TW202219192A - Photosensitive colored resin composition for color filter, cured product, color filter and display device - Google Patents

Abstract

A photosensitive colored resin composition for color filter, comprising a color material, a binder resin, a monomer, a photoinitiator and a solvent, wherein the color material contains at least one selected from the group consisting of a dye and a lake color material, and wherein the binder resin contains a copolymer which includes a polymeric structure such that a constitutional unit represented by the following general formula (A) and derived from hydroxyalkyl (meth)acrylate is contained in an amount of 5 mass % to 25 mass %, which has a weight average molecular weight of 11000 or more, and which has an acid value of 60 mgKOH/g to 130 mgKOH/g: (where R<SP>A</SP> is a methyl group or a hydrogen atom, and R<SP>B</SP> is an alkylene group containing 1 to 4 carbon atoms.).

Description

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

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

In recent years, with the advancement of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs (Personal Computer)) is also increasing, and the market for liquid crystal displays is gradually expanding. In addition, recently, organic light-emitting display devices such as organic EL (Electroluminescence) displays, which have high visibility due to self-luminescence, are also attracting attention as next-generation image display devices. With regard to the performance of these image display devices, further improvement in image quality, such as improvement in contrast ratio and color reproducibility, and reduction in power consumption are strongly desired.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image of a liquid crystal display device, the light passing through the color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. As the light source at this time, in addition to the conventional cold cathode tube, an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light is sometimes used. In addition, in organic light-emitting display devices, color filters are used for color adjustment and the like. Under such circumstances, the color filter is also required to have high brightness, high contrast, improvement of color reproducibility, and the like.

Here, a color filter generally has: a transparent substrate; a colored layer formed on the transparent substrate and including colored patterns of three primary colors of red, green, and blue; and a light-shielding portion formed on the transparent substrate by dividing the colored patterns superior. As a method for forming a coloring layer in a color filter, for example, it is formed by adding a binder resin, a photopolymerizable compound, and a photopolymer to a colorant dispersion liquid obtained by dispersing a colorant with a dispersant or the like. A photosensitive coloring resin composition is formed by using a starting agent, the photosensitive coloring resin composition is applied to a glass substrate and dried, then exposed using a mask and developed to form a colored pattern, and the pattern is formed by heating. fixed to form a colored layer. These steps are repeated for each color to form a color filter.

The photosensitive coloring resin composition for color filter formation is required to have excellent developability which can form a coloring layer accurately. Patent Document 1 proposes a colored photosensitive resin composition for a color filter, which contains a pigment, a binder resin, a polyfunctional monomer, a photoinitiator, a dispersant, and a solvent, and the binder resin contains A copolymer having the following main chain structure, the main chain structure is at least copolymerized from alkyl cyclohexyl (meth)acrylate having an alkyl cyclohexyl group and a monomer having an acid group, and the hydroxyl group of the above-mentioned copolymer is copolymerized. The value is in the range of 15 mgKOH/g to 200 mgKOH/g. According to patent document 1, the unexposed part of this colored photosensitive resin composition has few development residues, and the residual film rate of an exposed part is high.

Moreover, about the photosensitive coloring resin composition for color filter formation, the coloring layer which can form a high brightness is calculated|required. Therefore, studies are underway to use micronized pigments as colorants, or to use dyes or lake colorants as colorants with higher transmittance. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2009-276674

[Problems to be Solved by Invention]

In order to improve the brightness of the color filter, the inventors of the present invention tried to use dyes or lake colorants as the colorant of the photosensitive coloring resin composition. However, when a photosensitive coloring resin composition containing a dye or lake colorant is used to form a coloring layer pattern in which two or more coloring layers such as red, green, and blue are arranged in a predetermined pattern, it has been found that in the pixel The film thickness distribution becomes non-uniform, and the flatness of the pixels is impaired. The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a photosensitive colored resin composition for color filters, which can be formed by containing at least one colorant selected from dyes and lake colorants. A coloring layer with high brightness, excellent flatness, and suppressed development residues. Moreover, the objective of this invention is to provide the hardened|cured material of this photosensitive coloring resin composition, and the color filter and display apparatus formed using this photosensitive coloring resin composition. [Technical means to solve problems]

The photosensitive colored resin composition for color filters of the present invention contains a colorant, a binder resin, a monomer, a photoinitiator, and a solvent, and the colorant is selected from the group consisting of dyes and lake colorants At least one of the group, the above-mentioned binder resin contains the following copolymer, and the copolymer has 5-25 mass % of the hydroxyalkyl (meth)acrylate-derived compound represented by the following general formula (A). The polymer structure of the structural unit, the weight average molecular weight is 11000 or more, and the acid value is 60-130 mgKOH/g.

(通式(A)中，R ^A表示甲基或氫原子，R ^B表示碳數1～4之伸烷基) [Chemical 1] General formula (A)

(In the general formula (A), R ^A represents a methyl group or a hydrogen atom, and R ^B represents an alkylene group having 1 to 4 carbon atoms)

The present invention provides a cured product which is a cured product of the photosensitive colored resin composition for color filters of the present invention. The present invention provides a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is cured of the photosensitive colored resin composition for a color filter of the present invention. thing.

The present invention provides a display device having the above-mentioned color filter of the present invention. [Effect of invention]

According to the present invention, a photosensitive colored resin composition for a color filter can be provided, which can form high brightness by containing at least one colorant selected from dyes and lake colorants, has excellent flatness, and can be developed A colored layer in which the generation of residues is suppressed. Moreover, according to this invention, the hardened|cured material of this photosensitive coloring resin composition, and the color filter and display apparatus formed using this photosensitive coloring resin composition can be provided.

Hereinafter, the photosensitive colored resin composition for color filters of the present invention, a method for producing the same, and the cured product of the photosensitive colored resin composition for color filters of the present invention, the color filters of the present invention are used in this order. The color filter and display apparatus formed using the photosensitive coloring resin composition are demonstrated in detail. Furthermore, in the present invention, light includes electromagnetic waves of wavelengths in the visible and invisible regions, and radiation, such as radiation including microwaves and electron beams. Specifically, it means an electromagnetic wave with a wavelength of 5 μm or less and an electron beam. In the present invention, (meth)acryloyl group represents each of acryl group and methacryloyl group, (meth)acrylic acid represents each of acrylic acid and methacrylic acid, and (meth)acrylate represents acrylate and methyl ester. based on acrylates. In addition, in this specification, "-" which shows a numerical range is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit. In the present invention, the solid content refers to all of the components contained in the photosensitive colored resin composition except for the solvent, and also includes liquid components such as monomers.

I. Photosensitive Colored Resin Composition for Color Filters The photosensitive colored resin composition for color filters of the present invention (hereinafter, sometimes referred to as "photosensitive colored resin composition") contains a colorant, a binder resin, a monomer, a photoinitiator, and a solvent ,and The above-mentioned colorant includes at least one selected from the group consisting of dyes and lake colorants, and the above-mentioned binder resin includes the following copolymer, and the copolymer has the following general formula (A) in an amount of 5-25% by mass. It represents the polymer structure derived from the structural unit of hydroxyalkyl (meth)acrylate, and has a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH/g.

The photosensitive colored resin composition of the present invention contains at least one selected from the group consisting of dyes and lake colorants as a colorant. Compared with pigments, dyes and lake colorants have higher transmittance, so by using at least one selected from the group consisting of dyes and lake colorants as the colorant of the photosensitive coloring resin composition, it is possible to form High brightness tinting layer. However, the photosensitive colored resin composition is coated on a substrate, exposed in a predetermined pattern, and developed to form a colored layer, and this series of steps are sequentially performed on one substrate by changing the color of the toner, In this way, a coloring layer pattern is formed in which coloring layers of two or more colors such as red, green, and blue are arranged in a predetermined pattern. In the above-mentioned method for forming the coloring layer pattern, it has been found that the use of dyes or lakes. In the case of the photosensitive coloring resin composition, the film thickness distribution of the coloring layer formed after the second becomes non-uniform, and the flatness of the pixel is impaired. The uniformity of the film thickness distribution in the pixel is related to the chromaticity uniformity in the pixel, which is an important factor for improving the image quality. In particular, if the pixel density becomes higher as the resolution of the display device becomes higher, the uniformity of the film thickness distribution in the pixel will have an increasing influence on the image quality. The problem that the flatness of the pixels is impaired is particularly noticeable when dyes or lake colorants are used as the colorant of the photosensitive coloring resin composition.

4 is a schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a pigment. FIG. 4 shows the step of forming the blue colored layer 3B after the red colored layer 3R and the green colored layer 3G are sequentially formed on the substrate. 4(a) of FIG. 4 shows that a blue photosensitive coloring resin composition is used to form a blue light-shielding portion 2, a red coloring layer 3R, and a green coloring layer 3G that serve as boundaries between the coloring layers. The state of the color coating film 3B'. The blue coating film 3B' will follow the uneven shape of the coating surface, so the height of the coating film surface becomes relatively lower in the area where the blue coloring layer is to be formed, and in the area where the red coloring layer 3R and the green coloring layer 3G are provided become relatively high. The thickness of the blue coating film 3B' is fixed only in the region where the blue colored layer is to be formed, and the surface thereof becomes flat following the surface shape of the substrate. Next, this blue coating film 3B' is heated and dried. As shown in FIG. 4(b), the blue coating film 3B' after heating and drying maintained the same shape as before heating and drying. After heating and drying, the blue coating film 3B' is exposed to light in a predetermined pattern, and the region where the blue colored layer is to be formed is selectively hardened, and then developed, as shown in FIG. 4(c) , to form a Flat-shaped blue colored layer 3B.

On the other hand, FIG. 5 is a schematic diagram showing an example of a conventional method of forming a colored layer of a color filter using a photosensitive colored resin composition containing a dye or a lake coloring material. FIG. 5 shows the step of forming the blue coloring layer 3B after the red coloring layer 3R and the green coloring layer 3G are sequentially formed on the substrate. 5(a) of FIG. 5 shows that a blue photosensitive coloring resin composition is used to form a blue light-shielding portion 2, a red coloring layer 3R, and a green coloring layer 3G that serve as boundaries between the coloring layers. The state of the color coating film 3B'. At this stage, the blue coating film 3B' containing dyes or lake colorants is the same as the blue coating film 3B' containing pigments in Fig. 4(a), and the height of the coating film surface is higher than the blue coloring to be formed. The area of the layer becomes relatively lower, the area where the red coloring layer 3R and the green coloring layer 3G are provided becomes relatively high, and the thickness of the blue coating film 3B' is fixed only in the area where the blue coloring layer is to be formed, Its surface becomes flat following the surface shape of the substrate. Furthermore, the green coloring layer 3G shown in FIG. 5(a) is the second coloring layer formed on the substrate, which is different from the green coloring layer 3G containing pigment in FIG. 4(a), and has a flat surface. Sexually inappropriate shape. This point will be explained below. Then, when the blue coating film 3B' is heated and dried, the blue coating film flows due to the heating. Therefore, as shown in FIG. The region of the coloring layer 3R and the green coloring layer 3G and the part with a relatively high height of the coating film surface spans the boundary between the region where the red coloring layer 3R is provided and the region where the blue coloring layer is to be formed, and the green coloring layer 3G is provided The boundary between the area where the blue coloring layer is to be formed and the area where the blue coloring layer is to be formed flows into the part that exists in the area where the blue coloring layer is to be formed and the height of the coating film surface is relatively low. Therefore, the blue coating film 3B' after heating and drying loses the followability to the surface shape of the substrate, and the coating film surface is located near the boundary between the region where the red coloring layer 3R is provided and the region where the blue coloring layer is to be formed, and the The vicinity of the boundary between the area of the green coloring layer 3G and the area where the blue coloring layer is to be formed becomes relatively high, and the coating film surface becomes relatively low in the central portion, and the overall surface shape is concave in the central portion. After heating and drying, the blue coating film is exposed to light in a predetermined pattern, and the region where the blue coloring layer is to be formed is selectively hardened and then developed, thereby forming the central portion as shown in FIG. 5(c) . The blue colored layer 3B in the shape of the depression.

When the second and subsequent colored layers are formed on the substrate using the photosensitive coloring resin composition containing dyes or lake colorants, the coating film of the photosensitive coloring resin composition is heated and dried in the same manner as described above. It softens and flows as described above, and loses the followability to the surface shape of the substrate, so it is easy to form a coloring layer of a shape that is relatively high on the surface of the coating film near the junction adjacent to the coloring layer formed earlier on the substrate. For example, when a photosensitive colored resin composition containing dyes or lake colorants is used to form a red colored layer, a green colored layer and a blue colored layer on the substrate in sequence, the green colored layer is shown in Fig. 5(a) ), it is easy to form a shape in which the height of the coating film at the boundary portion adjacent to the red coloring layer is relatively high, and the height of the coating film at the center portion and the portion far from the red coloring layer is relatively low.

The fluidity of the coating film of the photosensitive colored resin composition when heated and dried varies depending on the colorant used, and the reason is presumed that when a pigment is used as the colorant, the fine particles of the pigment are dispersed in the photosensitive material. Therefore, when heating and drying, even if the coating film is softened, the viscosity will not decrease too much; in contrast, when dyes or lake colorants are used as colorants, the dyes or lake colorants are dissolved. In the photosensitive colored resin composition, or dispersed in the photosensitive colored resin composition in a state of being finer than the pigment particles, when the coating film is softened during heating and drying, the viscosity becomes lower and the fluidity becomes larger. .

In the present invention, the above-mentioned problems peculiar to the use of dyes or lake colorants as the colorant of the photosensitive coloring resin composition can be solved by using a binder resin containing the following copolymers, wherein the copolymers contain 5- 25% by mass of a polymer structure derived from a structural unit of hydroxyalkyl (meth)acrylate represented by the following general formula (A), with a weight average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH/g (Hereinafter, this copolymer may be referred to as a "copolymer containing a hydroxyalkyl (meth)acrylate unit"). In the case of using a binder resin containing a copolymer containing a hydroxyalkyl (meth)acrylate unit in a photosensitive coloring resin composition containing a dye or lake colorant, photosensitive coloring formed on a substrate When the coating film of the resin composition is heated and dried, the increase in fluidity is suppressed. Therefore, when the photosensitive colored resin composition is coated on the substrate, the flatness of the coating film is easily maintained after heating and drying. A colored layer with a shape excellent in flatness is formed. When the binder resin containing the copolymer containing the hydroxyalkyl (meth)acrylate unit mentioned above is used, the coloring layer of the shape excellent in flatness is formed, and the reason is presumed to be as follows. It is considered that when the coating film of the photosensitive coloring resin composition is heated and dried, the amount of solvent in the coating film decreases, so that the intermolecular distance between the molecules of the binder resin becomes smaller, and the hydrogen bond has an effect on the bonding force between the molecules of the binder resin. influence increases. The above-mentioned copolymers containing hydroxyalkyl (meth)acrylate units have adjusted the content of the structural units derived from hydroxyalkyl (meth)acrylates to an appropriate range. Therefore, when the photosensitive coloring resin composition is used When the coating film is heated and dried, the hydrogen bond between the binder resin molecules is promoted by the hydroxyl groups of the copolymer containing hydroxyalkyl (meth)acrylate units, so that the viscosity of the softened coating film increases, As a result, fluidization of the coating film can be suppressed. In addition, the weight average molecular weight of the above-mentioned copolymer containing hydroxyalkyl (meth)acrylate units has been adjusted to an appropriate range. Therefore, it is considered that when the coating film of the photosensitive coloring resin composition is heated and dried, the The molecular weight effect increases the viscosity of the softened coating film, thereby inhibiting the fluidization of the coating film. As another method of suppressing softening of the coating film of the photosensitive colored resin composition, a method of using another resin with a relatively high melt viscosity as a binder resin, or a method of using another functional group that promotes hydrogen bonding in the binder resin is also conceivable. A method in which a resin is used as a binder resin, but the above-mentioned copolymer containing a hydroxyalkyl (meth)acrylate unit is excellent in that the shape of the colored layer can be effectively flattened in a relatively small amount, And will not adversely affect the color tone of the coloring layer.

Furthermore, in the case of using the above-mentioned binder resin containing a copolymer containing a hydroxyalkyl (meth)acrylate unit, the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit has been adjusted to an appropriate value Within the range, development residues can be reduced. Generally speaking, the higher the acid value of the binder resin, the easier it is to form hydrogen bonds in the binder resin. Therefore, according to the above description, the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is higher. The larger the value, the higher the effect of flattening the shape of the colored layer. However, if the acid value of the binder resin is too large, the development residue on the substrate will increase. In the present invention, by adjusting the weight average molecular weight of the copolymer containing hydroxyalkyl (meth)acrylate unit and the content of the structural unit derived from hydroxyalkyl (meth)acrylate to an appropriate range, Since the shape of the colored layer can be effectively flattened, it is not necessary to maximize the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units from the viewpoint of flattening the colored layer. From the viewpoint of reducing residues, the above acid value is set to an appropriate range.

Hereinafter, each component contained in the photosensitive coloring resin composition for color filters of this invention is demonstrated. [color material] <Dye and Lake Color> In the present invention, at least one selected from the group consisting of dyes and lake colorants is used as the colorant. In the present invention, the dye refers to a colorant which can be dissolved in a solvent in an effective amount capable of exerting a coloring function. The lake coloring material refers to the one formed by using a lake-forming agent to make the dye lake. The dyes and lake colorants are dissolved in the matrix such as binder resin or dispersed in the state of extremely fine particles, which will not impair the transparency of the composition. At least one of the group is used as a colorant, which can increase the brightness of the color filter.

The dyes and lake colorants used in the present invention are not particularly limited. Examples of dyes include azo-based dyes, metal zirconium salt azo-based dyes, anthraquinone-based dyes, triarylmethane-based dyes, dibenzopyran-based dyes, cyanine-based dyes, naphthoquinone-based dyes, and quinone-based dyes. Imine-based dyes, methine-based dyes, phthalocyanine-based dyes, and the like. As a lake color material, what made the above-mentioned dye lake with a lake-forming agent, etc. are mentioned, for example. The lakeing agent can be appropriately selected and used according to the dye. For anionic dyes (acid dyes), a compound that produces the counter cation of the dye can be used as a lakeing agent; for cationic dyes (basic dyes), it can be used to produce the The compound of the counter anion of the dye acts as a lake-forming agent. As such a lake-forming agent, a well-known one can be used and is not particularly limited, and examples of the lake-forming agent for cationic dyes (basic dyes) include alkali metal salts or alkaline earth metal salts of organic anions, and Alkali salts, alkali metal salts, etc. of inorganic anions; Examples of the lake-forming agent for anionic dyes (acid dyes) include amine compounds that generate ammonium cations, and metal salts having desired metal ions. In addition, as the lake coloring material used in the present invention, for example, a lake obtained by forming a salt with a cationic dye (basic dye) having a univalent or higher valence and a polyanion having a valence higher than a divalent can be preferably used. Colorants, and lake colorants obtained from monovalent or divalent anionic dyes (acid dyes) and divalent or more polycations to form salts, etc. Specific examples of the dyes and lake colorants used in the present invention include the dyes described in Japanese Patent Laid-Open No. 2015-96947 and the dyes described in Japanese Patent Laid-Open No. 2016-27149. A blue dye, a compound (Aa) as a lake color material described in Japanese Patent Laid-Open No. 2017-16099, a dye (Ab), and the like.

