as 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 normal temperature, thereby aligning the enclosed liquid crystal.

[Organic light-emitting display device] Examples of the organic light-emitting display device of the present invention include an organic light-emitting display device having the above-mentioned color filter of the present invention and an organic light-emitting body. 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 the organic light-emitting display device of the present invention. As illustrated in FIG. 3 , the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80 . There may also be an organic protective layer 50 or an inorganic oxide film 60 between the color filter 10 and the organic light-emitting body 80 .

As a lamination method of the organic light-emitting body 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and The method of forming the cathode 76; or the method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60, etc. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other components in the organic light-emitting body 80 can be appropriately made using known ones. The organic light-emitting display device 100 produced in the above manner can be applied to either a passively driven organic EL display or an actively driven organic EL display. 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. The present invention is not limited by these descriptions. The weight average molecular weight (Mw) of the copolymer before salt formation is determined as a standard polystyrene conversion value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.

(Production Example 1: Preparation of alkali-soluble resin U1) 150 parts by mass of PGMEA was added to the polymerization tank, and after the temperature was raised to 100°C under a nitrogen atmosphere, 34 parts by mass of methyl methacrylate (MMA) and 35 parts by mass of benzyl methacrylate (BzMA) were continuously added dropwise over 1.5 hours. , 1 part by mass of 2-[2-hydroxy-5-[2-(methacryloxy)ethyl]phenyl]-2H-benzotriazole (RUVA-93, trade name, manufactured by Otsuka Chemical), 18 parts by mass of acrylic acid (MAA), 3 parts by mass of PERBUTYL O (manufactured by NOF Co., Ltd.), and 9 parts by mass of a chain transfer agent (n-dodecyl mercaptan). Thereafter, the reaction was continued while maintaining 100° C., and 2 hours after completion of the dropwise addition of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor was added to stop the polymerization. Next, while blowing air, 12 parts by mass of glycidyl methacrylate (GMA), which is an epoxy group-containing compound, was added. After the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added, and the process was carried out at 110°C for 15 hours. After the addition reaction, an alkali-soluble resin U1 solution (weight average molecular weight (Mw) 8000, acid value 75 mgKOH/g, solid content 40 mass%) was obtained. In addition, the above method for measuring the weight average molecular weight is to use polystyrene as a standard material, THF (Tetrahydrofuran, tetrahydrofuran) as an eluent, and use Shodex GPC System-21H to measure the weight average molecular weight. In addition, the acid value measurement method is based on JIS K 0070.

(Production Examples 2 to 12: Preparation of alkali-soluble resins U2 to U12) In Production Example 1, alkali-soluble resins U2 to U12 were prepared in the same manner as Production Example 1, except that the mass ratio of the monomers used was changed to the amounts described in Table 1. In addition, the weight average molecular weight in Production Examples 7 to 12 was adjusted by changing the amounts of PERBUTYL O and the chain transfer agent (n-dodecylmercaptan). The weight average molecular weight and acid value of the obtained alkali-soluble resin are also shown in Table 1.

(Comparative Production Example 1: Preparation of alkali-soluble resin P1) In Production Example 1, alkali-soluble resin P1 was prepared in the same manner as Production Example 1, except that RUVA-93 was not used and the mass ratio of other monomers used was changed to the amounts described in Table 1. The weight average molecular weight and acid value of the obtained alkali-soluble resin are also shown in Table 1.

(Comparative Production Examples 2 to 4: Preparation of alkali-soluble resin P2, and resins P3 and P4) In Production Example 1, in addition to changing the mass ratio of the monomers used to the amounts described in Table 1, and further changing the amounts of PERBUTYL O and the chain transfer agent (n-dodecyl mercaptan), they were the same as those in Production Example 1. 1 Prepare alkali-soluble resin P2, resins P3 and P4 in the same manner. The weight average molecular weight and acid value of the obtained resin are also shown in Table 1.