Among them, if the photosensitive coloring resin composition of the present invention contains a lake coloring material, even if the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is relatively large, it is easy to suppress the generation of development residues. It is preferable in this respect. The lake colorant has a salt structure of acid and alkali, so it has a higher affinity with hydroxyl groups. Therefore, compared with dyes and pigments, the lake colorant has a better relationship with the copolymer containing hydroxyalkyl (meth)acrylate units. Capacitance is better. Therefore, when the photosensitive colored resin composition of the present invention is combined with a lake-containing colorant and a copolymer containing a hydroxyalkyl (meth)acrylate unit, the solubility in the developing solution can be made uniform, thereby suppressing the The generation of developing residues. Among them, when the hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is within the following preferable range, the compatibility with the lake color material is further improved, so the effect of suppressing the development residue is particularly excellent.

In addition, among the lake colorants, the triarylmethane-based or dibenzopyran-based lake colorants tend to improve the brightness and heat resistance of the colored layer, and are preferred in this respect. The lake coloring material containing a triarylmethane type dye is especially preferable from a viewpoint that high brightness can be achieved at the time of blue coloring, and a viewpoint that heat resistance is easy to further improve. The triarylmethane-based dye and the dibenzopyran-based dye used for the lake colorant can be appropriately selected from known ones, and are not particularly limited. As a triarylmethane type dye, C.I. Basic Blue 7, 8, 11, 26 etc. are mentioned, for example. Examples of dibenzopyran-based dyes include C.I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9, 30, 102, Endosulfan G, Endosulfan B , Endosulfan 101, Endosulfan 640 and other dibenzopyran-based acid dyes; C.I. Basic Violet 11 and other dibenzopyran-based basic dyes; and so on.

In addition, the lake coloring material used in the present invention may have only one color developing site, but if it has two or more color developing sites, a colored layer with higher brightness and excellent heat resistance can be obtained , which is better in this regard. Here, the lake coloring material with two or more color rendering sites refers to the one formed by ionic bonding between a plurality of dye molecules having one color rendering site and a lake forming agent, and may also be a plurality of color rendering sites. One dye molecule in a chromogenic site is ionically bonded to the lake agent, or a plurality of dye molecules having a plurality of color rendering sites are ionically bonded with the lake agent. Among them, from the viewpoint of obtaining a colored layer with high brightness and excellent heat resistance, the colorant used in the present invention preferably contains a lake represented by the following general formula (1) or general formula (2). It is more preferable to contain a lake coloring material represented by the following general formula (1). The lake coloring material represented by the following general formula (1) is a lake coloring material obtained by forming a salt with a cationic dye (basic dye) with a divalent or more and a polyacid anion with a divalent or more, the following general formula ( 2) The lake coloring material represented is a lake coloring material obtained by forming a salt with two or more monovalent cationic dyes and a divalent or more polyacid anion. Any lake colorant may produce dye molecules that do not form salts with polyacid anions, especially when the number of cations in the lake colorant represented by the following general formula (1) is different from the number of anions, it is easy to generate Dye molecules that do not form salts with polyacid anions. Dye molecules that do not form salts with polyacid anions may form salts with acidic groups in copolymers containing hydroxyalkyl (meth)acrylate units. The lake coloring material represented by the following general formula (1) or general formula (2) not only has a higher affinity between the salt structure of acid and alkali and the hydroxyalkyl (meth)acrylate unit in the above-mentioned copolymer, but also The dye molecules that do not form salts with polyacid anions may also form salts with the structural units with acidic groups in the above-mentioned copolymers, so they include those of the lake colorants represented by the following general formula (1) or general formula (2). The photosensitive colored resin composition of the present invention forms a complex formed by associating the lake coloring material and the above-mentioned copolymer, and the effect of inhibiting thermal motion becomes large, so it is presumed that the heat resistance is improved. In addition, the lake coloring material represented by the following general formula (1) or general formula (2) also has a salt structure with an acid and a base, and the copolymer containing a hydroxyalkyl (meth)acrylate unit is also formed. The compatibility is good, so even if the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is relatively large, the generation of development residues can be suppressed. Among them, when the hydroxyl value of the copolymer containing hydroxyalkyl (meth)acrylate units is in the following preferable range, it is different from the lake represented by the following general formula (1) or general formula (2). The compatibility of the colorant is further improved, so the effect of suppressing the development residue is particularly excellent. When the acid value and hydroxyl value of the copolymer containing hydroxyalkyl (meth)acrylate units are in the following preferable ranges, it is easy to form the same compound represented by the following general formula (1) or general formula (2). The complex formed by the association of the lake color materials, so the effect of improving heat resistance is particularly excellent.

(Lake color material represented by general formula (1)) Hereinafter, the lake coloring material represented by the general formula (1) preferably used in the present invention will be described in detail.

(通式(1)中，A為與N直接鍵結之碳原子不具有π鍵之a價有機基，該有機基表示至少在與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基、或具有該脂肪族烴基之芳香族基，於碳鏈中可包含雜原子；B ^c-表示c價聚酸陰離子；R ⁱ～R ^v分別獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R ⁱⁱ與R ⁱⁱⁱ、R ^iv與R ^v可鍵結而形成環結構；R ^vi及R ^vii分別獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基；Ar ¹表示可具有取代基之二價芳香族基；存在複數個之R ⁱ～R ^vii及Ar ¹可分別相同，亦可不同；  a及c表示2以上之整數，b及d表示1以上之整數；e為0或1，於e為0時不存在鍵；f及g表示0以上4以下之整數，f＋e及g＋e為0以上4以下；存在複數個之e、f及g可分別相同，亦可不同) [Chemical 2] General formula (1)

(In the general formula (1), A is an a-valent organic group that does not have a π bond to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N , or an aromatic group having the aliphatic hydrocarbon group, which may contain heteroatoms in the carbon chain; B ^c- represents a c-valent polyacid anion; R ⁱ to R ^v independently represent a hydrogen atom, 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 can be bonded to form a ring structure; R ^vi and R ^vii independently represent an alkyl group that may have a substituent group, and a group that may have a substituent group. An alkoxy group, a halogen atom or a cyano group; Ar ¹ represents a divalent aromatic group which may have a substituent; R ⁱ to R ^vii and Ar ¹ present in plural may be the same or different respectively; a and c represent 2 or more b and d represent integers greater than or equal to 1; e is 0 or 1, and no bond exists when e is 0; f and g represent integers greater than 0 and less than 4, and f+e and g+e are greater than or equal to 0 and less than 4; e, f and g may be the same or different respectively)

Since the colorant represented by the above-mentioned general formula (1) contains an anion of divalent or more and a cation of divalent or more, in the aggregate of the colorant, a molecular association in which a plurality of molecules are associated through ionic bonds can be formed. The non-anion and the cation are only ionically bonded together in the form of 1 molecule to 1 molecule, so the apparent molecular weight is greatly increased compared with the previous lake pigment. By forming such molecular associations, the cohesion force in the solid state is further increased, the thermal motion is reduced, and the dissociation of ion pairs or the decomposition of cation moieties can be suppressed, so that it is presumed that the color of the lake is less likely to fade than the previous color lake.

A in the above-mentioned general formula (1) is an a-valent organic group whose carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group represents a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N The aliphatic hydrocarbon group, or the aromatic group having the aliphatic hydrocarbon group, may contain heteroatoms such as O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in the carbon chain. That is, the organic group means an aliphatic hydrocarbon group having 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 having a terminal directly bonded to N An aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group and which 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 properties such as hue or transmittance of the cationic color-developing site can remain the same as the monomer without being affected by the linking group A or other color-developing sites. color.

In A, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be straight chain, branched chain or cyclic as long as the carbon atom at the terminal directly bonded to N does not have a π bond In any of the shapes, the carbon atoms other than the terminal may have an unsaturated bond or a substituent, and may contain O, S, and N in the carbon chain. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc. may be included, and a hydrogen atom may be further substituted with a halogen atom or the like. In A, the aromatic group having the above-mentioned aliphatic hydrocarbon group includes a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, and may have The substituent may be a heterocyclic ring containing O, S and N. Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of the firmness of the skeleton. Examples of the cyclic aliphatic hydrocarbon group include cyclohexane, cyclopentane, noralkane, bicyclo[2.2.2]octane, tricyclo[ ^5.2.1.02,6 ]decane, and adamantane groups. . Moreover, as an aromatic group, the group containing a benzene ring, a naphthalene ring, etc. are mentioned, for example. For example, when A is a divalent organic group, a linear, branched, or cyclic alkylene having 1 to 20 carbon atoms, or an alkylene having 1 to 20 carbon atoms, such as a xylylene group, can be mentioned. The aromatic group obtained by substituting two of them, etc.

In the present invention, A preferably has two or more cyclic aliphatic hydrocarbon groups, and has a saturated aliphatic at the terminal directly bonded to N, from the viewpoint of achieving both firmness and freedom of molecular movement and improving heat resistance. It is an aliphatic hydrocarbon group, and may contain O, S, N aliphatic hydrocarbon groups in the carbon chain. A is more preferably a cycloextended alkyl group having two or more, a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and an aliphatic hydrocarbon group that may contain O, S, and N in the carbon chain, among which, more preferable It is a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by linear or branched aliphatic hydrocarbon groups. 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 which 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).

(通式(1a)中，R ^xi表示可具有碳數1以上4以下之烷基、或碳數1以上4以下之烷氧基作為取代基之碳數1以上3以下之伸烷基，R ^xii及R ^xiii分別獨立地表示碳數1以上4以下之烷基、或碳數1以上4以下之烷氧基，p表示1以上3以下之整數，q及r分別獨立地表示0以上4以下之整數；於R ^xi、R ^xii、R ^xiii及r存在複數個之情形時，該存在複數個之R ^xi、R ^xii、R ^xiii及r可彼此相通，亦可不同) [Chemical 3] General formula (1a)

(In general formula (1a), R ^xi represents an alkylene group having 1 to 3 or less carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms or less as a substituent, and R ^xii and R ^xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p represents an integer of 1 to 3 or less, and q and r each independently represent 0 to 4 or less Integer of ; when there are plural R ^xi , R ^xii , R ^xiii and r, the plural R ^xi , R ^xii , R ^xiii and r may be the same or different)

From the viewpoint of being excellent in both firmness and thermal motion of the color-developing site and improving heat resistance, examples of the alkylene group having 1 to 3 carbon atoms in R ^xi include methylene group, ethylidene group, and ethylene group. propyl group, etc., among them, methylene group or ethylidene group is preferable, and methylene group is more preferable. Examples of the alkyl group having from 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched. Moreover, as a C1-4 or less alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group can be mentioned, and a straight chain may be sufficient as it, and a branched chain may be sufficient.

Among R ^xii and R ^xiii , the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms or less can be exemplified by the same substituents as those that R ^xi may have.

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

As a preferable specific example of such a linking group A, the following are mentioned, but it is not limited to these.

[hua 4]

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

From the viewpoint of heat resistance, at least one of R ⁱⁱ to R ^v is preferably an optionally substituted cycloalkyl group or an optionally substituted aryl group. At least one of R ⁱⁱ to R ^v has a cycloalkyl group or an aryl group, which reduces the intermolecular interaction due to steric hindrance, thereby suppressing the influence of heat on the color-developing site, and is considered to be excellent in heat resistance.

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

(通式(1b)中，R ^xiv、R ^xv、及R ^xvi分別獨立地表示氫原子、可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基) [Chem. 5] General formula (1b)

(In the general formula (1b), R ^xiv , R ^xv , and R ^xvi each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkyl group having 1 to 4 carbon atoms the following alkoxy)

(通式(1c)中，R ^xvii、R ^xviii、及R ^xix分別獨立地表示氫原子、可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基) [Chem. 6] General formula (1c)

(In general formula (1c), R ^xvii , R ^xviii , and R ^xix each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted group having 1 to 4 carbon atoms the following alkoxy)

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 linear. , can also have branched chains. Moreover, as a C1-4 or less alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group can be mentioned, and a straight chain may be sufficient as it, and a branched chain may be sufficient. As a substituent which the said alkyl group and an alkoxy group may have, a halogen atom, a hydroxyl group, etc. are mentioned.

In the case of having a substituent represented by the above-mentioned general formula (1b), from the viewpoint of heat resistance, it is preferable that at least one of R ^xiv , R ^xv , and R ^xvi be carbon number 1 which may have a substituent An alkyl group of 4 or less, or an alkoxy group of 1 to 4 or less carbon atoms which may have a substituent, more preferably at least one of R ^xiv and R ^xv is an alkane of 1 to 4 carbon atoms which may have a substituent group, or an alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms which may have a substituent.

Moreover, in the case of having a substituent represented by the above-mentioned general formula (1c), from the viewpoint of heat resistance, it is preferable that at least one of R ^xvii , R ^xviii , and R ^xix be a carbon which may have a substituent An alkyl group having 1 or more and 4 or less carbon atoms, or an optionally substituted alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms, more preferably, at least one of R ^xvii and R ^xviii is an optionally substituted carbon group having 1 to 4 carbon atoms. an alkyl group, or an alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms which may have a substituent.

Preferred specific examples of the substituent represented by the general formula (1b) and the substituent represented by the general formula (1c) include the following, but are not limited thereto.

[hua 7]

R ^vi and R ^vii each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano group. The alkyl group in R ^vi and R ^vii is not particularly limited, but is preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, more preferably an alkane having 1 to 4 carbon atoms or less. base. Examples of the alkyl group having from 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched. Although it does not specifically limit as a substituent which an alkyl group may have, For example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, etc. are mentioned. Further, the alkoxy group in R ^vi and R ^vii is not particularly limited, but is preferably a straight-chain or branched alkoxy group having 1 to 8 carbon atoms, more preferably 1 or more carbon atoms 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. Although it does not specifically limit as a substituent which an alkoxy group may have, For example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, etc. are mentioned. As a halogen atom in R ^vi and R ^vii , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The substitution numbers of R ^vi and R ^vii , that is, f and g each independently represent an integer of 0 or more and 4 or less, and among them, preferably 0 or more and 2 or less, more preferably 0 or more and 1 or less. A plurality of f and g may be the same or different, respectively. In addition, R ^vi and R ^vii can be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the dibenzopyran skeleton, wherein, preferably -NR ⁱⁱ R ⁱⁱⁱ or -NR The substitution position of the amine group represented by ^iv R ^v is taken as a reference, and it is substituted to the meta position.

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 be a heterocyclic group. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, condensed polycyclic aromatic hydrocarbons such as a naphthalene ring, a tetralin ring, an indene ring, a perylene ring, an anthracene ring, and a phenanthrene ring; Chain polycyclic hydrocarbons such as benzene, diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton like diphenyl ether or the like. On the other hand, as the heterocyclic ring in the heterocyclic group, there may be mentioned 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; piperane, pyrone, pyridine, pyrone, 6-membered heterocycles such as pyrimidine, pyrimidine, pyridine, etc.; benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, quinoline, Condensed polycyclic heterocycles such as quinazoline and quinoline. These aromatic groups may further have an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group which may be substituted therewith, or the like as a substituent.

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

The valence a in A is the number of chromogenic 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, it is excellent in heat resistance. The upper limit of a is not particularly limited, but from the viewpoint of ease of manufacture, a is preferably 4 or less, more preferably 3 or less.

In the colorant represented by the general formula (1), the molecular weight of the cation part is preferably 1200 or more, more preferably 1300 or more, from the viewpoint of being excellent in heat resistance and easily suppressing discoloration during heating.

In the colorant represented by the general formula (1), from the viewpoint of high brightness and excellent heat resistance, the anion part (B ^c- ) is a c-valent polyacid anion, and is an anion of divalent or higher.

As the polyacid anion condensed from a plurality of _oxoacids , it may be a heteropolyacid anion (M _m On ) ^c- or a heteropolyacid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents polyatoms, X represents heteroatoms, m represents the compositional ratio of polyatoms, n represents the compositional ratio of oxygen atoms, and l represents the compositional ratio of heteroatoms. As polyatomic M, Mo, W, V, Ti, Nb etc. are mentioned, for example. Moreover, as a hetero atom X, Si, P, As, S, Fe, Co, etc. are mentioned, for example. Moreover, a part may contain counter cations, such as Na ⁺ and H ⁺ . Among them, from the viewpoint of being excellent in heat resistance, a polyacid having one or more elements selected from tungsten (W) and molybdenum (Mo) is preferred. Examples of such polyacids include tungstate ions [W ₁₀ O ₃₂ ] ^4- and molybdate ions [Mo ₆ O ₁₉ ] ^2- as heteromeric acids; or phosphotungstate ions as heteropoly acids [ PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , silicotungstic acid ion [SiW ₁₂ O ₄₀ ] ^4- , phosphomolybdate ion [PMo ₁₂ O ₄₀ ] ^3- , silico-molybdate ion [ SiMo ₁₂ O ₄₀ ] ^4- _, phosphotungstomolybdate ion [PW _{12 -s} Mo _s O ₄₀ ] ^3- (s is an integer of 1 to 11) _, [P ₂ W _{18 -t} Mo _t O ₆₂ ] ^6- (t is an integer of 1 or more and 17 or less), silicotungstic molybdate ion [SiW _{12 - u} Mo _u O ₄₀ ] ^4- (u is an integer of 1 or more and 11 or less), and the like. As the polyacid containing at least one of tungsten (W) and molybdenum (Mo), from the viewpoint of heat resistance and the ease of obtaining raw materials, among the above, a heteropolymeric acid is preferred, and more preferred is a polyacid containing Heteromeric acid of phosphorus (P). Furthermore, in terms of heat resistance, phosphotungstic molybdate ions [PW ₁₀ Mo ₂ O ₄₀ ] ^3- , [PW ₁₁ Mo ₁ O ₄₀ ] ^3- , and phosphotungstic acid ions [PW ₁₂ O ₄₀ ] are further preferred. ^3- any one.

In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular association, and b and d represent an integer of 1 or more. When b is 2 or more, a plurality of cations present in the molecular association may be one type alone or a combination of two or more types. Moreover, when d is 2 or more, the anion which exists in a plurality of molecular associations may be a single type or a combination of two or more types. From the viewpoint of easily improving heat resistance by combining with a copolymer containing a hydroxyalkyl (meth)acrylate unit, b and d in the general formula (1) are preferably integers different from each other. In the case where b and d in the general formula (1) are integers different from each other, the dye molecules as cations are likely to interact with the copolymer containing hydroxyalkyl (meth)acrylate units, and it is easy to form a different color. Since the compound formed by the association of the material and the copolymer, the effect of inhibiting thermal motion is increased, and it is presumed that the heat resistance is improved.

e in the general formula (1) is an integer of 0 or 1, and when e is 0, no bond exists. e=0 represents a triarylmethane skeleton, and e=1 represents a dibenzopyran skeleton. A plurality of e may be the same or different. Regarding the lake coloring material represented by the general formula (1) used in the present invention, one containing at least a triarylmethane skeleton can be preferably used. In addition, as a lake color material represented by general formula (1), for example, it can refer to the specification of International Publication No. 2012/144520, and the specification of International Publication No. 2018/003706 can be prepared. The lake coloring material represented by the general formula (1) may be used alone or in combination of two or more.

(Lake color material represented by general formula (2)) Next, the lake coloring material represented by the general formula (2) preferably used in the present invention will be described in detail.

(通式(2)中，R ^I～R ^VI分別獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R ^I與R ^II、R ^III與R ^IV、R ^V與R ^VI可鍵結而形成環結構；R ^VII及R ^VIII分別獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基；Ar ²表示可具有取代基之二價芳香族雜環基，存在複數個之R ^I～R ^VIII及Ar ²可分別相同，亦可不同；E ^m-表示m價聚酸陰離子；  m表示2以上之整數；j為0或1，於j為0時不存在鍵；k及l表示0以上4以下之整數，k＋j及l＋j為0以上4以下；存在複數個之j、k及l可分別相同，亦可不同) [Chemical 8] 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, R ^I and R ^II , R ^III and R ^IV , R ^V It can be bonded with R ^VI to form a ring structure; R ^VII and R ^VIII each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom or a cyano group; Ar ² represents a group that may have a substituent The divalent aromatic heterocyclic group, there are plural R ^I to R ^VIII and Ar ² which may be the same or different; E ^m- represents an m-valent polyacid anion; m represents an integer of 2 or more; j is 0 or 1. When j is 0, there is no bond; k and l represent integers above 0 and below 4, and k+j and l+j are above 0 and below 4; there are multiple j, k and l which may be the same or different respectively)

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 bond with R ^VI to form a ring structure. R ^I to R ^VI may be the same as R ⁱ to R ^v of the above general formula (1), respectively. In the general formula (2), R ^VII and R ^VIII each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. 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 above-mentioned general formula (1). In addition, in the general formula (2), E ^m- represents an m-valent polyacid anion, and the m-valent polyacid anion may be the same as the c-valent polyacid anion of the above-mentioned general formula (1).

In the general formula (2), m represents the number of cations and the number of anions, and represents an integer of 2 or more. In the general formula (2), a plurality of cations may be used alone or in combination of two or more. In addition, the anion may also be a single type or a combination of two or more types. In the general formula (2), j is 0 or 1, and when j is 0, no bond exists. j in the general formula (2) may be the same as e in the above-mentioned general formula (1). 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, as a lake color material represented by general formula (2), it can refer to Japanese Patent Laid-Open No. 2017-16099, for example, and can be prepared. The lake coloring material represented by the general formula (2) may be used alone or in combination of two or more.

Regarding the colorant used in the present invention, a plurality of colorants may be included in order to adjust the hue. When the colorant used in the present invention includes the lake colorant represented by the general formula (1) or the general formula (2), and further includes other colorants in order to adjust the hue, as the other colorant, From the viewpoint of obtaining a high-brightness coloring layer, it is preferably selected from dibenzopyran-based dyes and diphenyl dyes different from the lake coloring materials represented by the general formula (1) or (2) above. At least one of the group consisting of the lake colorant of the pyran-based dye and C.I. Pigment Blue 15:6.

(Dibenzopyran-based dyes) The dibenzopyran-based dye used in combination with the lake colorant represented by the general formula (1) or the general formula (2) may be a dye having a dibenzopyran skeleton in the molecule. A well-known dibenzopyran-based dye is used, and is not particularly limited. Among them, a dibenzopyran-based dye represented by the following general formula (3) or general formula (4) is preferred from the viewpoint of obtaining a high-brightness colored layer.

In the photosensitive colored resin composition of the present invention, by using the dibenzopyran-based dye represented by the following general formula (3), the brightness and light resistance of the colored layer can be improved.

(通式(3)中，R ¹及R ²分別獨立地為烷基或芳基，R ³及R ⁴分別獨立地為芳基或雜芳基) [Chemical 9] General formula (3)

(In the general formula (3), R ¹ and R ² are each independently an alkyl group or an aryl group, and R ³ and R ⁴ are each independently an aryl group or a heteroaryl group)

The characteristics of the dibenzopyran-based dye represented by the above general formula (3) are: in addition to having dibenzopyran as the basic skeleton, it also has only one functional group containing SO ₂ , which is bonded to a nitrogen atom. Any one of R ¹ to R ⁴ is not a hydrogen atom, and R ³ and R ⁴ are aryl groups or heteroaryl groups, so nitrogen atoms are not bound to only saturated hydrocarbon groups and do not have alkali metal ions. By using the dibenzopyran-based dye represented by the above-mentioned general formula (3) having such characteristics, the brightness and light resistance of the colored layer can be improved. Although there are unknown points about the above effects, the following is considered. The dibenzopyran-based dye represented by the general formula (3) has a cationic dibenzopyran skeleton and one anionic -SO ₃ ^- group, and is therefore electrically stable. Therefore, even if it is dispersed in a solvent, it is presumed that it does not dissociate and is excellent in stability. In addition, since the nitrogen atom has an aromatic substituent such as an aryl group or a heteroaryl group, the lone electron pair possessed by the nitrogen atom resonates not only with the dibenzopyran skeleton, but also with the aryl or heteroaryl group , it is presumed that the molecule is more stable. Furthermore, since the nitrogen atom is not directly bonded to the hydrogen atom, the hydrogen atom will not be detached from the nitrogen atom and the coloring material will not be unstable. Based on the above, the dibenzopyran-based dye represented by the general formula (3) is stable even under light irradiation and has excellent light resistance, and by using this colorant, a colored layer with excellent light resistance can be formed. In addition, fading of the colorant is suppressed, and as a result, the brightness of the colored layer can be improved. In addition, with respect to the dibenzopyran-based dye represented by the above general formula (3), R ³ and R ⁴ can be set to be different from each other, so that the range of molecular design is wide, and the adjustment range of spectroscopic properties and the like is also wide. , so it is easy to make the color material close to the target chromaticity, and then it is easy to improve the brightness. In addition, the dibenzopyran-based dye represented by the general formula (3) has a cationic dibenzopyran skeleton and only one anionic -SO ₃ ^- group, and only has an inner salt, so it does not have alkali metal ions. Thereby, when the coloring layer is formed by using the dibenzopyran-based dye represented by the general formula (3), the elution of alkali metal ions from the coloring layer to the liquid crystal layer can be suppressed when a liquid crystal panel is produced, so that it is possible to A colored layer excellent in electrical reliability is obtained. Furthermore, the dibenzopyran-based dye represented by the general formula (3) has only one functional group containing SO ₂ , so it is lower than PGMEA (Propylene Glycol Monomethyl Ether Acetate, propylene glycol monomethyl ether acetate) and the like. The affinity of polar solvents becomes high. Moreover, when dissolving the dibenzopyran-type dye represented by the said general formula (3) in a solvent, since a relatively low polarity solvent can be used, the stability of the photosensitive colored resin composition can be improved.

In the above general formula (3), the alkyl group in R ¹ and R ² is not particularly limited, for example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, etc. A straight-chain or branched alkyl group having 1 to 8 carbon atoms is preferable, and a straight-chain or branched alkyl group having 1 to 5 carbon atoms is more preferable. The substituent which the alkyl group may have is not particularly limited, and examples thereof include a halogen atom, an aryl group, an amine carboxyl group, a valent group represented by -CO-OR ^a , a valent group represented by -O-CO-R ^a' Represents a valent group, a valent group represented by -SO ₂ -R ^{a '} , a valent group represented by -R ^b -CO-OR ^c , a valent group represented by -R ^b' -O-CO-R ^c' A monovalent group, a monovalent group represented by -R ^{b '} -SO ₂ -R ^{c '} , and the like. The aryl group in R ¹ to R ⁴ is not particularly limited, and examples thereof include optionally substituted aryl groups having 6 to 20 carbon atoms, and among them, groups having a phenyl group, a naphthyl group, and the like are preferred. The heteroaryl group in R ³ and R ⁴ is not particularly limited, and examples thereof include optionally substituted heteroaryl groups having 5 to 20 carbon atoms, and preferably, for example, those containing a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom. Moreover, as a heteroaryl group, a furan, a thiophene, a pyrrole, a pyridine etc. are mentioned specifically, for example. The substituent which the aryl group or the heteroaryl group may have is not particularly limited, and examples thereof include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group, an amine carboxyl group, and a valent group represented by -CO-OR ^a . , a valent group represented by -O-CO-R ^a' , a valent group represented by -SO ₂ -R ^{a '} , a valent group represented by -R ^b -CO-OR ^c , -R ^b' - A valent group represented by O-CO-R ^c' , a valent group represented by -R ^{b '} -SO ₂ -R ^{c '} , and the like. The above-mentioned R ^a , R ^a' , R ^{a "} , R ^c , R ^c' and R ^{c "} represent an alkyl group, and the above-mentioned R ^b , R ^b' and R ^{b "} represent an alkylene group. These substituents are not resistant to heat resistance In this respect, it can be used preferably. By adjusting the electron-withdrawing and electron-donating properties based on these substituents, the spectroscopic characteristics can be adjusted. Furthermore, the alkanes in R ¹ to R ⁴ The group is preferably unsubstituted or the substituent is an aryl group, and the substituent of the aryl group or the heteroaryl group is preferably an alkyl group. In this case, the dibenzopyran represented by the general formula (3) is a The polarity of the dye is reduced, so the affinity with low-polarity solvents such as PGMEA is improved. Also, when the dibenzopyran-based dye represented by the above general formula (3) is dissolved in the solvent, a lower polarity can also be used. The use of a low-polarity solvent improves the stability of the photosensitive colored resin composition. In addition, R ¹ to R ⁴ may be the same or different, respectively, and the dibenzophenone represented by the general formula (3) R ¹ to R ⁴ of the pyran-based dye may be symmetric or asymmetric with respect to the dibenzopyran ring. Among them, when R ³ and R ⁴ are different from each other, the diphenyl group represented by the above general formula (3) The range of molecular design of the pyran-based dyes is wide, and the adjustment range of spectroscopic properties is also wide, so it is easy to make the colorant close to the target chromaticity, and it is easy to improve the brightness, which is preferable in this respect. In the general formula (3), the substitution position of the -SO ₃ ^- group of the benzene ring bonded to the dibenzopyran skeleton is not particularly limited, but it is preferably an ortho-group relative to the dibenzopyran skeleton. Position or para position, from the viewpoint of heat resistance and light resistance, preferably -SO ₃ ^- group is substituted at the ortho position with respect to the dibenzopyran skeleton. Although the mechanism of action is not clear, it is presumed as follows : When the -SO ₃ ^- group is in the ortho position, it can resonate with the carbon atom of the dibenzopyran skeleton bonded to the benzene ring to form a ring structure, so the heat resistance and light resistance are improved.

In addition, the dibenzopyran-based dye represented by the above-mentioned general formula (3) can be used by converting the -SO ₃ ^- group into the -SO ₃ H group. The method of converting the -SO ₃ ^- group into the -SO ₃ H group is not particularly limited. For example, the acid treatment method using weak acid liberation reaction, the method using a cation exchange resin, etc. are mentioned. The acid treatment method includes, for example, a method of converting the -SO ₃ ^- group into a -SO ₃ H group by dissolving the above colorant in a solvent such as methanol that dissolves an acid and adding an acid. The acid used in the acid treatment method is not particularly limited as long as it has a higher acidity than the acid for converting the -SO ₃ ^- group into the -SO ₃ H group. As an acid with high versatility, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid (PTS), trifluoromethanesulfonic acid, etc. are mentioned, for example. On the other hand, as an ion exchange resin used in the method using a cation exchange resin, the cation exchange resin of a sulfonic acid terminal, such as Diaion PK-216H (trade name made by Mitsubishi Chemical Corporation), etc. are mentioned. In addition, the sulfonation treatment of converting the -SO ₃ ^- group of the colorant into the -SO ₃ H group is performed after dissolving the color material in a good solvent, and the sulfo group (-SO 3 H) having a sulfo group (-SO ₃ H) may not be taken out as a solid. The colorant is then carried out in the preparation of the photosensitive colored resin composition, for example, when PGMEA or a dispersant is added. Alternatively, after the sulfonation of the colorant, the photosensitive colored resin composition may be prepared by taking out the colorant having a sulfo group as a solid by a reprecipitation method or a recrystallization method. Among them, the former method is preferable from the viewpoint of the recovery rate of the colorant.

The manufacturing method of the dibenzopyran-type dye represented by the said General formula (3) is not specifically limited, Specifically, the following method is mentioned, for example. The amine compound corresponding to the sulfofluoran compound was refluxed in the solvent, and the reaction solution was filtered at 60° C. to remove insoluble components, and then a part of the solvent was removed and poured into 6% hydrochloric acid. Then, a large amount of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake is washed with water or hot water, and then dried to obtain the colorant of the general formula (3). In addition, when R ¹ and R ³ and R ² and R ⁴ have different partial structures and are asymmetric with respect to the dibenzopyran ring of the general formula (3), the corresponding half-amine compounds are successively A small amount was added dropwise to the fully diluted methanol solution of the sulfofluoran compound, and the remaining half amine compound was added dropwise after the reaction, or the 1:1 solution of each amine compound was slowly added dropwise to the sulfofluoran compound. In methanol solution, the asymmetric colorant of general formula (3) can be obtained in high yield. In addition, the dibenzopyran-type dye represented by the said General formula (3) may be used individually by 1 type, and may be used in combination of 2 or more types.

In the photosensitive colored resin composition of the present invention, by using the dibenzopyran-based dye represented by the following general formula (4), generation of foreign matter can be suppressed, and a colored layer with improved brightness can be formed.

(通式(4)中，R ⁵及R ⁶分別獨立地為可具有取代基之脂肪族烴基或芳香族烴基，R ⁷及R ⁸分別獨立地為可具有取代基之芳香族烴基或芳香族雜環基，R ⁷及R ⁸之至少1個芳香族烴基或芳香族雜環基經脂肪族烴基取代，R ⁷及R ⁸彼此不同；L ¹及L ²分別獨立地為直接鍵、-SO ₂-、或-CO-，R ⁹為鹵化脂肪族烴基) [Chemical 10] General formula (4)

(In the general formula (4), R ⁵ and R ⁶ are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent, and R ⁷ and R ⁸ are each independently an aromatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent group. Heterocyclic group, at least one aromatic hydrocarbon group of R ⁷ and R ⁸ or aromatic heterocyclic group is substituted by aliphatic hydrocarbon group, R ⁷ and R ⁸ are different from each other; L ¹ and L ² are each independently a direct bond, -SO _2- , or -CO-, R ⁹ is halogenated aliphatic hydrocarbon group)

The dibenzopyran-based dye represented by the general formula (4) is characterized by having only one specific -L ¹ -N ^- -L ² -R in addition to having dibenzopyran as a basic skeleton ⁹ is a functional group including an anion moiety, any of R ⁵ to R ⁸ bonded to a nitrogen atom is not a hydrogen atom, R ⁷ and R ⁸ are aromatic hydrocarbon groups or aromatic heterocyclic groups, R ⁷ and R ⁸ At least one aromatic hydrocarbon group or aromatic heterocyclic group is substituted with an aliphatic hydrocarbon group, and R ⁷ and R ⁸ are different from each other. By using the dibenzopyran-based dye represented by the above-mentioned general formula (4) having such characteristics, the generation of foreign matter can be suppressed, and a colored layer with improved brightness can be formed. But consider the following. The dibenzopyran-based dye represented by the general formula (4) has a monovalent cationic dibenzopyran skeleton and an anionic -L ¹ -N ^- -L ² -R ⁹ group, and only Since it has an inner salt, it becomes electrically stable within 1 molecule. On the other hand, in the anionic -L ¹ -N ^- -L ² -R ⁹ group, a halogen with a higher negative charge is bonded at R ⁹ , whereby the electrons in the anion site are easily attracted to R ⁹ , the anionicity becomes weaker, so it is presumed that the ionic bond between the molecules becomes weaker. In addition, the dibenzopyran-based dye represented by the general formula (4) has a structure in which any of R ⁵ to R ⁸ bonded to a nitrogen atom is not a hydrogen atom, and R ⁷ and R ⁸ are aromatic An aliphatic hydrocarbon group or an aromatic heterocyclic group, at least one of R ⁷ and R ⁸ is substituted with an aliphatic hydrocarbon group, R ⁷ and R ⁸ are different from each other, and are asymmetric with respect to the dibenzopyran skeleton, so it is presumed that the crystallinity is low , it is not easy to agglomerate, and the solvent affinity becomes higher. From the synergistic effect thereof, it is presumed that the solvent solubility of the dibenzopyran-based dye represented by the above general formula (4) is improved, and the use of the dibenzopyran-based dye containing the above-mentioned general formula (4) is presumed. When the coloring resin composition is used to form a coloring layer, the generation of foreign matter can be suppressed. In addition, the dibenzopyran-based dye represented by the above-mentioned general formula (4) is not directly bonded to a hydrogen atom because the nitrogen atom bonded to the dibenzopyran skeleton does not detach a hydrogen atom from the nitrogen atom. In the case of the instability of the colorant, since the nitrogen atom has an aromatic substituent such as an aromatic hydrocarbon group or an aromatic heterocyclic group, the lone electron pair possessed by the nitrogen atom is not only related to the dibenzopyran skeleton, but also By resonating with the aromatic hydrocarbon group or the aromatic heterocyclic group, the dibenzopyran-based dye represented by the general formula (4) has a highly stable molecular structure. The dibenzopyran-based dye represented by the above-mentioned general formula (4) has a highly stable molecular structure as described above, and thus has good heat resistance. Furthermore, in the dibenzopyran-based dye represented by the general formula (4), since at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ is substituted with an aliphatic hydrocarbon group, R ⁷ and R ⁸ Since the dyes are different from each other, the dyes are not easily agglomerated with each other, and since the solvent solubility is high, foreign matter is not easily generated, so the light transmittance of the colored layer is not attenuated. In addition, in the dibenzopyran-based dye represented by the above general formula (4), R ⁷ and R ⁸ are different from each other, and the range of molecular design is wide, so the adjustment range of spectral characteristics and the like is also wide, so it is easy to make the dye Approaching the target chromaticity, it is easy to increase the brightness. As described above, when the dibenzopyran-based dye represented by the above-mentioned general formula (4) is used, it can be presumed that the reduction in luminance after baking in the color filter manufacturing step is suppressed due to good heat resistance, and the In the color filter manufacturing process, the agglomeration of dyes and the generation of foreign matter can be suppressed, the structure can be designed according to the required chromaticity, and the spectroscopic properties can be adjusted, thereby improving the brightness of the coloring layer.