[Table 1] Table 1 Acid value weight average molecular weight MMA ikB BMA RUVΑ-93 MAA GMA mgKOH/g wt% wt% wt% wt% wt% wt% Manufacturing example 1 U1 75 8000 34 35 1 18 12 Manufacturing example 2 U2 75 8000 33 35 2 18 12 Manufacturing example 3 U3 75 8000 30 35 5 18 12 Manufacturing example 4 U4 75 8000 27 35 8 18 12 Manufacturing example 5 U5 75 8000 25 35 10 18 12 Manufacturing example 6 U6 75 8000 20 35 15 18 12 Manufacturing example 7 U7 75 4000 30 35 5 18 12 Manufacturing example 8 U8 75 6000 30 35 5 18 12 Manufacturing example 9 U9 75 11000 30 35 5 18 12 Manufacturing example 10 U10 75 15000 30 35 5 18 12 Manufacturing example 11 U11 75 20000 30 35 5 18 12 Manufacturing example 12 U12 75 30000 30 35 5 18 12 Comparative manufacturing example 1 P1 75 8000 35 35 18 12 Comparative manufacturing example 2 P2 75 2000 30 35 5 18 12 Comparative manufacturing example 3 P3 0 40000 23.7 76.3 Comparative Manufacturing Example 4 P4 37 1500 6.6 66.2 21.5 5.7 In addition, the abbreviations of the monomers used in the table are as follows. MMA: Methyl methacrylate BzMA: Benzyl methacrylate RUVA-93: 2-[2-hydroxy-5-[2-(methacryloxy)ethyl]phenyl]-2H-benzotriazole (Trade name, manufactured by Otsuka Chemical) MAA: methacrylic acid GMA: glycidyl methacrylate BMA: n-butyl methacrylate

(Synthesis Example 1: Synthesis of Lake Color Material 1) (1) Synthesis of intermediate 1 Referring to the production method of intermediate A-2, intermediate B-1, and compound 1-3 described in Japanese Patent Laid-Open No. 2018-3013, intermediate 1 represented by the following chemical formula (a) was obtained (yield 87%). The obtained compound was confirmed to be the target compound based on the following analysis results. ・MS (ESI) (m/z): 677 (+), bivalent ・Elemental analysis values: CHN measured values (81.81%, 7.31%, 5.85%); theoretical values (81.77%, 7.36%, 5.90%)

[Chemical 11] Chemical formula (a)

(2) Synthesis of lake color material 1: 2.59 g (0.76 mmol) of 12 phosphotungstic acid n hydrate manufactured by Kanto Chemical Co., Ltd. was heated and dissolved in a mixture of 40 mL of methanol and 40 mL of water, and the above intermediate 1 was added. 1.6 g (1.19 mmol), stir for 1 hour. Filter out the sediment and wash with water. The obtained precipitate was dried under reduced pressure to obtain lake color material 1 represented by the following chemical formula (b) (yield 95%). The obtained compound was confirmed to be the target compound based on the following analysis results.・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 12] Chemical formula (b)

(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, Ltd.) 44.0 g, Na ₂ MoO ₄・2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) 1.90 g was dissolved in 230 g of purified water. To this solution, 64.9 g of 85% phosphoric acid was added using a dropping funnel while stirring. The obtained solution was heated to reflux for 8 hours. The reaction solution was cooled to room temperature, and 1 drop of bromine water was added. While stirring, 45 g of potassium chloride was added. The mixture was further stirred for 1 hour, and then the precipitate was separated by filtration. By drying the obtained solid at 90°C, 29.4 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was obtained. (2) Synthesis of lake color material 2. Add 5.30 g of CI Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) into 350 ml of purified water, stir and dissolve at 40°C, and prepare a BB7 solution. In addition, 10.0 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) prepared in the above (1) was dissolved in 40 ml of purified water. The K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution was put into the BB7 solution, and the mixture was stirred at 40°C for 1 hour. Then, the internal temperature was raised to 80° C., and the mixture was further stirred for 1 hour to perform lake formation. After cooling, filter and wash three times with 300 ml of purified water. By drying the obtained solid at 90°C, 10.4 g of lake color material 2 was obtained, which was a blue-black solid with an average primary particle diameter of 40 nm and was used as a lake color material of triarylmethane dye and polyacid. .

(Synthesis Example 3: Synthesis of acidic dispersant A1 (polymer having at least one selected from the structural units represented by the above general formula (I))) (1) Synthesis of giant monomer 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, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and heat to a temperature of 90°C while stirring under a nitrogen stream. . 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 (AIBN for short) was reacted for 3 hours. Next, the nitrogen gas flow 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 The mixture was stirred for 3 hours to obtain a 49.5% by mass solution of macromonomer MM-1. The obtained macromonomer MM-1 was subjected to GPC measurement. The results showed that the weight 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 85.0 parts by mass of PGMEA was added to a reactor equipped with a condenser tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated to 90° C. while stirring under a nitrogen stream. 67.34 parts by mass of the above macromonomer MM-1 solution (33.33 parts by mass of solid content), 16.67 parts by mass of glycidyl methacrylate (GMA for short), 1.24 parts by mass of n-dodecyl mercaptan, and 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 mixture of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and then matured at the same temperature for 1 hour to obtain 25.0% by mass solution of graft copolymer A1. The obtained graft copolymer A1 was subjected to GPC measurement. The results showed that the weight 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) A polymer (acidic dispersant A1) having at least one structural unit selected from the group represented by the general formula (I) is produced by a method equipped with a condensation tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer. 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA", manufactured by Nissan Chemical Co., Ltd.) were added to the reactor, and the mixture was heated to a temperature of 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 and heated and stirred for 2 hours to obtain a polymer (acidic dispersant) having at least one structural unit selected from the group consisting of the structural units represented by the above-mentioned general formula (I). A1) Solution (solid content 25.0% by mass). The progress of the esterification reaction between GMA and PPA in the obtained acidic dispersant A1 was confirmed by acid value measurement and ¹ H-NMR (Nuclear Magnetic Resonance, Nuclear Magnetic Resonance) measurement (it was confirmed that the peak derived from the epoxy group disappeared) . The acid value of the acidic dispersant A1 obtained was 98 mgKOH/g.