In the above general formula (4), the aliphatic hydrocarbon group in R ⁵ and R ⁶ may be any of linear, branched, and cyclic, and is not particularly limited, and examples thereof include 1 to 20 carbon atoms. The linear or branched aliphatic hydrocarbon group, or the cyclic aliphatic hydrocarbon group (alicyclic hydrocarbon group) having 5 to 8 carbon atoms (alicyclic hydrocarbon group), etc., preferably has 10 or less carbon atoms from the viewpoint of heat resistance. The aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkyl group which is a saturated aliphatic hydrocarbon group. The substituent which the aliphatic hydrocarbon group may have is not particularly limited, and examples thereof include a halogen atom, an aromatic hydrocarbon group, an amine carboxyl group, a valent group represented by -CO-OR ^d , -O-CO-R A valent group represented by ^d' , a valent group represented by -SO ₂ -R ^{d "} , a valent group represented by -R ^e -CO-OR ^f , -R ^e' -O-CO-R ^f' A valent group represented by -R ^{e "} -SO ₂ -R ^{f "} , and the like. The aromatic hydrocarbon group in R ⁵ to R ⁸ is not particularly limited, and examples thereof include those which may have a substituent. Aromatic hydrocarbon groups having 6 or more carbon atoms and 20 or less carbon atoms, preferably a group having a phenyl group, a naphthyl group, etc. The aromatic heterocyclic groups in R ⁷ and R ⁸ are not particularly limited, and may include carbon atoms which may have a substituent The aromatic heterocyclic group having a number of 5 or more and 20 or less is preferably, for example, one containing a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom. As the aromatic heterocyclic group, for example, furan, thiophene, Pyrrole, pyridine, etc. The substituent which the aromatic hydrocarbon group or the aromatic heterocyclic group may have is not particularly limited, and examples thereof include aliphatic hydrocarbon group, halogen atom, alkoxy group, hydroxyl group, carbamoyl group, -CO A valence group represented by -OR ^d , a valence group represented by -O-CO-R ^d' , a valence group represented by -SO ₂ -R ^{d "} , a valence group represented by -R ^e -CO-OR ^f A monovalent group, a valent group represented by -R ^e' -O-CO-R ^f' , a valent group represented by -R ^{e '} -SO ₂ -R ^{f "} , etc. The above-mentioned ^Re , Re ^' , R ^{e "} , R ^d , R ^d' , R ^{d "} , R ^f , R ^f' and R ^{f "} represent aliphatic hydrocarbon groups. These substituents do not adversely affect heat resistance and the like, and can be preferably used in this respect. Spectroscopic properties can be adjusted by adjusting the electron-withdrawing properties and electron-donating properties based on these substituents. In addition, the aliphatic hydrocarbon group here may be the same as the aliphatic hydrocarbon group in R ⁵ and R ⁶ .

From the viewpoint of suppressing the generation of foreign matter and easily forming a colored layer with improved brightness, at least one of R ⁵ and R ⁶ is preferably an aliphatic hydrocarbon group, preferably R ⁵ and R ⁶ are aliphatic hydrocarbon groups, Of these, straight-chain aliphatic hydrocarbon groups are preferred. The aliphatic hydrocarbon group is preferably a linear alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, and more preferably a linear alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. From the viewpoint of suppressing the generation of foreign matter and easily forming a colored layer with improved brightness, at least one of R ⁷ and R ⁸ is preferably an aromatic hydrocarbon group, and preferably R ⁷ and R ⁸ are an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a phenyl group. In addition, at least one of R ⁷ and R ⁸ of the optionally substituted aromatic hydrocarbon group or the aromatic heterocyclic group is substituted with an aliphatic hydrocarbon group, and R ⁷ and R ⁸ are different from each other. As the aliphatic hydrocarbon group substituted with the hydrogen atom of the aromatic hydrocarbon group or the aromatic heterocyclic group, a straight-chain aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group is preferably a linear alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, and more preferably a linear alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Also, it is preferable that both of R ⁷ and R ⁸ are substituted with aliphatic hydrocarbon groups as described above. In addition, from the viewpoint of suppressing the generation of foreign matter and easily forming a coloring layer with improved brightness, at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ is preferably every aromatic hydrocarbon group or The aromatic heterocyclic group is substituted with two or more aliphatic hydrocarbon groups. In addition, when any one of the aliphatic hydrocarbon groups contained in R ⁵ , R ⁶ , R ⁷ and R ⁸ is a straight-chain alkyl group having 2 or more carbon atoms, and furthermore, a straight-chain alkyl group having 3 or more carbon atoms, it is easy to adjust the molecular weight. trends in electron density. In the case where at least one of R ⁵ and R ⁶ is substituted with a straight-chain aliphatic hydrocarbon group, and at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ is substituted with a straight-chain alkyl group having 2 or more carbon atoms In this case, it is easy to suppress the generation of foreign matter, so that it is easy to form a coloring layer with improved brightness.

In addition, among R ⁵ to R ⁸ , the aliphatic hydrocarbon group is preferably unsubstituted, or when it is a branched or straight-chain alkyl group, the substituent is an aromatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group. The substituent of the cyclic group is preferably an aliphatic hydrocarbon group. The reason for this is that in this case, the polarity of the dibenzopyran-based dye represented by the general formula (4) is lowered, so that the affinity with low-polarity solvents such as PGMEA is improved. Moreover, when dissolving the said coloring material in a solvent, the low polarity solvent with lower polarity can also be used, and the stability of the photosensitive colored resin composition of this invention can be improved by using a low polarity solvent. Among these, it is preferable to have only aliphatic hydrocarbon group as a substituent of an aromatic hydrocarbon group or an aromatic heterocyclic group from a viewpoint of improving the affinity with a low polar solvent.

L ¹ and L ² in the -L ¹ -N ^- -L ² -R ⁹ group are each independently a direct bond, -SO ₂ -, or -CO-, and preferably -SO ₂ - or -CO- Furthermore, -SO ₂ - is preferable from the viewpoint of suppressing the generation of foreign matter and easily forming a coloring layer having excellent heat resistance and improved brightness.

R ⁹ in the -L ¹ -N ^- -L ² -R ⁹ group is a halogenated aliphatic hydrocarbon group, and examples of the halogen include a fluorine atom, a chlorine atom, an iodine atom, and the like, among which a fluorine atom is preferred. The halogenated aliphatic hydrocarbon group for R ⁹ is preferably a linear or branched halogenated aliphatic hydrocarbon group with 1 to 8 carbon atoms, more preferably a linear or branched halogenated aliphatic group with 1 to 5 carbon atoms. A hydrocarbon group, more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms. The substitution ratio of halogen atoms in the aliphatic hydrocarbon group (number of halogen atoms/total number of hydrogen atoms in the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more, and more preferably 100%. Among them, R ⁹ is preferably a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms.

In addition, in the above general formula (4), the substitution position of the -L ¹ -N ^- -L ² -R ⁹ group of the benzene ring bonded to the dibenzopyran skeleton is not particularly limited, but is preferably In order to be in the ortho position or the para position with respect to the dibenzopyran skeleton, from the viewpoint of various tolerances of the dibenzopyran-based dye represented by the general formula (4), -L ¹ - is preferred. The N ^- -L ² -R ⁹ group is substituted to the ortho position with respect to the dibenzopyran skeleton. Although its mechanism of action is not clear, it is presumed as follows: if the -L ¹ -N ^- -L ² -R ⁹ group is in the ortho position, it can resonate with the carbon atom of the dibenzopyran skeleton to which the benzene ring is bonded. A ring structure is formed, and the stability of the molecule becomes high, so that the various tolerances of the colorant are improved.

Although it does not specifically limit about the manufacturing method of the dibenzopyran-type dye represented by the said General formula (4), For example, the following method is mentioned. The sulfofluoran compound and the amine compound corresponding to R ⁷ and R ⁸ were refluxed in a solvent at 60°C, and the reaction solution was filtered at 60°C to remove insoluble components, and then a part of the solvent was removed and injected into 6% hydrochloric acid. Then, a large amount of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake is washed with water or hot water, and then dried, whereby the intermediate of the pigment represented by the above-mentioned general formula (4) can be obtained. Furthermore, in the present invention, in order to produce a pigment of the general formula (4) that is asymmetric with respect to the dibenzopyran ring, a part of the structure of R ⁷ and R ⁸ is different, and a small amount of the corresponding hemiamine compound is successively used. Add dropwise to the fully diluted methanol solution of sulfofluoran compound, after the reaction, add the remaining half amine compound dropwise, or slowly add the 1:1 solution of each amine compound dropwise to the methanol solution of sulfofluoran compound In this way, an asymmetric intermediate of the pigment represented by the general formula (4) can be obtained in high yield. Next, in a polar solvent such as 1-methyl-2-pyrrolidone, in the presence of a base such as potassium carbonate, the intermediate of the dye represented by the general formula (4), and R ⁵ and R ⁶ correspond to The halide was stirred at 80°C for 2 hours to carry out the reaction. After the reaction was completed, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 17.5% hydrochloric acid at 0 to 10° C. and stirred for 1 hour. Then, the precipitate was collected by filtration, and the residue was dried at 60° C. for 24 hours to obtain a dye precursor represented by the general formula (4). Next, the color precursor of the asymmetric general formula (4) and trifluoromethylsulfonamide were dissolved in chloroform, and triethylamine was added dropwise to conduct the reaction. Then, the obtained reaction solution was washed with water, and then the organic layer was separated. The organic layer is dried with sodium sulfate, purified by column chromatography, and concentrated under reduced pressure, whereby the dibenzopyran-based dye represented by the above-mentioned general formula (4) can be obtained. In addition, when L ¹ is represented by -CO-, a fluoran compound can be used in place of the sulfofluoran compound, and the dibenzopyran system represented by the above-mentioned general formula (4) can be obtained in the same manner. dye.

The dibenzopyran-based dye represented by the general formula (4) has high solvent solubility in low-polarity solvents, so even if a solvent having an alcoholic hydroxyl group is not used, it has a concentration required for the coloring layer application. Solvent solubility. The dibenzopyran-based dyes represented by the general formula (4) are preferably propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, and At least one of ethylene glycol ethyl methyl ether, the solubility of the dibenzopyran-based dye represented by the above general formula (4) at 23°C is 2.0 (g/100 g solvent) or more, more preferably 2.5 ( g/100 g solvent) or more. In addition, the dibenzopyran-type dye represented by the said general formula (4) may be used individually by 1 type, and may be used in combination of 2 or more types.

(Lake color of dibenzopyran dyes) It does not specifically limit as the lake coloring material of the dibenzopyran-based dye used in combination with the lake coloring material represented by the above-mentioned general formula (1) or the general formula (2), for example, the same as the above-mentioned general formula can be used. (1) The lake coloring material of a known dibenzopyran-based dye which is different from the lake coloring material represented by the general formula (2). Among them, from the viewpoint of being excellent in heat resistance and dispersibility of the colorant and obtaining a high-brightness colored layer, a lake-forming agent containing a metal atom can be preferably used to lake a dibenzopyran-based dye. It is the metallic lake color of the dibenzopyran series dyes. Furthermore, the metallic lake coloring material is a metallic lake coloring material added as a lake-forming agent.

As the lake coloring material of the dibenzopyran-based dye different from the lake coloring material represented by the general formula (1) or the general formula (2), among them, 9 in the dibenzopyran skeleton is preferred. It is a lake color of dibenzopyran-based dyes with a phenyl group in the position. Specifically, a lake coloring material obtained by lakeing a dibenzopyran-based dye represented by the following general formula (5) with a lake-forming agent can be preferably used, especially A metal lake coloring material obtained by lake-forming a dibenzopyran-based dye represented by the following general formula (5) with a lake-forming agent containing a metal atom.

(通式(5)中，R ^1'、R ^2'、R ^3'及R ^4'分別獨立地表示氫原子、烷基、芳基、或雜芳基，R ^1'與R ^3'、R ^2'與R ^4'分別可鍵結而形成環結構，R ^1'與二苯并哌喃環之5位碳原子、R ^3'與二苯并哌喃環之7位碳原子、R ^2'與二苯并哌喃環之4位碳原子、或R ^4'與二苯并哌喃環之2位碳原子分別可鍵結而形成環結構；上述芳基、或雜芳基所具有之氫原子可經酸性基或其鹽、或者鹵素原子取代；R ^5'表示酸性基或其鹽，x為0～5之整數；其中，通式(5)具有至少2個酸性基或其鹽，且其中1個形成內鹽) [Chem. 11] General formula (5)

(In general formula (5), R ^1' , R ^2' , R ^3' and R ^4' each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, R ^1' and R ^3' , R ^2' and R ^4' can be bonded respectively to form a ring structure, R ^1' and the 5th carbon atom of the dibenzopyran ring, R ^3' and the 7th carbon atom of the dibenzopyran ring, R ^2' It can be bonded to the 4-position carbon atom of the dibenzopyran ring, or R ^4' and the 2-position carbon atom of the dibenzopyran ring, respectively, to form a ring structure; the hydrogen possessed by the above-mentioned aryl group or heteroaryl group The atom may be substituted by an acidic group or a salt thereof, or a halogen atom; R ^5' represents an acidic group or a salt thereof, and x is an integer of 0 to 5; wherein, the general formula (5) has at least 2 acidic groups or a salt thereof, and 1 of which forms an inner salt)

As for the alkyl group in R ^1' to R ^4' , among them, a straight-chain or branched alkyl group having 1 to 20 carbon atoms which may have a substituent is preferable, and a straight-chain or branched alkyl group having 1 to 8 carbon atoms is more preferable. The branched-chain alkyl group is more preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. Although it does not specifically limit as a substituent which an alkyl group may have, For example, an aryl group, a halogen atom etc. are mentioned, This aryl group may further have a halogen atom, or an acidic group or its salt as a substituent. Among the aryl groups in R ^1' to R ^4' , preferably aryl groups having 6 to 20 carbon atoms which may have a substituent, and more preferably groups having a phenyl group, a naphthyl group, or the like. In addition, as for the heteroaryl group in R ^1' to R ^4' , among them, preferably a heteroaryl group having 5 to 20 carbon atoms which may have a substituent, and preferably one containing nitrogen atom, oxygen atom, and sulfur atom as hetero atoms By. Examples of the substituent which the aryl group or the heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group or a salt thereof, a hydroxyl group, an alkoxy group, a nitrile group, an amine carboxyl group, and a carboxyl group. Acid group, etc.

The fact that R ^1' and R ^3' , and R ^2' and R ^4' are respectively bonded to form a ring structure means that R ^1' and R ^3' , and R ^2' and R ^4' respectively form a ring structure through a nitrogen atom. . The ring structure is not particularly limited, and examples thereof include nitrogen-containing heterocycles having 5 to 7 members, and specific examples thereof include a pyrrolidine ring, a piperidine ring, and an oxaline ring. Also, the so-called R ^1' and the carbon atom at the 5th position of the dibenzopyran ring, R ^3' and the carbon atom at the 7th position of the dibenzopyran ring, and R ^2' and the carbon atom at the 4th position of the dibenzopyran ring. , or R ^4' is bonded to the 2-position carbon atom of the dibenzopyran ring to form a ring structure, which means that R ^1' to R ^4' , and the above-mentioned carbon atoms at the specified position of the dibenzopyran ring. The combination forms a ring structure via a nitrogen atom and a part of the dibenzopyran skeleton, respectively. The ring structure is not particularly limited, and examples thereof include nitrogen-containing heterocycles having 5 to 7 members.

Specific examples of the acidic group or its salt include a carboxyl group (-COOH), a carboxyl group (-COO-), a carboxylate group (-COOM, where M represents a metal atom), a sulfonic acid group (-SO ₃ - ), a sulfo group (-SO ₃ H), a sulfonate group (-SO ₃ M, where M represents a metal atom), etc., among which, it is preferable to have a sulfo group (-SO ₃ -), a sulfo group (- At least one of SO ₃ H), or sulfonate group (—SO ₃ M). In addition, as the metal atom M, a sodium atom, a potassium atom, etc. are mentioned.

Specific examples of the dibenzopyran-based dye represented by the general formula (5) include Acid Red 50, Acid Red 52, Acid Red 289, Acid Violet 9, Acid Violet 30, Acid Blue 19, and the like.

＜Lakeizer＞ The lake-forming agent used for the lake-forming of the metallic lake color material of the dibenzopyran-based dye may be a lake-forming agent containing a metal atom. As a lake-forming agent containing a metal atom, a lake-forming agent containing a metal atom that becomes a metal cation with a divalent or higher value is preferable, and specific examples thereof include barium chloride, calcium chloride, calcium carbonate, and aluminum chloride. , aluminum sulfate, aluminum acetate, lead acetate, magnesium sulfate, zirconium chloride, zirconium sulfate, zirconium carbonate, polyaluminum chloride, polyaluminum sulfate, etc., among which, it is more preferable to contain a metal atom that becomes a metal cation of trivalent or more Lakers. Furthermore, from the viewpoint of easy synthesis of the lake color material and excellent dispersibility of the lake color material, a lake-forming agent containing aluminum is preferable. That is, as the metallic lake coloring material of the dibenzopyran-based dye, the aluminum lake coloring material of the dibenzopyran-based dye is preferable, and the dibenzophenone represented by the above-mentioned general formula (5) is particularly preferable. Aluminium lake colorant for pyran dyes. By using a lake-forming agent containing aluminum as a trivalent cation, it is estimated that the above-mentioned lake-forming agent containing aluminum as a trivalent cation is used as a lake rather than a lake-forming agent containing a metal atom as a divalent metal cation The chemical agent has stronger cohesion. Therefore, the solubility of the laked dibenzopyran-based dye in the solvent is greatly reduced, and the property is closer to that of a pigment. Therefore, it also has the following advantages: the dispersibility and heat resistance of the colorant are excellent, and the lake colorant is easily recovered (filtered and separated) when the colorant is produced.

Among them, polyaluminum chloride represented by the following general formula (6) is preferable from the viewpoint of excellent heat resistance of the colorant and the viewpoint of easily suppressing the sublimation of the colorant as the lake-forming agent containing aluminum.

(通式(6)中，n為2～20之整數，m為(n/2)～(3n－1)之整數) [Chemical 12] General formula (6)

(In the general formula (6), n is an integer of 2 to 20, and m is an integer of (n/2) to (3n-1))

In the polyaluminum chloride represented by the above general formula (6), n represents the number of aluminum atoms, and is 2 to 20. By using relatively small polyaluminum chloride with 2-20 aluminum atoms as the lake-forming agent, the dispersed particle size of the colorant will not become too large, and the dispersibility of the colorant can be improved. In this invention, it is preferable that n is an integer of 2-10 among them.

Moreover, in the polyaluminum chloride represented by the said general formula (6), m represents the number of a hydroxyl group ( ^OH- group), and is an integer of (n/2)-(3n-1). Furthermore, when n is an odd number, the lower limit of m is {(n+1)/2} which becomes the smallest integer within the above range.

Aluminum in polyaluminum chloride has trivalent cation, and the hydroxyl group has monovalent anion, so the whole polyaluminum chloride has (3n-m) cation. In the present invention, from the viewpoint of strong cohesion, easy recovery of the colorant, or excellent dispersibility of the colorant, it is preferable that the basicity is high, and m is preferably an integer of 2n to (3n-1). . Among them, from the viewpoint of improving the dispersibility of the colorant and the contrast of the coating film, the polyaluminum chloride represented by the general formula (6) is preferably n is an integer of 2 to 10, and m is 2n to ( 3n-1) integer.

In addition, the polyaluminum chloride represented by the general formula (6) is preferred from the viewpoints that the heat resistance of the colorant is further improved, the sublimation of the colorant is easily suppressed, and the dispersibility of the colorant is easily improved. The basicity defined by (m/3n×100(%)) is 15 to 99%, more preferably 60 to 97%, and further preferably 70 to 95%.

(C.I. Pigment Blue 15:6) The C.I. Pigment Blue 15:6 preferably used in the present invention is a copper phthalocyanine pigment having an ε-type crystal structure, and is preferred from the viewpoint of excellent dispersion stability. The C.I. Pigment Blue 15:6 used in the present invention can be subjected to an alkaline treatment or an acid treatment. From the viewpoint of excellent dispersibility and storage stability, it is preferable when the dispersant used in combination is acidic. In order to carry out alkaline treatment; when the dispersant used in combination is alkaline, acid treatment is preferably carried out. Among them, the C.I. Pigment Blue 15:6 used in the present invention is preferably alkali-treated, and the alkali-treated C.I. Pigment Blue 15:6 is preferably used in combination with an acidic dispersant.

In the present invention, a colorant derivative having an alkaline moiety or a derivative of a colorless compound having an alkaline moiety is suitably used in the alkaline treatment. Moreover, in this invention, what has a basic site includes the aspect which has a basic group as a substituent, the aspect which an acidic group and a basic compound form a salt at a substituent, etc. are mentioned. Examples of the basic moiety possessed by the colorant derivative or the colorless compound derivative in the present invention include an amine group, an ammonium sulfonate, a sulfonamido group having an amine group, and an amide group having an amine group. , basic heterocyclic groups, etc.

As for the colorant used in the colorant derivative having an alkaline moiety, a well-known colorant can be appropriately selected and used, preferably one having a structure that is easily adsorbed to C.I. Pigment Blue 15:6, preferably the same or similar The pigment skeleton, or has a structure that is easy to interact. Moreover, it is preferable that it does not damage the color tone of C.I. Pigment Blue 15:6 used in the alkaline treatment. Among the colorant derivatives having a basic moiety, blue colorant derivatives are preferred. As the blue colorant used in the colorant derivative having a basic moiety, phthalocyanine-based colorants, triarylmethane-based colorants, anthraquinone-based colorants, naphthol-based colorants, and benzimidazolone-based colorants can be used As for the colorant and the like, it is preferable to use a phthalocyanine-based colorant only from the viewpoint of color tone and heat resistance. Among them, from the viewpoint of improving dispersibility and brightness, as the colorant used in the colorant derivative having a basic moiety, it is preferable to use a phthalocyanine-based colorant having the same properties as The skeleton of C.I. Pigment Blue 15:6 used in the alkaline treatment is the same. Moreover, among these, it is preferable to use copper phthalocyanine as a blue coloring material used for the color material derivative|guide_body which has a basic part from a viewpoint of dispersibility and brightness improvement.

Regarding the leuco compound used in the derivative of the leuco compound having a basic moiety, the following compound can be used as a standard. Even if the derivative of the leuco compound is used for basic treatment of C.I. Pigment Blue 15:6, C.I. The color of Pigment Blue 15:6 will not change before and after alkaline treatment. As the colorless compound, for example, a condensed ring compound such as a naphthalene-based compound and a triazine-based compound, or an aromatic polycyclic compound in which a plurality of aromatic rings are bonded can be used. Examples of the trisic aromatic polycyclic compound include a structure in which three substituents having an aromatic hydrocarbon group, such as a phenylamino group, are substituted on the trisic ring. Among them, from the viewpoint of improving dispersibility and brightness, it is preferable to use a tris-based aromatic polycyclic compound.

As a method of preparing, for example, C.I. Pigment Blue 15:6 containing a colorant derivative having a basic moiety as C.I. Pigment Blue 15:6 having a structure derived from a basic compound, for example, a method of After dry grinding the color derivative with basic part and C.I. Pigment Blue 15:6, the color derivative with basic part is mixed. In this case, as a dry pulverizer, a ball mill, a vibration mill, an attritor, etc. can be used, and the pulverization temperature can be freely set within 20 to 130°C. In addition, as a method for preparing C.I. Pigment Blue 15:6 containing a colorant derivative having a basic moiety, there may be mentioned a method in which a colorant derivative having a basic moiety, C.I. Pigment Blue 15:6, and chlorine Water-soluble inorganic salts such as sodium chloride, calcium chloride, and ammonium sulfate, and water-soluble organic solvents such as glycol-based organic solvents are mixed, and kneaded by a solvent-salt milling method using a kneader-type mill. Before dispersing the colorant, prepare or prepare the alkaline treated C.I. Pigment Blue 15:6 to disperse the colorant, thereby improving the dispersibility of the colorant.

In C.I. Pigment Blue 15:6 containing a colorant derivative having a basic moiety or a colorless compound derivative, from the viewpoint of dispersibility and storage stability, a colorant derivative having a basic moiety or a colorless compound The content of the derivative of C.I. Pigment Blue 15:6 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably 8 parts by mass or more . On the other hand, from the viewpoint of being excellent in brightness, the content of the colorant derivative having a basic moiety or the derivative of the leuco compound is 100 parts by mass relative to C.I. Pigment Blue 15:6, preferably 50 parts by mass or less, and more Preferably it is 40 mass parts or less, More preferably, it is 30 mass parts or less.

Furthermore, with respect to C.I. Pigment Blue 15:6 treated with an alkaline treatment or an acid treatment, for example, mass analysis, elemental analysis, surface analysis, potentiometric titration, and a combination thereof can be used for analysis as appropriate. Moreover, as an acidic dispersing agent used in combination with the alkaline-treated C.I. Pigment Blue 15:6, the same acidic dispersing agent which can be used for the following color material dispersion liquid can be mentioned.

In the present invention, from the viewpoint of easily improving the brightness of the colored layer, the total content of dyes and lake colorants is preferably 5 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the total amount of colorants. It is preferably 10 parts by mass or more and 100 parts by mass or less. Among them, from the viewpoint of obtaining a high-brightness colored layer, and from the viewpoint that the compatibility of the colorant with the copolymer containing hydroxyalkyl (meth)acrylate units is improved, and the effect of suppressing the development residue is improved, compared with the viewpoint of The total amount of the colorant is 100 parts by mass, and the content of the lake colorant is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less. Furthermore, from the viewpoint of obtaining a high-brightness coloring layer, the total content of the lake colorant represented by the general formula (1) or the general formula (2) is preferably 100 parts by mass of the total amount of the colorant. 20 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less. If the total content of the lake colorant represented by the general formula (1) or the general formula (2) is more than the above lower limit value, the total content of the colorant and the copolymer containing hydroxyalkyl (meth)acrylate units Compatibility improvement is also preferable from the viewpoint of improving the effect of suppressing development residue, and the viewpoint of improving heat resistance. In the case where the colorant contains the lake colorant represented by the above general formula (1) or the general formula (2), and the combination of the colorant different from the lake colorant, it is carried out in such a way that the desired hue can be obtained. Toning, although not particularly limited, can be obtained from the viewpoint of obtaining a high-brightness colored layer, the compatibility of the colorant with the copolymer containing hydroxyalkyl (meth)acrylate units is improved, and the effect of suppressing development residues is improved. From the viewpoint and the viewpoint of improving heat resistance, the total content of the lake colorant represented by the general formula (1) or the general formula (2) is preferably 20 parts by mass relative to 100 parts by mass of the total amount of the colorant. More than 98 mass parts or less, and 30 mass parts or more and 95 mass parts or less may be sufficient. The colorant includes a lake coloring material represented by the above general formula (1) or general formula (2), and a dye selected from the group consisting of dibenzopyran series and the above general formula (1) or general formula (2). In the case of at least one of the group consisting of the lake colorants of dibenzopyran-based dyes with different lake colorants, from the viewpoint of obtaining the desired hue, relative to the total amount of colorants 100 Parts by mass, the total content of the dibenzopyran-based dye and the lake colorant of the dibenzopyran-based dye may be 2 parts by mass or more, and may also be more than 5 parts by mass. From the viewpoint of lowering the properties, it is preferably 30 parts by mass or less, and may be 25 parts by mass or less. In addition, when the colorant contains the lake colorant represented by the general formula (1) or the general formula (2), and C.I. Pigment Blue 15:6, from the viewpoint of obtaining the desired hue, relative to the color The total amount of materials is 100 parts by mass, and the content of C.I. Pigment Blue 15:6 may be 20 parts by mass or more, and may be 30 parts by mass or more. On the other hand, from the viewpoint of suppressing the decrease in brightness of the colored layer and suppressing the generation of development residues And from a viewpoint of suppressing the fall of the heat resistance of a coloring material, 80 mass parts or less are preferable, and 70 mass parts or less may be sufficient.

Moreover, the content of the dye and the lake coloring material is usually 0.5 mass % or more and 35 mass % or less, preferably 1 mass % or more and 30 mass % or less with respect to the total solid content of the photosensitive colored resin composition of the present invention. , more preferably 2 mass % or more and 25 mass % or less.

＜Other pigments＞ The photosensitive colored resin composition of the present invention may further contain other pigments different from the above-mentioned C.I. Pigment Blue 15:6 within a range that does not impair the effects of the present invention to adjust the color tone. As the other pigments, various organic pigments and inorganic pigments that have been used as colorants for color filters can be used, and are not particularly limited, but organic pigments are preferred from the viewpoint of being excellent in color rendering properties and heat resistance. .

In the case of blue applications, as the other pigments mentioned above, blue pigments such as copper phthalocyanine pigments having an ε-type or β-type crystal structure, and C.I. Pigment Violet can be preferably used from the viewpoint of excellent dispersion stability. 23 and other purple pigments. As a copper phthalocyanine pigment having an ε-type or β-type crystal structure, among them, the group consisting of C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 and 15:5 can be preferably used at least one of the group. In addition, the above-mentioned other pigments can be acid-treated or alkaline-treated similarly to C.I. Pigment Blue 15:6 to improve dispersion stability. As for the other pigments mentioned above, similarly, when the dispersant used in combination is acidic, it is preferably subjected to alkaline treatment, and when the dispersant used in combination is alkaline, it is preferably subjected to acidic treatment.

In the present invention, the other pigments described above are preferably used in an amount within a range that does not impair the effects of the present invention. Specifically, the content of the other pigments is preferably 25% by mass or less relative to the total solid content of the photosensitive colored resin composition, or 100 parts by mass relative to the total amount of dyes and lake colorants , the content of the above-mentioned other pigments is set to 80 parts by mass or less. Furthermore, the smaller of the above-mentioned two upper limit amounts is set as a more preferable upper limit amount.

[binder resin] <Copolymer containing hydroxyalkyl (meth)acrylate units> The binder resin contained in the photosensitive colored resin composition of the present invention contains the following copolymer (copolymer containing a hydroxyalkyl (meth)acrylate unit) containing 5 to 25% by mass of the following The polymer structure of the structural unit derived from the hydroxyalkyl (meth)acrylate represented by the general formula (A) has a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH/g. The above-mentioned copolymer containing a hydroxyalkyl (meth)acrylate unit is an alkali-soluble copolymer containing a structural unit derived from a hydroxyalkyl (meth)acrylate in the chain structure of the polymer backbone. The polymer structure of the copolymer containing a hydroxyalkyl (meth)acrylate unit may be a structure having only a main chain or a structure having a main chain and a side chain. The main chain of the copolymer containing a hydroxyalkyl (meth)acrylate unit typically has a chain structure formed by linking structural units produced by addition polymerization of a monomer having an ethylenically unsaturated bond, Furthermore, the structural unit produced by addition polymerization or polycondensation polymerization of the monomer which has a functional group other than an ethylenically unsaturated bond can be contained. The side chains of copolymers containing hydroxyalkyl (meth)acrylate units are typically formed by linking groups generated by the reaction of functional groups on the main chain with functional groups of the monomers used to form the side chains. It is bonded to the main chain, and can also be branched from the main chain through carbon-carbon bonds. As an example of forming a side chain by reacting a functional group on the main chain with a functional group of a monomer for forming a side chain, for example, when a carboxyl group exists on the main chain, the monomer having a glycidyl group is reacted with The carboxyl group reacts to form an ester linking group, and a side chain including a structural unit derived from a monomer having a glycidyl group can be introduced. As another example, when a hydroxyl group exists in the main chain, the following side chain can be introduced by reacting a monomer having an isocyanate group with the hydroxyl group to form a urethane linking group. The chain contains structural units derived from monomers having isocyanate groups. The side chain may have a pendant structure having a structural unit of one monomer, or may have a polymer structure formed by linking two or more structural units. In addition, when the side chain has a polymer structure, it may be composed of only a structural unit derived from a monomer having an ethylenically unsaturated bond, or may include a single unit derived from a functional group other than an ethylenically unsaturated bond. Structural units produced by addition or condensation polymerization. The copolymer containing a hydroxyalkyl (meth)acrylate unit has, in addition to a hydroxyl group derived from a hydroxyalkyl (meth)acrylate, an acidic group capable of imparting alkali solubility and a group containing an ethylenic double bond as necessary Atomic groups such as other functional groups such as bulky groups, groups that adjust molecular structure such as bulky groups, etc., can be present in either the main chain or the side chain.

A preferable example of a copolymer containing a hydroxyalkyl (meth)acrylate unit includes a copolymer in which the following side chain is bonded to the following main chain, and the side chain includes an ethylenically unsaturated bond, etc. A structural unit of a photopolymerizable functional group, the main chain includes a structural unit derived from hydroxyalkyl (meth)acrylate, a structural unit with an acidic group, a structural unit with a bulky group, and other structures as required unit. The copolymer containing such a hydroxyalkyl (meth)acrylate unit is provided with alkali solubility by the acidic group on the main chain, and is provided with crosslinking bondability by the photopolymerizable functional group in the side chain. When the copolymer containing a hydroxyalkyl (meth)acrylate unit has a photopolymerizable functional group, in the curing step of the resin composition in the production of a color filter, the binder resins or the binder resins A crosslinking bond can be formed with a monomer or the like which is a photopolymerizable compound. As a result, the film strength of the cured film is further improved, the development resistance is improved, and the thermal shrinkage of the cured film is suppressed, and the adhesiveness with the substrate becomes excellent.

As the above-mentioned preferred hydroxyalkyl (meth)acrylate unit-containing copolymer, a hydroxyalkyl (meth)acrylate unit-containing copolymer into which a side chain having a photopolymerizable functional group is introduced can be produced, for example, as follows Copolymers: hydroxyalkyl (meth)acrylates with alkylene groups having 1 to 4 carbon atoms, ethylenically unsaturated monomers with acidic groups, ethylenically unsaturated monomers with bulky groups, and Other ethylenically unsaturated monomers as needed are copolymerized to synthesize the main chain part, and then the photopolymerizable functional group with a functional group that reacts with the functional group on the main chain to generate a bond and a photopolymerizable functional group The monomer of the functional group reacts with it. Hereinafter, the structural unit which comprises the main chain and the side chain of the copolymer containing a hydroxyalkyl (meth)acrylate unit, and the monomer for forming this structural unit are demonstrated.

(Structural unit derived from hydroxyalkyl (meth)acrylate represented by general formula (A)) The structural unit derived from hydroxyalkyl (meth)acrylate (hereinafter, sometimes referred to as "hydroxyalkyl (meth)acrylate unit") represented by the following general formula (A) has the following chemical structure, The chemical structure is that the ethylenic double bond of the hydroxyalkyl (meth)acrylate having an alkylene group having 1 to 4 carbon atoms is cleaved due to an addition reaction, resulting in two single bonds.

(通式(A)中，R ^A表示甲基或氫原子，R ^B表示碳數1～4之伸烷基) [Chem. 13] General formula (A)

(In the general formula (A), R ^A represents a methyl group or a hydrogen atom, and R ^B represents an alkylene group having 1 to 4 carbon atoms)

As the structural unit derived from hydroxyalkyl (meth)acrylate represented by the above-mentioned general formula (A), it is preferable that R ^A in the above-mentioned general formula (A) is a methyl group derived from hydroxyalkane methacrylate The structural unit of the base ester. Specific examples of the hydroxyalkyl (meth)acrylate unit represented by the general formula (A) include those derived from hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ( 2-hydroxypropyl meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxyisobutyl (meth)acrylate, etc. ( Structural unit of hydroxyalkyl meth)acrylate, etc. Among them, the structural unit derived from 2-hydroxyethyl (meth)acrylate, the structural unit derived from 2-hydroxypropyl (meth)acrylate, and the structural unit derived from 2-hydroxy-1-(meth)acrylate are preferred. The structural unit of methyl ethyl ester is particularly preferably a structural unit derived from 2-hydroxyethyl (meth)acrylate.

In the present invention, with respect to 100% by mass of the total amount of the structural units constituting the copolymer, the percentage of the hydroxyalkyl (meth)acrylate unit contained in the copolymer containing the hydroxyalkyl (meth)acrylate unit The amount is 5 mass % or more and 25 mass % or less. By making the quantity of a hydroxyalkyl (meth)acrylate unit into the said range, the coloring layer which is excellent in flatness and the development residue is suppressed can be obtained. When the amount of the hydroxyalkyl (meth)acrylate unit is less than 5% by mass, when the coating film of the photosensitive coloring resin composition is heated and dried, the fluidization of the coating film cannot be sufficiently suppressed, so the The flatness of the obtained coloring layer was deteriorated. On the other hand, when the amount of the hydroxyalkyl (meth)acrylate unit exceeds 25% by mass, the viscosity of the photosensitive colored resin composition may increase, resulting in poor coating properties or the photosensitive colored resin composition. The solvent re-solubility decreases, and foreign matter or unevenness is easily generated in the coloring layer obtained thereby. Among these, it is preferable that the quantity of the hydroxyalkyl (meth)acrylate unit contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is 5 mass % or more and 20 mass % or less.

(Structural unit with acidic group) In the structural unit which has an acidic group, as an acidic group, a carboxyl group, a phosphoric acid group, a sulfo group etc. are mentioned, for example, Among them, a carboxyl group is preferable from a viewpoint of easy introduction of the side chain which has a photopolymerizable functional group. As the structural unit having an acidic group, for example, a structural unit derived from an ethylenically unsaturated monomer having a carboxyl group can be preferably used. The structural unit derived from an ethylenically unsaturated monomer having a carboxyl group has the following chemical structure, which is that the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a carboxyl group is broken due to an addition reaction, resulting in 2 a single key. Furthermore, in the present invention, a structural unit derived from an ethylenically unsaturated monomer means a structural unit in which a radically polymerizable carbon-carbon double bond of the ethylenically unsaturated monomer becomes a carbon-carbon single bond. Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleic acid, fumaric acid, Icon acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, monomers having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, together with maleic anhydride, succinic anhydride, phthalic anhydride, cyclic Addition reaction products of cyclic acid anhydrides such as hexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. In addition, acid anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and glass transition temperature.

The amount of the structural unit having an acidic group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 8% by mass or more with respect to 100% by mass of the total amount of the structural units constituting the copolymer 30 mass % or less. By making the quantity of the structural unit which has an acidic group in the said range, sufficient alkali solubility can be provided to the coating film of the photosensitive coloring resin composition, and the fall of solvent solubility can be suppressed. When the amount of the structural unit having an acidic group is less than 8% by mass, the acid value is too low, and sufficient alkali solubility may not be obtained. On the other hand, when the quantity of the structural unit which has an acidic group exceeds 30 mass %, the polarity of the photosensitive resin composition is too high, and it may become difficult to melt|dissolve in a solvent. The amount of the structural unit having an acidic group is more preferably 10 mass % or more and 28 mass % or less, and still more preferably 12 mass % or more and 28 mass % or less.