(Synthesis Example 4: Acidic dispersant A2 (containing an A block containing a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer, and a B block containing a structural unit derived from an alkyl (meth)acrylate) Synthesis of block copolymer) Referring to Example 1 described in International Publication No. 2016/132863, the following triblock copolymer was synthesized, which contains: 20 parts by mass of methyl methacrylate (MMA) and 40 parts by mass of n-butyl methacrylate (BMA) a block of 20 parts by mass of methacrylic acid (MAA) and 20 parts by mass of BMA; and a block of 20 parts by mass of MMA and 40 parts by mass of BMA. The obtained block copolymer had a weight average molecular weight (Mw) of 11,000, a molecular weight distribution (Mw/Mn) of 1.50, and an acid value of 130 mgKOH/g.

(Synthesis Example 5: Synthesis of potential antioxidants) Mix 0.01 mol of the phenolic compound represented by the following chemical formula (c), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine, and add 0.025 mol of 4-dimethylaminopyridine at room temperature under a nitrogen atmosphere. Stir at 60°C for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchange water, and 200 g of chloroform was added to separate oil and water. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue to perform crystallization. The obtained white powdery crystals were dried under reduced pressure at 60° C. for 3 hours to obtain potential antioxidant (AO1). Furthermore, the structure of the obtained potential antioxidant was confirmed using IR (Infrared Radiation, infrared radiation) and NMR.

[Chemical 13] Chemical formula (c)

(Comparative synthesis example 1: synthesis of triarylmethane dye 1) Triarylmethane dye 1 was synthesized in the same manner as dye A described in Example 1 of Japanese Patent Application Laid-Open No. 2011-133844. First, as described in Example 1 of Japanese Patent Application Laid-Open No. 2011-133844, (toluenesulfonyl)triflate triethylamine salt was synthesized. Next, C.I. Basic Blue 7(N-[4-[[4-(diethylamino)phenyl][4-(ethylamino)-1-naphthyl]methylene]-2, 5-cyclohexadien-1-ylidene]-N-ethylethane ammonium chloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 g was dissolved in 30 mL of methanol, and (toluenesulfonyl group) was added while stirring 3.93 g of trifluoromethanesulfonyl acylimidate triethylamine salt, and further stirred at room temperature for 1 hour. Concentrate the methanol in the solution using an evaporator, add 100 mL of water, filter out the precipitate, and wash with water. The filter cake was dried under reduced pressure to obtain triarylmethane dye 1.

(Example 1: Production of photosensitive colored resin composition 1) (1) Preparation of color dispersion D1 Into a 225 mL mayonnaise bottle, add 61 parts by mass of PGMEA, 5 parts by mass of the alkali-soluble resin P1 solution of Comparative Production Example 1 (solid content 40 mass %), and the acidic dispersant A1 solution of Synthesis Example 3 (solid content 25.0 mass%) 24 parts by mass and stir. 110 parts by mass of the triarylmethane-based lake color material of Synthesis Example 1 and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm were added thereto, and oscillation was carried out for 1 hour using a paint oscillator (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing. , and then changed to 200 parts of zirconia beads with a particle size of 0.1 mm, and dispersed for 4 hours using a paint oscillator as formal crushing to obtain color dispersion D1.