(structural unit with bulky base) As a structural unit which has a bulky group, the structural unit derived from the ethylenically unsaturated monomer which has a bulky group is mentioned, for example. The structural unit derived from an ethylenically unsaturated monomer having a bulky group has the following chemical structure, and the chemical structure is that the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a bulky group is broken by addition reaction. , resulting in 2 single bonds. When the copolymer containing a hydroxyalkyl (meth)acrylate unit has a bulky group, shrinkage during curing of the adhesive resin is suppressed, peeling from the substrate is alleviated, and adhesion to the substrate is improved. In addition, the bulky group may be contained in the form of a monovalent group, or may be contained in the form of a bivalent or higher group. Examples of such bulky groups include hydrocarbon rings such as an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and combinations thereof. The hydrocarbon ring may have substituents such as an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, a halogen atom, and the like. Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, noroxane, isoxane, tricyclo[5.2.1.0(2,6)]decane (bicyclo aliphatic hydrocarbon rings such as pentane) and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and stilbene; chain polycyclic rings such as biphenyl, triphenyl, diphenylmethane, triphenylmethane, and stilbene, or Cardo structure (9,9-diaryl fluoride); a group obtained by substituting a part of these groups with a substituent, etc. In the case where an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance and adhesiveness of the colored layer are improved, and the brightness of the obtained colored layer is improved, which is preferable in this respect. In addition, when the structural unit includes the above-mentioned Cardo structure, the curability of the colored layer is improved, the discoloration of the colorant can be suppressed, and the solvent resistance (swelling of NMP (N-Methyl pyrrolidone, N-methyl pyrrolidone) is suppressed) is improved. , which is particularly good in this regard.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, and iso(meth)acrylate Base ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., from the viewpoint that the cross-sectional shape of the coloring layer after development is also maintained unchanged during heat treatment. In other words, it is preferable to use at least one selected from cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene .

The amount of the structural unit having a bulky group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 20% by mass with respect to 100% by mass of the total amount of the structural units constituting the copolymer More than 70 mass % or less. By making the quantity of the structural unit which has a bulky group within this range, the adhesiveness of a coating film with respect to a board|substrate becomes excellent. When the amount of the structural unit having a bulky base is less than 20% by mass, the adhesiveness of the coating film to the substrate may become insufficient. On the other hand, in the case where the amount of the structural unit having a bulky group exceeds 70% by mass, the hydroxyalkyl (meth)acrylate unit, the acidic group or the photopolymerizable functional group may not be sufficiently introduced, resulting in photosensitivity. The developability or film-forming property of the colored resin composition, or the flatness of the obtained colored layer becomes insufficient. The amount of the structural unit having a bulky group is more preferably 20 mass % or more and 60 mass % or less, and still more preferably 20 mass % or more and 55 mass % or less.

(Other structural units that make up the main chain) By including a structural unit with neither functional group nor bulky group on the main chain of the copolymer containing hydroxyalkyl (meth)acrylate units, physical properties can be adjusted, such as inhibiting alkali solubility and improving solvent solubility , improve solvent re-solubility, etc. As the ethylenically unsaturated monomer from which other structural units constituting the main chain of the copolymer containing hydroxyalkyl (meth)acrylate units are derived, for example, methyl (meth)acrylate, ethyl (meth)acrylate can be used. (Meth)acrylate which has no functional group and has a low molecular ester residue, such as an ester.

(Structural unit constituting a side chain having a photopolymerizable functional group) The side chain having a photopolymerizable functional group may have a side chain structure composed of only one structural unit having a photopolymerizable functional group, or may have a polymer structure formed by linking two or more structural units. When the side chain is a side chain structure having a structural unit of one monomer, it has the following chemical structure, and the chemical structure is that the photopolymerizable functional group-containing monomer reacts with the functional group on the main chain to generate a bond The functional group produces a linking group bonded to the main chain. Examples of the photopolymerizable functional group-containing monomer having a photopolymerizable functional group and a functional group that reacts with a functional group on the main chain to generate a bond include, for example, an ethylenically unsaturated bond as a photopolymerizable functional group. , and has an epoxy group as a functional group that reacts with a functional group on the main chain to generate a bond such as glycidyl (meth)acrylate; and has an ethylenically unsaturated bond as a photopolymerizable functional group, and Compounds having an isocyanate group as a functional group that reacts with a functional group on the main chain to generate a bond; and the like. When a monomer having a photopolymerizable functional group and an epoxy group is used, a side chain having a photopolymerizable functional group can be formed by reacting the monomer with the carboxyl group on the main chain. In this case, when the photopolymerizable functional group is introduced into the copolymer containing the hydroxyalkyl (meth)acrylate unit, the reaction between the carboxyl group on the main chain and the epoxy group is consumed, so that the acid value is Since it becomes smaller, the photocurability and developability of the copolymer containing a hydroxyalkyl (meth)acrylate unit change in a linked manner. Therefore, the amount of the monomer having a carboxyl group or a structural unit derived from the monomer, and the amount of the monomer having a carboxyl group or a structural unit derived from the The amount of monomers of photopolymerizable functional groups and epoxy groups or structural units derived from the monomers. Moreover, when using the monomer which has a photopolymerizable functional group and an isocyanate group, the side chain which has a photopolymerizable functional group can be formed by making this monomer react with the hydroxyl group on a main chain. Among these photopolymerizable functional group-containing monomers, a monomer having a photopolymerizable functional group and an epoxy group is preferably used. In the present invention, from the viewpoint of improving the flatness of the colored layer, what is important is the amount of hydroxyalkyl (meth)acrylate units in the copolymer containing hydroxyalkyl (meth)acrylate units, but Monomers with photopolymerizable functional groups and epoxy groups have high reactivity with carboxyl groups and hardly consume the hydroxyl groups in copolymers containing hydroxyalkyl (meth)acrylate units, so it is easy to adjust (methyl) ) amount of hydroxyalkyl acrylate units.

When the copolymer containing a hydroxyalkyl (meth)acrylate unit has an ethylenically unsaturated group in the side chain, the film strength of the cured film is improved, the development resistance is improved, and the adhesion to the substrate is excellent. From a viewpoint, the range of 100-2000 is preferable, and, as for the ethylenically unsaturated bond equivalent, the range of 140-1500 is especially preferable. When this ethylenically unsaturated bond equivalent is 100 or more, it is excellent in development resistance and adhesiveness. Moreover, since the ratio of other structural units, such as the structural unit which has the said acidic group and the structural unit which has a bulky group, can be relatively increased as it is 2000 or less, it is excellent in developability and heat resistance. Here, the ethylenically unsaturated bond equivalent refers to the weight average molecular weight per 1 mole of the ethylenically unsaturated bond in the copolymer containing hydroxyalkyl (meth)acrylate units, and is represented by the following mathematical formula (1) .

Mathematical formula (1) Equivalent of ethylenically unsaturated bonds (g/mol)=W(g)/M(mol) (In the mathematical formula (1), W represents the mass (g) of the copolymer containing hydroxyalkyl (meth)acrylate units, and M represents the amount contained in the copolymer containing hydroxyalkyl (meth)acrylate units The number of moles of ethylenic double bond (mol)

The above-mentioned ethylenically unsaturated bond equivalent can be calculated, for example, by measuring per 1 unit of the copolymer containing hydroxyalkyl (meth)acrylate units in accordance with the test method for iodine value described in JIS K 0070:1992. The number of ethylenic double bonds contained in g.

The amount of the structural unit having a photopolymerizable functional group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 2.5 with respect to 100% by mass of the total amount of the structural units constituting the copolymer. Mass % or more and 35 mass % or less. By making the quantity of the structural unit which has a photopolymerizable functional group in the said range, the photocurability of the copolymer containing a hydroxyalkyl (meth)acrylate unit can be improved. When the amount of the structural unit having a photopolymerizable functional group is less than 2.5% by mass, the photocurability of the copolymer containing a hydroxyalkyl (meth)acrylate unit may not be sufficiently obtained. On the other hand, when the quantity of the structural unit which has a photopolymerizable functional group exceeds 35 mass %, the acidic group of a main chain will be excessively consumed, and sufficient alkali solubility may not be acquired. The amount of the structural unit having a photopolymerizable functional group is more preferably 4 mass % or more and 32 mass % or less, and still more preferably 5 mass % or more and 31 mass % or less.

In this invention, the weight average molecular weight (Mw) of the copolymer containing a hydroxyalkyl (meth)acrylate unit is made 11,000 or more. By setting the weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit to 11,000 or more, when the coating film of the photosensitive colored resin is heated and dried, it can be The molecular weight effect of the copolymer of alkyl ester units increases the viscosity of the softened coating film and inhibits the fluidization of the coating film. When the weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is less than 11,000, the fluidization of the coating film cannot be sufficiently suppressed during heat drying. The weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is not particularly limited, but is preferably 25,000 or less. When the weight-average molecular weight (Mw) of the copolymer containing hydroxyalkyl (meth)acrylate units exceeds 25,000, the viscosity of the photosensitive resin composition becomes too high and may deviate from the viscosity suitable for coating . The weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is more preferably 11,000 or more and 20,000 or less, and still more preferably 11,000 or more and 19,000 or less.

In addition, in this invention, the weight average molecular weight (Mw) is the value measured by GPC (gel permeation chromatography). The measurement was performed by using HLC-8220GPC manufactured by Tosoh Corporation, using N-methylpyrrolidone added with 0.01 mol/liter of lithium bromide as the elution solvent, and using Mw: 8×10 ⁵ (F-80) , Mw: 4×10 ⁵ (F-40), Mw: 2×10 ⁵ (F-20), Mw: 1×10 ⁵ (F-10), Mw: 4×10 ⁴ (F-4), Mw : 2×10 ⁴ (F-2), Mw: 5×10 ³ (A-5000), Mw: 2.5×10 ³ (A-2500), Mw: 1×10 ³ (A-1000), Mw: 5 ×10 ² (A-500) (manufactured by Tosoh Co., Ltd. above) was used as a polystyrene standard sample for the calibration curve, and TSK-GEL ALPHA-M×2 (manufactured by Tosoh Co., Ltd.) was used as a measurement column.

In this invention, the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is 60 mgKOH/g or more and 130 mgKOH/g or less. By setting the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units to 60 mgKOH/g or more, sufficient alkali solubility can be imparted to the coating film of the photosensitive colored resin, and the shape of the colored layer can be flattened The effect of transformation is excellent. On the other hand, by making the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit into 130 mgKOH/g or less, when developing a coating film, the development residue on a board|substrate can be reduced. The acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is preferably 65 mgKOH/g or more and 125 mgKOH/g or less, more preferably 65 mgKOH/g or more and 110 mgKOH/g or less, and still more preferably 70 More than mgKOH/g and less than 100 mgKOH/g. When the photosensitive coloring resin composition of the present invention contains a lake coloring material as a coloring material, the effect of suppressing the generation of development residues is high, so the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit can be improved. 100 mgKOH/g or more, 110 mgKOH/g or more, or 120 mgKOH/g or more. The higher the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit, the easier it is to flatten the colored layer.

The hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 50 mgKOH/g or more and 200 mgKOH/g or less. When the hydroxyl value of the copolymer containing hydroxyalkyl (meth)acrylate units is less than 50 mgKOH/g, the hydrophobicity of the coating film of the photosensitive coloring resin composition becomes too high, which may lead to deterioration of developability. Difference. On the other hand, when the hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit exceeds 200 mgKOH/g, the solvent resolubility of the photosensitive coloring resin composition is deteriorated, resulting in poor coating properties. Danger of damage. The hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is more preferably 70 mgKOH/g or more and 190 mgKOH/g or less, and still more preferably 80 mgKOH/g or more and 180 mgKOH/g or less.

The copolymer containing a hydroxyalkyl (meth)acrylate unit is usually added to the photosensitive colored resin composition for color filters of the present invention in the state of a varnish obtained by being dissolved in a solvent. Although not particularly limited, the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably such that the solid content concentration becomes 60 mass % from the viewpoint of easily obtaining a colored layer excellent in flatness. The viscosity of the varnish obtained by dissolving it in a solvent when heated to 90°C is 500 mPa·s or more, more preferably 600 mPa·s or more, and still more preferably 700 mPa·s or more. On the other hand, the above-mentioned viscosity may be 10,000 mPa·s or less, or 9,000 mPa·s or less. If the said viscosity is below the said upper limit value. Since the photosensitive colored resin composition is easily dried, the productivity of the color filter can be improved. In addition, the solvent for dissolving the copolymer containing a hydroxyalkyl (meth)acrylate unit is not particularly limited, and for example, the solvent contained in the photosensitive resin composition for a color filter of the present invention can be used. the same solvent.

<Other binder resins> The photosensitive colored resin composition of this invention may contain other binder resin in combination with the copolymer containing a hydroxyalkyl (meth)acrylate unit. As other binder resins, acrylic resins having a structure obtained by removing hydroxyalkyl (meth)acrylate units from the structure of the above-mentioned copolymer containing hydroxyalkyl (meth)acrylate units, including Structural units other than the hydroxyalkyl (meth)acrylate unit and side chain acrylic resins, styrene-acrylic resins, polyolefin resins, etc. are obtained by polymerizing ethylenically unsaturated bond-containing monomers Photosensitive or non-photosensitive polymers. Furthermore, as other binder resins, polymers which have been used as binder resins for forming colored layers of color filters, such as epoxy-based resins, urethane-based resins, polyester-based resins, Photosensitive or non-photosensitive resins such as polyimide resins and phenolic resins.

In the photosensitive colored resin composition of the present invention, the content of the binder resin is usually 4 mass % or more and 25 mass % or less, preferably 5 mass % or more with respect to the total solid content of the photosensitive coloring resin composition. 22 mass % or less, more preferably 5 mass % or more and 20 mass % or less. Moreover, in the photosensitive colored resin composition of the present invention, the content of the copolymer containing a hydroxyalkyl (meth)acrylate unit is usually 50 parts by mass or more and 95 parts by mass relative to 100 parts by mass of the total amount of the binder resin. part or less, preferably 60 parts by mass or more and 92 parts by mass or less, more preferably 65 parts by mass or more and 90 parts by mass or less.

[Monomer (photopolymerizable compound)] The monomer as a photopolymerizable compound used in the photosensitive colored resin composition of the present invention is not particularly limited as long as it can be polymerized with a photoinitiator, but it is preferable to contain two or more polymerizable monomers. Multifunctional monomer with double bond. As the polyfunctional monomer, a polyfunctional monomer having two or more ethylenically unsaturated double bonds is preferred, and a polyfunctional (meth)acrylic acid having two or more acrylyl groups or methacrylyl groups is particularly preferred ester. The polyfunctional (meth)acrylate may be appropriately selected from previously known polyfunctional (meth)acrylates. As a specific example, the polyfunctional (meth)acrylate etc. which are described in Unexamined-Japanese-Patent No. 2013-029832 are mentioned, for example. Moreover, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), it is preferable that the polyfunctional monomer has three or more (trifunctional) polymerizable double bonds, such as Poly(meth)acrylates of trivalent or higher polyhydric alcohols or dicarboxylic acid-modified products thereof can be preferably used. Specifically, preferred are: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate succinic acid modified product, pentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Tris(2-(meth)acryloyloxyethyl)phosphate, etc. If a phosphorus atom-containing polyfunctional (meth)acrylate such as tris(2-(meth)acryloyloxyethyl)phosphate is used, it is easy to inhibit the fading of the lake color, and it is easy to improve the post-baking effect. The brightness is better in this respect. These polyfunctional (meth)acrylates may be used alone or in combination of two or more.

In the photosensitive coloring resin composition of the present invention, the viscosity of the coating film of the photosensitive coloring resin composition is easily moderated and the flatness of the obtained coloring layer is improved. The content of the polyfunctional monomer is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, particularly preferably 100 parts by mass, based on 100 parts by mass.

In the photosensitive colored resin composition of the present invention, the content of the monomer is not particularly limited, but is preferably 5% by mass or more and 60% by mass or less with respect to the total solid content of the photosensitive coloring resin composition, more preferably It is 10 mass % or more and 50 mass % or less. When the content of the monomer is equal to or more than the above-mentioned lower limit value, the photohardening reaction tends to proceed, whereby elution of the exposed portion during development can be suppressed, and when the content of the monomer is equal to or less than the above-mentioned upper limit value, the alkaline development can be improved. sex.

等9-氧硫𠮿

類。 其中，就感度優異之觀點而言，本發明中所使用之光起始劑較佳為包含選自肟酯類及α-胺基酮類中之至少一種，就圖案形成時之線寬之調整及耐顯影性之觀點而言，較佳為α-胺基酮類。具有三級胺結構之α-胺基酮類在分子內具有作為氧猝滅劑之三級胺結構，因此起始劑所產生之自由基不易因氧而失活，可提高感度，就該方面而言較佳。 又，就抑制水斑，且提高感度之觀點而言，將肟酯類與α-胺基酮類加以組合而用作光起始劑亦較佳。再者，所謂水斑意指當使用使鹼性顯影性變高之成分時，於鹼性顯影後，利用純水進行沖洗後，產生如水滲入之痕跡。此種水斑會於後烘烤後消失，因此製品無問題，但會產生以下問題，即，顯影後在圖案化面之外觀檢查中會以不均異常之形式被檢測出，而無法區分正常品與異常品。因此，若在外觀檢查中降低檢查裝置之檢查感度，則結果會引起最終之彩色濾光片製品之良率降低，從而成為問題。 又，就調整感度，抑制水斑，耐顯影性提高之觀點而言，較佳為將選自肟酯類及α-胺基酮類中之至少一種、與9-氧硫𠮿

類加以組合而作為光起始劑。 [Photoinitiator] The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and may be used alone or in combination of two or more kinds of previously known various initiators. Examples of the photoinitiator include benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (for example, Hicure ABP, Kawaguchi Aromatic ketones such as pharmaceutical companies), 4-methoxy-4'-dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoins such as ethyl benzoin; 2-(o-chlorobenzene) yl)-4,5-phenylimidazole dimer and other biimidazoles; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyl Oxadiazole compounds; 2-(4-butoxy-naphtho-1-yl)-4,6-bis-trichloromethyl-S-tris-triss and other halomethyl-S-triss; 1, 2-Octanedione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzyl) Acetyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Publication No. 2010 - Oxime esters such as oxime ester-based photoinitiators described in Japanese Patent Publication No. 527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Laid-Open No. 2013-041153, etc.; 2-methyl-1-(4 -Methylthiophenyl)-2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholine) phenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( α-amino ketones such as 4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF);

Wait for 9-oxysulfur 𠮿

kind. Among them, from the viewpoint of excellent sensitivity, the photoinitiator used in the present invention preferably contains at least one selected from the group consisting of oxime esters and α-amino ketones, and it is preferable to adjust the line width during pattern formation. From the viewpoint of development resistance, α-amino ketones are preferred. The α-amino ketones with tertiary amine structure have a tertiary amine structure as oxygen quencher in the molecule, so the free radicals generated by the initiator are not easily deactivated by oxygen, which can improve the sensitivity. is better. Moreover, from the viewpoint of suppressing water spots and improving sensitivity, it is also preferable to use oxime esters and α-amino ketones in combination as a photoinitiator. In addition, the so-called water spot means that when a component which increases the alkaline developability is used, after alkaline development, after rinsing with pure water, a trace like water infiltration occurs. Such water spots will disappear after post-baking, so there is no problem with the product, but there will be the following problems, that is, in the appearance inspection of the patterned surface after development, it will be detected in the form of uneven abnormality, and it is impossible to distinguish normal Goods and Unusual Goods. Therefore, when the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which is a problem. In addition, from the viewpoint of adjusting sensitivity, suppressing water spots, and improving development resistance, it is preferable to combine at least one selected from oxime esters and α-amino ketones with 9-oxothiocyanate

are combined as photoinitiators.