(2) Preparation of photosensitive adhesive component B1 Added 26.4 parts by mass of the alkali-soluble resin U1 solution (solid content 40% by mass) obtained in Production Example 1, a photopolymerizable compound (trade name ARONIX M-403, dipentaerythritol penta- and hexaacrylate, manufactured by Toagosei Co., Ltd. ) 12.3 parts by mass, photopolymerizable compound (trade name ARONIX M-305, pentaerythritol tri- and tetraacrylate, manufactured by Toa Gosei Co., Ltd.), 12.3 parts by mass, photoinitiator 1: Irgacure907 (BASF Production, α-aminoacetophenone-based photoinitiator) 2.4 parts by mass and photoinitiator 2: OXE-02 (BASF production, oxime ester-based photoinitiator with carbazole skeleton) 2.4 parts by mass, synthesis In Example 5, 0.8 parts by mass of latent antioxidant (AO1) and 45.4 parts by mass of PGMEA were used to obtain photosensitive adhesive component B1. (3) Preparation of photosensitive colored resin composition 1 Mix 3.33 parts by mass of the colorant dispersion D1 obtained above, 35.0 parts by mass of the photosensitive adhesive component B1, 0.2 parts by mass of a fluorine-based surfactant (trade name: MEGAFAC F559, manufactured by DIC Co., Ltd.), and silane coupling agent (trade name: The photosensitive colored resin composition of Example 1 was prepared using 2 parts by mass of KBM503 (manufactured by Shin-Etsu Silicones) and 61.67 parts by mass of PGMEA.

(Examples 2 to 18, 20 to 22: Production of photosensitive colored resin compositions 2 to 18, 20 to 22) In the photosensitive adhesive component B1 of Example 1, as the alkali-soluble resin, as shown in Table 2, it was changed to add at least one of the alkali-soluble resin U2 solution to the resin U12 solution, and optionally further add the alkali-soluble resin P1. The solution is used instead of the alkali-soluble resin U1 solution, and the type of antioxidant, the type of polymerizable compound, and the addition of thiol are changed as appropriate to prepare photosensitive adhesive components B2 to B18 and B20 to B22. Except for this, photosensitive colored resin compositions 2 to 18 and 20 to 22 were obtained in the same manner as the photosensitive colored resin composition 1 of Example 1.

(Example 19: Production of photosensitive colored resin composition 19) (1) Preparation of color dispersion D2 Into a 225 mL mayonnaise bottle, add 61 parts by mass of PGMEA, 5 parts by mass of the alkali-soluble resin P1 solution of Comparative Production Example 1 (solid content 40 mass %), and the acidic dispersant A1 solution of Synthesis Example 3 (solid content 25.0 mass%) 24 parts by mass and stir. 10 parts by mass of the triarylmethane-based lake color material 2 of Synthesis Example 2 and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm were added thereto, and oscillation was performed for 1 hour using a paint oscillator (manufactured by Asada Iron Works Co., Ltd.) as a preload Crushed, then changed to 200 parts of zirconia beads with a particle size of 0.1 mm, and dispersed for 4 hours using a paint shaker as formal crushing to obtain color dispersion D2. (2) Preparation of photosensitive colored resin composition 19 In Example 6, a photosensitive colored resin composition 19 was obtained in the same manner as the photosensitive colored resin composition 6 of Example 6, except that the color material dispersion liquid D1 was changed to the color material dispersion liquid D2.

(Comparative Examples 1 to 2, 6 to 7: Production of comparative photosensitive colored resin compositions 1 to 2, 6 to 7) In the photosensitive adhesive component B1 of Example 1, the alkali-soluble resin was changed to the alkali-soluble resin P1 solution instead of the alkali-soluble resin U1 solution. In Comparative Examples 2 and 6-7, as shown in Table 2, alkali was used. The soluble resin P2 solution, resin P3 solution, or resin P4 solution was obtained in the same manner as the photosensitive colored resin composition 1 of Example 1 except that the photosensitive adhesive components CB1 to CB2 and CB6 to CB7 were prepared and used. Compare photosensitive colored resin compositions 1 to 2 and 6 to 7.

(Comparative Examples 3 to 5: Production of comparative photosensitive colored resin compositions 3 to 5) In the photosensitive adhesive component B1 of Example 1, the alkali-soluble resin was changed to the alkali-soluble resin P1 solution instead of the alkali-soluble resin U1 solution, and as shown in Table 2, the photosensitive adhesive component CB3 was prepared using an ultraviolet absorber. Comparative photosensitive colored resin compositions 3 to 5 were obtained in the same manner as the photosensitive colored resin composition 1 of Example 1, except that ∼CB5 was used.

(Comparative Example 8: Production of comparative photosensitive colored resin composition 8) (1) Preparation of color dispersion CD1 In a 225 mL mayonnaise bottle, add 57.5 parts by mass of PGMEA, 7.5 parts by mass of the alkali-soluble resin P1 solution (solid content 40% by mass) of Comparative Production Example 1, and the PGMEA solution of acidic dispersant A2 of Synthesis Example 4 (solid content). Ingredients 20.0 mass %) 25 parts by mass and stirred. PB15: 68.8 parts by mass, 1.2 parts by mass of PV23, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added thereto, and oscillation was performed for 1 hour using a paint oscillator (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing, and then changed to particles. 200 parts of zirconia beads with a diameter of 0.1 mm were dispersed using a paint shaker for 4 hours as formal crushing to obtain a color dispersion CD1. (2) Preparation of comparative photosensitive colored resin composition 8 In the photosensitive adhesive component B1 of Example 1, the alkali-soluble resin P1 solution was used instead of the alkali-soluble resin U1 solution, and the content of each component was changed as shown in Table 2. Otherwise, the same photosensitive adhesive as in Example 1 was used. The photosensitive adhesive component CB8 is prepared in the same manner as the adhesive component B1. Mix 3.33 parts by mass of colorant dispersion liquid CD1, 35.0 parts by mass of photosensitive adhesive component CB8, 0.2 parts by mass of fluorine-based surfactant (trade name MEGAFAC F559, manufactured by DIC Co., Ltd.), and silane coupling agent (trade name KBM503, manufactured by Shin). -Etsu Silicones) 2 parts by mass and 61.67 parts by mass of PGMEA were mixed to obtain comparative photosensitive colored resin composition 8.

[Evaluation Method] The photosensitive colored resin compositions of Examples and Comparative Examples were coated on a glass substrate with a thickness of 0.7 mm using a spin coater so that the film thickness after baking became 2.2 μm (NH TECHNO GLASS Co., Ltd. Co., Ltd., "NA35"), and then use a hot plate to heat and dry at 80°C for 3 minutes. Thereafter, a mask with a line of 40 μm was separated, and an ultrahigh-pressure mercury lamp was used to irradiate ultraviolet light of 60 mJ/cm ² . Then, a 0.05 mass% potassium hydroxide aqueous solution was used as an alkaline developer to perform spray development for 60 seconds. Thereafter, post-baking was performed in a clean oven at 230° C. for 30 minutes to produce a pattern-forming substrate, in which a colored layer was formed on the glass substrate in a pattern of 40 μm lines.

＜Line width increase suppression of coloring layer＞ Using an optical microscope, measure the width of the thin line pattern of the colored layer at 5 locations in contact with the 40 μm opening width of the chrome mask used for exposure, and evaluate the line width by the difference between the average line width and the target line width. Offset. (Line width increase suppression evaluation criteria) AA: The difference between the target line width and the target line width is within 5.0 μm. A: The difference between the target line width and the target line width exceeds 5.0 μm and is within 5.5 μm. B: The difference between the target line width exceeds 5.5 μm and is within 7.0 μm. C: The difference with respect to the target line width exceeds 7.0 μm If the evaluation result is A, the line width increase suppression is good, and if the evaluation result is AA, the line width increase suppression is excellent.

<Evaluation of development residual film rate> The photosensitive colored resin compositions of the Examples and Comparative Examples were coated on a glass substrate (NH) with a thickness of 0.7 mm using a spin coater so that the film thickness after baking became 2.2 μm. (manufactured by TECHNO GLASS Co., Ltd., "NA35"), and then heated and dried using a hot plate at 80°C for 3 minutes. Thereafter, an ultrahigh-pressure mercury lamp was used to irradiate ultraviolet light of 60 mJ/cm ² without interposing a light shield, and then a film thickness meter was used to measure the film thickness T1 of the photoresist coating film. Then, spray development was performed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer, and the film thickness T2 after development was measured. It is calculated in the form of development residual film rate = T2/T1 [%]. (Evaluation criteria for development film remaining film rate) AA: Development film remaining film rate is 98% or more A: Development film remaining film rate is 97% or more and less than 98% B: Development film remaining film rate is 94% or more and less than 97% C: The residual film rate after development is less than 94%

<Evaluation of brightness and heat resistance> Then, the photosensitive colored resin compositions of the examples and comparative examples were coated on a glass substrate with a thickness of 0.7 mm using a spin coater so that the chromaticity after baking became y=0.088 ( Manufactured by NH TECHNO GLASS Co., Ltd., "NA35"). Afterwards, heat and dry on a hot plate at 80°C for 3 minutes. Use an ultra-high-pressure mercury lamp to irradiate ultraviolet light of 60 mJ/ ^cm2 without a light shield. Then use a clean oven at 230°C for 30 minutes to bake. This results in a cured film (colored film). The brightness (Y), L, a, b (L ₀ , a ₀ , b ₀ ) of the obtained colored substrate were measured using the "Microspectroscopy Device OSP-SP200" manufactured by Olympus Corporation, and the following evaluation criteria were used Make an evaluation. Next, the step of post-baking the substrate with the cured film formed thereon for 30 minutes in a clean oven at 230°C and then leaving it to cool for 30 minutes was repeated three times, and the L, a, and b (L ₁ , b) of the obtained colored substrate were measured. a ₁ , b ₁ ). From 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 10.6 or more A: Brightness (Y) is 10.0 or more and less than 10.6 B: Brightness (Y) is 9.5 or more and less than 10.0 C: Brightness (Y) does not reach 9.5