The total content of the photoinitiators used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, and it is relatively high relative to the total solid content of the photosensitive colored resin composition. Preferably it is 0.1 mass % or more and 12.0 mass % or less, More preferably, it exists in the range of 1.0 mass % or more and 8.0 mass % or less. When the content is equal to or more than the above lower limit value, photohardening proceeds sufficiently, and elution of the exposed portion at the time of development is suppressed. On the other hand, if it is equal to or less than the above upper limit value, yellowing of the obtained colored layer is suppressed. Decrease in brightness can be suppressed.

[Antioxidants] It is preferable that the photosensitive coloring resin composition of this invention further contains an antioxidant from the viewpoint of improving heat resistance, suppressing discoloration of a coloring material, and improving brightness. By containing an antioxidant, the photosensitive colored resin composition of the present invention can control the excessive free radical chain reaction in the micropores without damaging the curability when forming the micropores of the cured film, so that the desired shape can be formed more easily of micropores. Moreover, it is preferable to use an antioxidant in combination with an oxime ester type photoinitiator from a viewpoint of easily obtaining the said effect. The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from previously known antioxidants. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. From the viewpoint of heat resistance, and changing the shape of micropores From the viewpoint of being favorable, it is preferable to use a hindered phenol-based antioxidant. It can also be a latent antioxidant as described in International Publication No. 2014/021023.

Examples of hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF Corporation), isocyanurate 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl) cyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4- Hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methyl) phenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF Corporation ), 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester (trade name: Irgamod 195, manufactured by BASF Corporation), and the like. Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, BASF) is preferable from the viewpoint of heat resistance and light resistance manufactured by the company).

As content of an antioxidant, 0.1 mass % or more and 10.0 mass % or less are preferable with respect to the solid content total amount in a photosensitive colored resin composition, and 0.5 mass % or more and 5.0 mass % or less are more preferable. If it is more than the said lower limit, it will be excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the photosensitive resin composition can be made into high sensitivity.

When the antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the antioxidant is preferably 1 with respect to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator. The amount is not less than 250 parts by mass, more preferably not less than 3 parts by mass and not more than 80 parts by mass, and still more preferably not less than 5 parts by mass and not more than 65 parts by mass. Within the above-mentioned range, the effect of the above-mentioned combination is excellent.

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

[solvent] The solvent used in the present invention is not particularly limited as long as it is an organic solvent that can dissolve or disperse the components of the photosensitive colored resin composition without reacting with each other. A solvent can be used individually by 1 type or in combination of 2 or more types. Specific examples of the solvent include alcohol-based solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxy ethoxy ethanol, ethoxy ethoxy alcohol, and the like. Carbitol-based solvents such as ethyl alcohol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate , ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexyl acetate and other ester solvents; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, cyclohexanone, and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, Glycol ether acetate solvents such as 3-methoxybutyl acetate and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol Carbitol acetate solvents such as acetate (BCA) and carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, etc. Alcohol ether solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other aprotic amide solvents; γ-butyrolactone and other lactones cyclic ether-based solvents such as tetrahydrofuran; unsaturated hydrocarbon-based solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon-based solvents such as N-heptane, N-hexane, and N-octane; toluene and xylene Organic solvents such as aromatic hydrocarbons. Among these solvents, from the viewpoint of solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used. 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 from the viewpoint of solubility of other components or coating suitability. acetate (BCA), carbitol acetate, 3-methoxy-3-methylbutyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate more than one of the groups.

Although content of a solvent is not specifically limited, It is preferable that it is 75 mass % or more and 95 mass % or less with respect to the total amount of the photosensitive colored resin composition, More preferably, it is 80 mass % or more and 90 mass % or less. By making the content of the solvent in the photosensitive colored resin composition more than or equal to the above lower limit value, the solubility and coating suitability of other components can be improved, and on the other hand, by making the above content equal to or less than the above upper limit value, The usage-amount of the photosensitive coloring resin composition used at the time of formation of a color filter can be reduced.

II. The manufacturing method of the photosensitive colored resin composition for color filters The manufacturing method of the photosensitive colored resin composition of the present invention is not particularly limited. For example, the above-mentioned components such as colorants, binder resins, monomers, and photoinitiators can be mixed into a solvent to dissolve or disperse them. In order to manufacture the photosensitive coloring resin composition by this, it is preferable to manufacture the photosensitive coloring resin composition by preliminarily preparing a color material dispersion liquid obtained by dispersing a color material in a solvent using a dispersant, or by making a color material dispersion liquid. The colorant solution obtained by dissolving the material in the solvent, the colorant dispersion or the colorant solution, and the photosensitive coloring resin other than the colorant such as the binder resin, monomer, photoinitiator, etc., are used by a known dispersion method. The components of the composition are mixed into a solvent to dissolve or disperse them. Furthermore, in the case of using two or more colorants, the photosensitive colored resin composition can be produced by preparing a colorant dispersion or a colorant solution for each color of the colorant, and then adding each colorant The dispersion liquid or the colorant solution, and the components of the photosensitive colored resin composition other than the colorant such as the binder resin and the photoinitiator are mixed into the solvent, and these are dissolved or dispersed. The colorant dispersion liquid and the colorant solution are used as pre-preparations for preparing the colored resin composition. That is, the colorant dispersion liquid and the colorant solution are pre-prepared in the preparation stage of preparing the colored resin composition, and the P/V ratio, that is, (the mass of the colorant component in the composition)/(the colorant component in the composition is not included) The solid content quality) is relatively high. Specifically, the P/V ratio of the colorant dispersion liquid and the colorant solution is usually 1.0 or more.

The photosensitive colored resin composition of the present invention produced using the colorant dispersion liquid contains a dispersant. The photosensitive colored resin composition of the present invention containing a lake color material or a pigment is preferably produced using a color material dispersion liquid in which a lake color material or a pigment is dispersed, and therefore preferably contains a dispersant. Hereinafter, the color material dispersion liquid used for manufacture of the photosensitive colored resin composition of this invention is demonstrated in detail. The colorant dispersion liquid used in the present invention includes a solvent, a dispersant, and the above-mentioned colorant dispersed in the solvent by using the dispersant, and may further include other components such as a dispersing aid as required.

[Dispersant] As a dispersing agent, it can select suitably from those previously used as a dispersing agent, and can be used. As the dispersing agent, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferred from the viewpoint of being able to uniformly and finely disperse. Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts and (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid. Ammonium salts or (partial) alkylamine salts; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or their modifications; polyurethanes; unsaturated polyacrylates amides; polysiloxanes; long-chain polyaminoamide phosphates; polyethylenimine derivatives (by reaction of poly(lower alkyleneimine) with polyesters containing free carboxyl groups) The obtained amides or their equivalent bases); polyallylamine derivatives (by making polyallylamine, and selected from polyesters with free carboxyl groups, polyamides or co-condensates of esters and amides (polyesters). The reaction product obtained by reacting one or more of the three compounds of amide) and the like.

The dispersant can be appropriately selected and used according to the type of colorant with good dispersibility, and is not particularly limited. 5) The situation of dispersing the metallic lake coloring materials of the dibenzopyran-based dyes represented, and making these lake coloring materials and dyes such as dibenzopyran-based dyes or pigments such as C.I. Pigment Blue 15:6 In the case of co-dispersion, it is preferable to use an acidic dispersant which is an acidic polymer dispersant as a dispersant. In addition, in this invention, a dye can be melt|dissolved in a solvent, and can be used. In the case of dispersing the pigment, it is preferable to use at least one selected from the group consisting of an acidic or basic polymer dispersant and a urethane-based dispersant according to the type of the pigment, and it is more preferable to use an acidic or basic polymer dispersant. Alkaline polymer dispersant. In the case of dispersing an alkaline-treated pigment, it is preferable to use an acidic dispersant as an acidic polymer dispersant, and in the case of dispersing an acid-treated pigment, it is preferable to use an alkaline polymer dispersant Alkaline dispersing agent. As the acidic dispersant for dispersing the lake coloring 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 described below is suitably used. . As an acidic dispersing agent for dispersing a pigment, for example, a carboxyl group-containing block copolymer is suitably used. As the basic dispersant, for example, at least one selected from the group consisting of polymers comprising repeating units having tertiary amines and polymers comprising repeating units having tertiary amines are suitably used. A salt-type polymer in which at least a part of the amine group forms a salt with an organic acid compound. The urethane-based dispersant is a compound having one or more urethane bonds (-NH-COO-) in one molecule. As the urethane-based dispersant, for example, a reaction product of polyisocyanates having two or more isocyanate groups in one molecule and polyesters having hydroxyl groups at one or both ends is 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 dispersant for lake pigments, particularly preferably It can be used as a dispersant for the lake coloring material represented by the above general formula (1) or general formula (2). If a polymer having a structural unit represented by the following general formula (I) is used as an acidic dispersant, the dispersibility and heat resistance of the lake color material can be improved, and the chromaticity change of the lake color material after heating can be suppressed . In addition, when a lake colorant and a pigment are used in combination as a colorant, by using a polymer having a structural unit represented by the following general formula (I) as a dispersant, the dispersibility and storage stability of the pigment can be improved , a coloring layer with improved substrate adhesion and coating film uniformity can be formed. The polymer having the structural unit represented by the following general formula (I) is an ethylenically unsaturated monomer polymer, so it is presumed as follows: the heat resistance of the skeleton is higher than that of the polyether-based or polyester-based polymer, And there are a plurality of acidic phosphorus compound groups (-P(=O)(-R ¹² )(OH)) and their salts (-P(=O)(-R ¹² )(O ^- X ⁺ )) has a strong adsorption force on the surface of the micronized colorant. In addition, it is presumed that if the surface of the colorant is in a state of being covered by at least one of the acidic phosphorus compound group and its salt, the attack (hydrogen abstraction or substitution reaction) of the pigment skeleton of the lake coloring material by reactive oxygen species such as peroxy radicals is suppressed. etc.), thereby suppressing the deterioration (oxidative deterioration) of the lake color material.

(通式(I)中，L ¹¹為直接鍵或二價連結基，R ¹¹為氫原子或甲基，R ¹²為羥基、烴基、-[CH(R ¹³)-CH(R ¹⁴)-O] _x1-R ¹⁵、-[(CH ₂) _y1-O] _z1-R ¹⁵、或-O-R ¹⁶所表示之一價基，R ¹⁶為烴基、-[CH(R ¹³)-CH(R ¹⁴)-O] _x1-R ¹⁵、-[(CH ₂) _y1-O] _z1-R ¹⁵、-C(R ¹⁷)(R ¹⁸)-C(R ¹⁹)(R ²⁰)-OH、或-CH ₂-C(R ²¹)(R ²²)-CH ₂-OH所表示之一價基； R ¹³及R ¹⁴分別獨立地為氫原子或甲基，R ¹⁵為氫原子、烴基、-CHO、-CH ₂CHO、-CO-CH=CH ₂、-CO-C(CH ₃)=CH ₂或-CH ₂COOR ²³所表示之一價基，R ²³為氫原子或碳數為1個以上5個以下之烷基；R ¹⁷、R ¹⁸、R ¹⁹、R ²⁰、R ²¹及R ²²分別獨立地為氫原子、烴基、或具有選自醚鍵及酯鍵中之一種以上之烴基，R ¹⁷及R ¹⁹可彼此鍵結而形成環結構；於形成上述環狀結構之情形時，該環狀結構可進而具有取代基R ²⁴，R ²⁴為烴基、或具有選自醚鍵及酯鍵中之一種以上之烴基；上述烴基可具有取代基；X表示氫原子或有機陽離子；x1表示1以上18以下之整數，y1表示1以上5以下之整數，z1表示1以上18以下之整數) [Chemical 14]

(In the general formula (I), L ¹¹ is a direct bond or a divalent linking group, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydroxyl group, a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ )-O ] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , or a valent group represented by -OR ¹⁶ , where R ¹⁶ is a hydrocarbon group, -[CH(R ¹³ )-CH(R ¹⁴ ) -O] _x1 -R ¹⁵ , -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , -C(R ¹⁷ )(R ¹⁸ )-C(R ¹⁹ )(R ²⁰ )-OH, or -CH ₂ A valent group represented by -C(R ²¹ )(R ²² )-CH ₂ -OH; R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH=CH ₂ , -CO-C(CH ₃ )=CH ₂ or a valent group represented by -CH ₂ COOR ²³ , R ²³ is a hydrogen atom or the number of carbon atoms is 1 or more and 5 or less R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, R ¹⁷ and R ¹⁹ can be bonded to each other to form a ring structure; in the case of forming the above-mentioned ring structure, the ring structure may further have a substituent R ²⁴ , R ²⁴ is a hydrocarbon group, or has one or more selected from ether bonds and ester bonds 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, and z1 represents an integer from 1 to 18)

In the general formula (I), L ^{1 1} is a direct bond or a divalent linking group. Here, L ^{1 1} is a direct bond, meaning that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without a linking group. The divalent linking group in L ^{1 1} is not particularly limited as long as it can link 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, linear, branched or cyclic alkylene having a hydroxyl group, aryl, -CONH - group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof and the like. Furthermore, in the present invention, the direction of the bond of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be the carbon atom side of the main chain and -NH may be the phosphorus atom side of the side chain, and conversely, -NH may be the carbon atom side of the main chain. atom side and -CO is 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 divalent linking group containing a -CONH- group or a -COO- group. For example, when L ¹¹ is a divalent linking group including a -COO- group, L ¹¹ is preferably a -COO-L ¹¹ '- group (here, L ¹¹ ' is one or more carbon atoms which may have a hydroxyl group) 8 or less 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 of 1 or more and 18 or less, and y represents an integer of 1 or more and 5 or less , z represents an integer of 1 or more and 18 or less, and w represents an integer of 1 or more and 18 or less).

In L ^{1 1} ', the alkylene group having 1 to 8 carbon atoms may be any of linear, branched, or cyclic, such as methylene, ethylidene, trimethylene, For propylidene groups, various butylene groups, various pentylene groups, various hexylene groups, various octylidene groups, etc., a part of hydrogen can also be substituted into hydroxyl groups. x is an integer of 1 or more and 18 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, y is 1 or more and 5 or less, preferably 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less. w is an integer of 1 or more and 18 or less, and preferably an integer of 1 or more and 4 or less.

Preferable 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), for example )CH ₂ -O-, -COO-CH ₂ C(CH ₂ CH ₃ )(CH ₂ OH)CH ₂ -O-, etc., but not limited thereto.

Examples of the hydrocarbon group in R ^{1 2} include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group. The above-mentioned alkyl group having 1 or more carbon atoms and 18 or less carbon atoms may be any of linear, branched and cyclic, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl , cyclopentyl, cyclohexyl, adamantyl, isosyl, dicyclopentyl, adamantyl, adamantyl substituted by lower alkyl, etc. The alkenyl group having 2 or more carbon atoms and 18 or less carbon atoms may be linear, branched or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond exists at the terminal of the alkenyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and the like, which may further have a substituent. The number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, It may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less. The above-mentioned alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, and a nitro group. Further, as the substituent of the aromatic ring such as the above-mentioned aryl group or aralkyl group, in addition to the linear and branched alkyl groups having 1 to 4 or less carbon atoms, alkenyl groups, nitro groups and halogens can also be mentioned. atom etc. In addition, the carbon number of the substituent is not included in the above-mentioned preferable carbon number. In the above R ^{1 2} , x1 is the same as the above x, y1 is the same as the above y, and z1 is the same as the above z. As the hydrocarbon group in R ^{1 5} to R ²² , for example, the same ones as the hydrocarbon group in the above-mentioned R ^{1 2} can be mentioned.

Among R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² , the hydrocarbon groups having one or more selected from ether bonds and ester bonds are -R'-O-R'', -R'-(C =O)-O-R'', or -R'-O-(C=O)-R''(R' and R'' are hydrocarbon groups, or have at least one of ether bond and ester bond. A base represented by a hydrocarbon group). One group may have two or more ether bonds and ester bonds. When the hydrocarbon group is monovalent, an alkyl group, an alkenyl group, an aralkyl group, and an aryl group can be cited, and when the hydrocarbon group is divalent, an alkylene group, an alkenylene group, an aryl group, and a combination thereof can be cited base.

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

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

Furthermore, 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 valent base. In the case of having a structure in which a carbon atom is directly bonded to a phosphorus atom, it is unlikely to be hydrolyzed, so it is presumed that a resin layer excellent in alkali resistance can be formed. Among them, R ¹² is preferably a methyl group, an ethyl group, an optionally substituted aryl group or an aralkyl group, from the viewpoints of excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles, A valent group represented by vinyl, allyl, -[CH(R ¹³ )-CH(R ¹⁴ )-O] _x1 -R ¹⁵ , or -[(CH ₂ ) _y1 -O] _z1 -R ¹⁵ , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is -CO-CH= _{CH 2} ^or -CO-C(CH ₃ )=CH ₂ . 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 refer to those in which the cationic moiety contains carbon atoms. Examples of organic cations include ammonium cations such as imidazolium cations, pyridinium cations, amidinium cations, piperidinium cations, pyrrolidinium cations, tetraalkylammonium cations, and trialkylammonium cations, and trialkylpernium cations. Phosphonium cations such as permanium cations, tetraalkylphosphonium cations, etc. Among them, from the viewpoint of dispersibility and alkali developability, protonated nitrogen-containing organic cations are preferred. Among them, when the organic cation has an ethylenically unsaturated double bond, sclerosing property can be imparted, which is preferable in this respect.

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

In the polymer, in the structural unit represented by the general formula (I), two structural units, in which X is a hydrogen atom and a structural unit in which X is an organic cation, can be included. In the case of including the two structural units, there is no particular limitation as long as good dispersibility and dispersion stability are exhibited, and X is the total number of structural units of the structural units represented by the general formula (I). The ratio of the number of structural units of the organic cation is preferably 0 mol % or more and 50 mol % or less.

There is no particular limitation on the synthesis method of the polymer having the structural unit represented by the general formula (I). polymer. The polymer having the structural unit represented by the general formula (I) is preferably a polymer having at least one of an epoxy group and a cyclic ether group in the side chain, and an acidic phosphorus compound. The reaction product, and at least a portion of the acidic phosphorus compound group 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 site. Such a polymer is excellent in dispersibility and storage stability, and from the viewpoint of forming a high-contrast coating film even after long-term storage, it is preferable to have a structure represented by the above-mentioned general formula (I). unit, a graft copolymer with a structural unit represented by the following general formula (II), or a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the following general formula (III) segmented copolymer.