(Heat resistance evaluation criteria) AA: ΔEab does not reach 1.5 A: ΔEab is 1.5 or more and less than 2.0 B: ΔEab is 2.0 or more and less than 3.0 C: ΔEab is 3.0 or more

<UV resistance evaluation> Then, the photosensitive colored resin compositions of the examples and comparative examples were coated on a glass substrate (NH) with a thickness of 0.7 mm using a spin coater so that the chromaticity after baking became y=0.088. Manufactured by TECHNO GLASS Co., Ltd., "NA35"). Afterwards, heat and dry it on a hot plate at 80°C for 3 minutes. Use an ultra-high-pressure mercury lamp to irradiate ultraviolet light of 60 mJ/ ^cm2 without a light shield, and then bake it in a clean oven at 230°C for 30 minutes. This results in a cured film (colored film). The brightness (Y), L, a, and b (L ₀ , a ₀ , b ₀ ) of the obtained colored substrate were measured using the "Microspectroscopy Device OSP-SP200" manufactured by Olympus Corporation, based on the following evaluation criteria. Evaluation. Next, the substrate on which the cured film was formed was irradiated with ultraviolet light of 20 mJ/cm ² for 15 minutes using a low-pressure mercury lamp, and L, a, and b (L ₂ , a ₂ , b ₂ ) of the obtained colored substrate were measured. From the measured value, the color difference (ΔEab) before and after treatment was calculated according to the following formula. Color difference (ΔEab)={(L ₂ -L ₀ ) ² + (a ₂ -a ₀ ) ² + (b ₂ -b ₀ ) ² } ^1/2 (UV resistance evaluation standard) AA: ΔEab does not reach 1.5 A: ΔEab is 1.5 or more and less than 2.0 B: ΔEab is 2.0 or more and less than 3.0 C: ΔEab is 3.0 or more

<Evaluation of Development Residues> The photosensitive colored resin compositions of the examples and comparative examples were each coated on a glass substrate (NH TECHNO GLASS) with a thickness of 0.7 mm using a spin coater so that the film thickness after baking became 2.2 μm. Co., Ltd., "NA35"), and then heated and dried using a hot plate at 80°C for 3 minutes. Thereafter, a mask with a line of 40 μm was separated, and an ultrahigh-pressure mercury lamp was used to irradiate ultraviolet light of 60 mJ/cm ² . Then, a 0.05 mass% potassium hydroxide aqueous solution was used as an alkaline developer to perform spray development for 60 seconds. Thereafter, the pattern of the colored layer in the portion in contact with the opening width of the chrome mask used for exposure was 80 μm, and the presence of residue was visually evaluated using an optical microscope. (Residue evaluation criteria) AA: No development residue A: Microscopic residue is present on a part of the surface B: Microscopic residue is present on the entire surface C: Residue is present on the entire surface

[Table 2] Table 2. photosensitive adhesive Solvent alkali soluble resin Resin photopolymerizable compound photoinitiator Thiol Antioxidants UV absorber PGMEA U1 U2 U3 U4 U5 U6 U7 U8 U9 U10 U11 U12 P1 P2 P3 P4 M1 M2 M3 M4 I1 I2 AO1 AO2 U1 U2 U3 B1 45.4 26.4 12.3 12.3 2.4 2.4 0.8 B2 45.4 13.2 13.2 12.3 12.3 2.4 2.4 0.8 B3 45.4 26.4 12.3 12.3 2.4 2.4 0.8 B4 45.4 26.4 12.3 12.3 2.4 2.4 0.4 0.4 B5 45.4 26.4 12.3 12.3 2.4 2.4 0.4 B6 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B7 45.4 14 12.4 12.3 12.3 2.4 2.4 0.8 B8 45.4 6.5 19.9 12.3 12.3 2.4 2.4 0.8 B9 45.4 8.7 17.7 12.3 12.3 2.4 2.4 0.8 B10 45.4 5.2 21.2 12.3 12.3 2.4 2.4 0.8 B11 45.4 7 19.4 12.3 12.3 2.4 2.4 0.8 B12 45.4 3.5 22.9 12.3 12.3 2.4 2.4 0.8 B13 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B14 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B15 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B16 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B17 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B18 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B19 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B20 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B21 45.4 10.5 15.9 12.3 12.3 2.4 2.4 0.8 B22 46.6 10.5 15.9 12.3 12.3 2.4 2.4 0.8 0.8 CB1 45.4 26.4 12.3 12.3 2.4 2.4 0.8 CB2 45.4 15.9 10.5 12.3 12.3 2.4 2.4 0.8 CB3 46.2 26.4 12.3 12.3 2.4 2.4 0.8 0.525 CB4 46.2 26.4 12.3 12.3 2.4 2.4 0.8 0.525 CB5 46.2 26.4 12.3 12.3 2.4 2.4 0.8 0.525 CB6 45.4 23.4 3 12.3 12.3 2.4 2.4 0.8 CB7 45.4 21.4 5 12.3 12.3 2.4 2.4 0.8 CB8 46.4 24.6 11.5 11.5 3.6 3.6 0.8

[Table 3] Table 3. (A)Dispersion liquid photosensitive adhesive surfactant Silane coupling agent Solvent Line width Development residual film rate brightness Heat resistance (ΔEab) UV resistance (ΔEab) Development residue D1 D2 CD1 Kind parts by mass F559 KBM503 PGMEA determination determination determination determination determination determination Example 1 3.33 B1 35.0 0.2 2 61.67 A AA AA AA A AA Example 2 3.33 B2 35.0 0.2 2 61.67 A AA AA AA A AA Example 3 3.33 B3 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 4 3.33 B4 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 5 3.33 B5 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 6 3.33 B6 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 7 3.33 B7 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 8 3.33 B8 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 9 3.33 B9 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 10 3.33 B10 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 11 3.33 B11 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 12 3.33 B12 35.0 0.2 2 61.67 AA A AA AA AA A Example 13 3.33 B13 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 14 3.33 B14 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 15 3.33 B15 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 16 3.33 B16 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 17 3.33 B17 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 18 3.33 B18 35.0 0.2 2 61.67 AA AA AA AA AA A Example 19 3.33 B19 35.0 0.2 2 61.67 AA AA AA A AA AA Example 20 3.33 B20 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 21 3.33 B21 35.0 0.2 2 61.67 AA AA AA AA AA AA Example 22 3.33 B22 35.0 0.2 2 61.67 AA AA AA AA AA AA Comparative example 1 3.33 CB1 35.0 0.2 2 61.67 B AA AA AA C AA Comparative example 2 3.33 CB2 35.0 0.2 2 61.67 AA AA AA AA C AA Comparative example 3 3.33 CB3 35.0 0.2 2 61.67 AA AA AA AA C AA Comparative example 4 3.33 CB4 35.0 0.2 2 61.67 AA AA AA AA C AA Comparative example 5 3.33 CB5 35.0 0.2 2 61.67 AA AA AA AA C AA Comparative example 6 3.33 CB6 35.0 0.2 2 61.67 C AA AA AA AA C Comparative example 7 3.33 CB7 35.0 0.2 2 61.67 AA C AA AA C B Comparative example 8 3.33 CB8 35.0 0.2 2 61.67 AA AA C AA AA AA

In the table, abbreviations are as follows. Resins U1 to U12: alkali-soluble resins U1 to U12 of Production Examples 1 to 12 Resins P1 to P2: Alkali-soluble resins P1 to P2 of Comparative Production Examples 1 to 2 Resins P3 to P4: Resins P3 to P4 of Comparative Production Examples 3 to 4 M1: Photopolymerizable compound, ARONIX M-403, dipentaerythritol penta- and hexaacrylate, manufactured by Toa Gosei Co., Ltd. M2: Photopolymerizable compound, ARONIX M-305, pentaerythritol tri- and tetraacrylate, manufactured by Toa Gosei Co., Ltd. M3: Photopolymerizable compound, ARONIX M-460, diglycerin ethylene oxide modified acrylate, manufactured by Toa Gosei Co., Ltd. M4: Photopolymerizable compound, Kayarad DPEA-12, ethylene oxide modified (12) dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. Photoinitiator 1 (I1): Irgacure907, manufactured by BASF, α-aminoacetophenone photoinitiator Photoinitiator 2 (I2): OXE-02, manufactured by BASF, an oxime ester photoinitiator with carbazole skeleton Thiol: Karenz MT PE1, manufactured by Showa Denko Antioxidant (AO1): potential antioxidant in Synthesis Example 5 Antioxidant (AO2): IRGANOX1010, manufactured by BASF Ultraviolet absorber (U1): Tinuvin928, manufactured by BASF UV absorber (U2): Tinuvin405, manufactured by BASF Ultraviolet absorber (U3): Tinuvin479, manufactured by BASF

[Result summary] Regarding the photosensitive coloring of Examples 1 to 22 in which an alkali-soluble resin (U) containing a structural unit having a benzotriazole skeleton and having a weight average molecular weight of 3000 or more is combined with a triarylmethane dye lake material. The resin composition is shown to be capable of improving brightness, forming a colored layer with a thin line width, suppressing changes in film thickness and development residue before and after development, and having excellent UV resistance. On the other hand, regarding the photosensitive colored resin composition of Comparative Example 1 which does not contain an ultraviolet absorber, it is shown that even if it contains an antioxidant as in the Example, the line width shift amount is large, the line width becomes thick, and the line width cannot be reduced as expected. A thinner line width is required to form a colored layer, resulting in poor UV resistance. Regarding Comparative Example 2 using an alkali-soluble resin P2 that contains a structural unit having a benzotriazole skeleton but has a weight average molecular weight of 2000, the alkali-soluble resin P2 has a smaller molecular weight, and the alkali-soluble resin P2 is heated at a high temperature of 230°C. Volatilizes and cannot improve the UV resistance of the final colored layer, resulting in poor UV resistance. Regarding Comparative Examples 3 to 5 using ultraviolet absorbers as low molecular compounds, the ultraviolet absorbers as low molecular compounds volatilize in the high-temperature heating step of 230°C and cannot improve the UV resistance and UV resistance of the finally obtained colored layer. Poor. Furthermore, in Comparative Example 6 using resin P3 containing a structural unit having a benzotriazole skeleton but with an acid value of 0 mgKOH/g and a high molecular weight, development residue remained near the pattern, resulting in apparent line width deviation. The displacement appears to be large. Regarding Comparative Example 7 using resin P4 which contains a structural unit with a benzotriazole skeleton but has a weight average molecular weight of 1500, the molecular weight of the resin P4 is small. The resin P4 volatilizes in the high-temperature heating step of 230°C and cannot improve the final obtained The UV resistance of the colored layer is poor. Furthermore, in Comparative Example 7, it was observed that the film thickness of the residual film decreased after development and development residue was generated. On the other hand, the photosensitive colored resin composition of Comparative Example 8, which does not use a triarylmethane-based dye but uses a pigment, was implemented in order to be the same as a lake color material using a triarylmethane-based dye. For example, for the same line width offset, a large amount of light starting dose must be used. In this case, the residual film rate of development will not be a problem, but the display brightness will be low.

1:Substrate 2:Light shielding part 3: Coloring layer 5: Tiny holes 10: Color filter 20:Opposite 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 luminophore 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 the liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.

1:Substrate

2:Light shielding part

3: Coloring layer

10: Color filter

Claims (8)

A photosensitive colored resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and The above-mentioned color material contains a lake color material of a triarylmethane-based dye, The alkali-soluble resin contains an alkali-soluble resin (U). The alkali-soluble resin (U) contains a structural unit having a benzotriazole skeleton and has a weight average molecular weight of 3,000 or more. 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, wherein the alkali-soluble resin (U) contains 1 mass % or more and 10 mass % or less of benzotriazine based on all the structural units of the alkali-soluble resin (U). The structural unit of the azole skeleton. The photosensitive colored resin composition of Claim 1 or 2, which further contains at least one of an antioxidant and a latent antioxidant. The photosensitive colored resin composition according to claim 1 or 2, wherein the lake color material of the triarylmethane-based dye contains a color material represented by the following general formula (1), [Chemical 1] General formula (1) (In the general formula (1), A is an a-valent organic group with no π bond on the carbon atom directly bonded to N. The organic group represents an aliphatic hydrocarbon group having at least a saturated aliphatic hydrocarbon group at the end directly bonded to N. , or an aromatic group having the aliphatic hydrocarbon group, which may contain heteroatoms in the carbon chain; B ^c- represents a c-valent polyacid anion; R ⁱ to R ^v each independently represent a hydrogen atom and an alkyl group that may have a substituent Or an aryl group 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, or an alkyl group that may have a substituent. Alkoxy group, halogen atom or cyano group; Ar ¹ represents a divalent aromatic group which may have a substituent; plural R ⁱ to R ^vii and Ar ¹ may be the same or different respectively; a and c represent 2 or more Integers, b and d represent integers above 1; f and g represent integers above 0 and below 4; there are a plurality of f and g which may be the same or different respectively). A cured product of the photosensitive colored resin composition according to any one of claims 1 to 5. A color filter provided with at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claim 6. A display device having the color filter of claim 7.