(通式(II)中，L ²¹表示直接鍵或二價連結基，R ²⁵表示氫原子或甲基，Polymer表示具有下述通式(IV)所表示之結構單元之聚合物鏈； 通式(III)中，R ²⁶為氫原子或甲基，R ²⁷為烴基、-[CH(R ²⁸)-CH(R ²⁹)-O] _x2-R ³⁰、-[(CH ₂) _y2-O] _z2-R ³⁰、-[CO-(CH ₂) _y2-O] _z2-R ³⁰、-CO-O-R ^30'或-O-CO-R ^{30 "}所表示之一價基，R ²⁸及R ²⁹分別獨立地為氫原子或甲基，R ³⁰為氫原子、烴基、-CHO、-CH ₂CHO或-CH ₂COOR ³¹所表示之一價基，R ^30'為烴基、-[CH(R ²⁸)-CH(R ²⁹)-O] _x2'-R ³⁰、-[(CH ₂) _y2'-O] _z2'-R ³⁰、-[CO-(CH ₂) _y2'-O] _z2'-R ³⁰所表示之一價基，R ^{30 "}為碳數為1個以上18個以下之烷基，R ³¹為氫原子或碳數為1個以上5個以下之烷基；上述烴基可具有取代基； x2及x2'表示1以上18以下之整數，y2及y2'表示1以上5以下之整數，z2及z2'表示1以上18以下之整數) [Chemical 15]

(In general formula (II), L ²¹ represents a direct bond or a divalent linking group, R ²⁵ represents a hydrogen atom or a methyl group, and Polymer represents a polymer chain having a structural unit represented by the following general formula (IV); General formula In (III), R ²⁶ is a hydrogen atom or a methyl group, and R ²⁷ is a hydrocarbon group, -[CH(R ²⁸ )-CH(R ²⁹ )-O] _x2 -R ³⁰ , -[(CH ₂ ) _y2 -O] A valent group represented by _z2 -R ³⁰ , -[CO-(CH ₂ ) _y2 -O] _z2 -R ³⁰ , -CO-OR ^30' or -O-CO-R ^{30 "} , R ²⁸ and R ²⁹ respectively independently a hydrogen atom or a methyl group, R ³⁰ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or a valent 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 One valent group represented, R ^{30 "} is an alkyl group with more than 1 carbon number but less than 18, R ³¹ is a hydrogen atom or an alkyl group with more than 1 carbon number but less than 5; the above-mentioned hydrocarbon group may have a substituent; x2 and x2' represent integers from 1 to 18, y2 and y2' represent integers from 1 to 5 and below, z2 and z2' represent integers from 1 to 18)

(通式(IV)中，R ³²為氫原子或甲基，R ³³為烴基、-[CH(R ³⁴)-CH(R ³⁵)-O] _x3-R ³⁶、-[(CH ₂) _y3-O] _z3-R ³⁶、-[CO-(CH ₂) _y3-O] _z3-R ³⁶、-CO-O-R ³⁷或-O-CO-R ³⁸所表示之一價基，R ³⁴及R ³⁵分別獨立地為氫原子或甲基，R ³⁶為氫原子、烴基、-CHO、-CH ₂CHO或-CH ₂COOR ³⁹所表示之一價基，R ³⁷為烴基、-[CH(R ³⁴)-CH(R ³⁵)-O] _x4-R ³⁶、-[(CH ₂) _y4-O] _z4-R ³⁶、-[CO-(CH ₂) _y4-O] _z4-R ³⁶所表示之一價基，R ³⁸為碳數為1個以上18個以下之烷基，R ³⁹為氫原子或碳數為1個以上5個以下之烷基，上述烴基可具有取代基； n表示5以上200以下之整數；x3及x4表示1以上18以下之整數，y3及y4表示1以上5以下之整數，z3及z4表示1以上18以下之整數) [Chemical 16]

(In general formula (IV), R ³² is a hydrogen atom or a methyl group, R ³³ is a hydrocarbon group, -[CH(R ³⁴ )-CH(R ³⁵ )-O] _x3 -R ³⁶ , -[(CH ₂ ) _y3 A valent group represented by -O] _z3 - ^R36 , -[CO-( _CH2 ) _y3 -O] _z3 - ^R36 , -CO- ^OR37 or -O-CO- ^R38 , ^R34 and ^R35 each independently a hydrogen atom or a methyl group, R ³⁶ is a hydrogen atom, a hydrocarbon group, a valent 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 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 200 or less x3 and x4 represent integers between 1 and 18, y3 and y4 represent integers between 1 and 5, and z3 and z4 represent integers between 1 and 18)

(Graft Copolymer) As an acidic dispersant, a preferred graft copolymer includes, 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). copolymer. In the above general formula (II), L ²¹ is a direct bond or a divalent linking group. The divalent linking group in L ²¹ is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. As a divalent linking group in ^L21 , the thing similar to the divalent linking group in said ^L11 is mentioned, for example.

In the above general formula (II), Polymer represents a polymer chain having a structural unit represented by the above general formula (IV). In the general formula (IV), the hydrocarbon group in R ³³ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group . As for these, for example, the same thing as the above-mentioned R ¹² can be mentioned.

R ³⁶ is preferably a hydrogen atom, or a valent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO or -CH ₂ COOR ³⁹ , and R ³⁷ is preferably an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ³⁴ )-CH(R ³⁵ )-O] _x4 -R ³⁶ , -[(CH ₂ ) _y4 -O] _z4 -R ³⁶ , a valent group represented by -[CO-(CH ₂ ) _y4 -O] _z4 -R ³⁶ . R ³⁸ is an alkyl group having 1 to 18 carbon atoms, and R ³⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As for the alkyl group, aralkyl group and aryl group having 1 or more and 18 or less carbon atoms in the above R ³⁶ and R ³⁷ , the same ones as those of the above R ¹² can be exemplified. The alkyl group in the above-mentioned R ³⁸ and R ³⁹ is the same as that of the above-mentioned 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. The substituents include, for example, alkenyl groups, nitro groups, halogen atoms such as F, Cl, and Br, in addition to linear, branched, and cyclic alkyl groups having 1 or more carbon atoms and 5 or less carbon atoms. . In addition, the carbon number of the substituent is not included in the above-mentioned preferable carbon number. In the above R ³³ and R ³⁷ , x3 and x4 are the same as the above x, y3 and y4 are the same as the above y, and z3 and z4 are the same as the above z.

Furthermore, the above-mentioned R ³³ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ may be further modified by alkoxy group, hydroxyl group, carboxyl group, amino group, epoxy group within the range that does not hinder the dispersibility of the above-mentioned graft copolymer. , isocyanate group, hydrogen bond forming group and other substituent groups. Moreover, after synthesizing the graft copolymer having these substituents, a polymerizable group may be added by reacting a compound having a functional group reacting with the substituent and a polymerizable group. For example, a graft copolymer having a carboxyl group can be reacted with glycidyl (meth)acrylate, or a graft copolymer having an isocyanate group can be reacted with hydroxyethyl (meth)acrylate to obtain addition polymerizable properties. base.

The polymer chain having the structural unit represented by the general formula (IV) is preferably derived from methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate among the above-mentioned structural units , 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 and the like.

In the embodiment of the present invention, among the above R ³³ and R ³⁷ , those having excellent solubility in organic solvents are preferably used, and may be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when organic solvents such as ether alcohol acetates, ethers, and esters, which are commonly used as organic solvents for colorant dispersions, are used as the organic solvent, methyl and ethyl are preferred. , isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc. Here, the reason why the above-mentioned R ³³ and R ³⁷ are set as such is that the structural unit including the above-mentioned R ³³ and R ³⁷ is soluble in the above-mentioned organic solvent, and the acid phosphorus compound group of the above-mentioned monomer and the site of the salt thereof are relatively soluble in the above-mentioned organic solvent. Particles such as colorants have high adsorption properties, whereby the dispersibility and stability of particles such as colorants can be particularly excellent.

The weight average molecular weight of the polymer chain in the polymer is preferably within the range of 500 or more and 15,000 or less, more preferably within the range of 1,000 or more and 8,000 or less. By being in the said range, the sufficient steric repulsion effect as a dispersing agent can be maintained, and the time required for dispersion|distribution of the particle|grains, such as a colorant, by a steric effect can also be suppressed.

In addition, regarding the polymer chain in the polymer, the standard is preferably that the solubility at 23° C. is 50 (g/100 g solvent) or more with respect to the organic solvent used in combination.

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 one type alone or two or more types may be mixed in the graft copolymer.

The structural unit represented by the general formula (I) is preferably contained in a ratio of 3 mass % or more and 80 mass % or less in total, more preferably 10 mass % or more with respect to all the structural units of the graft copolymer. 70 mass % or less, more preferably 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-mentioned range, the ratio of the affinity sites to the particles in the graft copolymer becomes appropriate, and the organic solvent can be suppressed. As the solubility decreases, the adsorption to particles such as colorants becomes good, and excellent dispersibility and dispersion stability can be obtained. In addition, since the acidic phosphorus compound group of the graft copolymer can be stably localized in the periphery of the colorant, a color filter excellent in heat resistance and contrast can be obtained. On the other hand, the structural unit represented by the general formula (II) is preferably contained in a ratio of 20% by mass to 97% by mass, more preferably 25% by mass, with respect to all the structural units of the graft copolymer. More than 95 mass % or less, more preferably 40 mass % or more and 90 mass % or less. In addition, in this invention, the content ratio of each structural unit in a copolymer is calculated from the addition amount at the time of synthesizing a copolymer.

The weight average molecular weight of the graft copolymer is preferably within a range of 1,000 or more and 500,000 or less, more preferably within a range of 3,000 or more and 400,000 or less, and still more preferably within a range of 5,000 or more and 300,000 or less. By being in the said range, the particle|grains, such as a colorant, can be uniformly dispersed.

The graft copolymer used in the embodiment of the present invention may 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, another structural unit can be introduced by appropriately selecting an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer from which the structural unit represented by the general formula (I) is derived, and copolymerization. And import other structural units.

(block copolymer) The block copolymer that is preferable as an acidic dispersant includes, for example, a block portion containing a structural unit represented by the above general formula (I) and a block containing a structural unit represented by the above general formula (III). part of the block copolymer. In this block copolymer, in the block part containing the structural unit represented by the said general formula (I), it is preferable that the structural unit represented by the said general formula (I) contains 3 or more in total. 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 30 the following. The structural unit represented by the above-mentioned general formula (I) only needs to function as a colorant-affinity site, and may include one kind of structural unit or two or more kinds of structural units. In the case of including two or more structural units, in the block portion including the structural unit represented by the general formula (I), the two or more structural units may be randomly arranged.

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

The above-mentioned block copolymer has a block portion containing the structural unit represented by the above-mentioned general formula (III), thereby making the solvent affinity become good, the dispersibility and dispersion stability of the colorant are good, and the heat resistance is also good, Furthermore, it is excellent in 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 , -[ A valent group represented by CO-(CH ₂ ) _y2 -O] _z2 -R ³⁰ , -CO-OR ^30' or -O-CO-R ^{30 "} . As the hydrocarbon group in R ²⁷ , the same as the above-mentioned R ¹² can be selected. The hydrocarbon groups shown in are the same.

Further, the above R ³⁰ is a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or a valent group represented by -CH ₂ COOR ³¹ , and R ^30' is a hydrocarbon group, -[CH(R ²⁸ )-CH(R ²⁹ ) A valent group represented by -O] _x2' -R ³⁰ , -[(CH ₂ ) _y2' -O] _z2' -R ³⁰ , -[CO-(CH ₂ ) _y2' -O] _z2' -R ³⁰ , 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-mentioned hydrocarbon group may have a substituent. About the above R ³⁰ The hydrocarbon group may be the same as the hydrocarbon group shown in the above R ^12. In the above R ²⁷ and R ^30' , x2 and x2' are the same as the above x, y2 and y2' are the same as the above y, z2 and z2' are the same as the above z is the same.In addition, R ²⁷ in the structural unit represented by the general formula (III) may be the same or different from each other.

Among the above-mentioned R ²⁷ and R ^30' , those having excellent solubility in organic solvents are preferably used, and for example, the same ones as those of the above-mentioned R ³³ and R ³⁷ can be mentioned. In addition, R ²⁷ , R ³⁰ , R ^{30 ′} , R ^{30 "} and R ³¹ in the general formula (IV) can be alkoxy, hydroxyl, carboxyl, Substituents such as amino groups, epoxy groups, isocyanate groups, and hydrogen bond forming groups can be substituted, and the above-mentioned substituents can be added by reacting with a compound having the above-mentioned substituents after synthesizing the above-mentioned block copolymer. In addition, after synthesizing a block copolymer having these substituents, a compound having a functional group reactive with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, a glycidyl group may be added. The block copolymer is reacted with (meth)acrylic acid, or the block copolymer having an isocyanate group is reacted with hydroxyethyl (meth)acrylate to add a polymerizable 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 the solvent-affinity portion and the colorant-affinity portion effectively function to improve the colorant dispersion. From the viewpoint of dispersibility, the number of the structural units 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 unit represented by the general formula (III) is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass, with respect to all the structural units in the above-mentioned block copolymer. More than 90 mass % or less.

The block portion including the structural unit represented by the general formula (III) may be selected so as to function as a solvent affinity portion, and the structural unit represented by the general formula (III) may include one kind of structural unit, or Can contain two or more structural units. In the embodiment of the present invention, when the structural unit represented by the general formula (III) includes two or more kinds of structural units, in the block portion of the structural unit represented by the general formula (III), two or more kinds of structural units are included. The structural units can be arranged randomly.

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 structural unit 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 block portion is preferably in the range of 0.01 or more and 1 or less, and more preferably 0.1 or more and 0.7 or less from the viewpoints of dispersibility and dispersion stability of the colorant within the range.

As the bonding sequence of the above-mentioned block copolymer, as long as it has a block portion containing the structural unit represented by the general formula (I) and a block portion containing the structural unit represented by the general formula (III), the colorant can be What is necessary is to disperse stably, and it is not particularly limited, but from the viewpoint of excellent interaction with the colorant, and from the viewpoint of effectively suppressing the aggregation of dispersants, it is preferable to include the structural unit represented by the general formula (I) above. The block portion is only bonded to one end of the above-mentioned block copolymer.

The weight average molecular weight of the above-mentioned block copolymer is not particularly limited, but from the viewpoint of improving 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, still more preferably It is above 6000 and below 300000.

The acid value of the polymer having the structural unit represented by the general formula (I) is preferably 20 mgKOH/g or more, more preferably 30 mgKOH, from the viewpoints of the dispersibility and storage stability of the colorant. /g or more, more preferably 40 mgKOH/g or more. On the other hand, from the viewpoint of being excellent in 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 further Preferably it is 100 mgKOH/g or less. In the present invention, the acid value refers to the 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.

<Other acidic dispersants> In the color material dispersion liquid of the present invention, other acidic dispersants different from the polymer having the structural unit represented by the general formula (I) may be further contained. As another acidic dispersing agent, the dispersing agent which has an acidic group is mentioned. Here, examples of the acidic group include a carboxyl group, a sulfo group, a phosphoric acid group, and the like, but as an acidic group contained in a dispersant of other acidic dispersants, a carboxyl group is preferred from the viewpoint of excellent dispersibility. .

From the viewpoint of excellent dispersibility, the acid value of other acidic dispersants is preferably in the range of 30 mgKOH/g or more and 250 mgKOH/g or less, preferably 40 mgKOH/g or more, and more preferably 50 mgKOH/g. or more, more preferably 70 mgKOH/g or more. On the other hand, from the viewpoint of suppressing development residues, the acid value of other acidic dispersants is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less, and still more preferably 180 mgKOH/g or less.

In the present invention, as another acidic dispersant, it is preferable to have a carboxyl group from the viewpoint of improving the inhibitory property of developing residues by using in combination with a polymer having a structural unit represented by the above-mentioned general formula (I). The polymer dispersant; among them, by combining with a polymer having a structural unit represented by the above general formula (I), the inhibition of developing residues is improved, and the uniformity of the coating film becomes better. From a viewpoint, a block copolymer comprising the following A block and the following B block is preferable, the A block comprises a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer, and the B block comprises a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer. Structural unit of alkyl (meth)acrylate. Hereinafter, a block copolymer comprising the following A block and the following B block may be abbreviated as a "carboxyl group-containing block copolymer", and the A block comprises a compound derived from a carboxyl group-containing ethylenically unsaturated monomer. Structural units, the B block contains structural units derived from alkyl (meth)acrylates. The carboxyl group-containing block copolymer is suitable, for example, as a dispersant for metallic lake colorants and pigments of dibenzopyran-based dyes.

(block copolymer containing carboxyl group) {A block} In the carboxyl group-containing block copolymer, the A block is a polymer block comprising a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer. As the carboxyl group-containing ethylenically unsaturated monomer used in the A block, for example, the same carboxyl group-containing ethylenically unsaturated monomer as the carboxyl group-containing ethylenically unsaturated monomer used in the copolymer containing a hydroxyalkyl (meth)acrylate unit can be mentioned. By. When two or more structural units are contained in the A block, each structural unit in the A block may be contained in any aspect such as random copolymerization, block copolymerization, etc. Preferably, it is contained in the form of random copolymerization. In the A block, the structural units derived from the carboxyl group-containing ethylenically unsaturated monomer are preferably 40% by mass or more, more preferably 70% by mass or more, and still more preferably only 70% by mass or more relative to all the structural units in the A block A polymer block composed of structural units derived from carboxyl-containing ethylenically unsaturated monomers.

The A block may be composed only of structural units derived from the carboxyl group-containing ethylenically unsaturated monomer, or may also include ethylenic properties derived from and carboxyl group within the range where the acidity of the A block is stronger than that of the B block. Structural units of ethylenically unsaturated monomers different from unsaturated monomers. When the A block contains a structural unit derived from an ethylenically unsaturated monomer different from the carboxyl group-containing ethylenically unsaturated monomer, it is preferable to set it as all the structural units of the A block. 60 mass % or less, and more preferably 30 mass % or less. As an ethylenically unsaturated monomer different from the said carboxyl group-containing ethylenically unsaturated monomer, the structural unit used for the following B block is mentioned.

From the viewpoint of dispersibility and dispersion stability, the content of the A block is preferably 5% by mass or more, more preferably 10% by mass or more, based on all the structural units of the block copolymer, and on the other hand, preferably It is 95 mass % or less, More preferably, it is 40 mass % or less.

{B block} In the carboxyl group-containing block copolymer, the B block is a polymer block containing a structural unit derived from an alkyl (meth)acrylate. As the alkyl (meth)acrylate monomer used in the B block, it can be used with the alkyl (meth)acrylate monomer used in the polymer chain having the structural unit represented by the above general formula (IV). The body is the same, use one kind or a mixture of two or more kinds. In addition to the structural unit derived from the alkyl (meth)acrylate, the structural unit derived from another ethylenically unsaturated monomer may be contained in the B block. As a structural unit derived from another ethylenically unsaturated monomer, the structural unit which differs from the structural unit derived from the alkyl (meth)acrylate among the structural units represented by the said general formula (III) is mentioned.

When two or more structural units are contained in the B block, each structural unit in the B block may be contained in any aspect such as random copolymerization, block copolymerization, etc., and is preferred from the viewpoint of uniformity. It is contained in the form of random copolymerization.

The B block is preferably 10 mass % or less of structural units derived from an ethylenically unsaturated monomer having an acidic group with respect to all the structural units of the B block, more preferably 5 mass % or less, and still more preferably 2 mass % or less. In the present invention, the B block is more preferably a polymer block that does not contain a structural unit derived from an ethylenically unsaturated monomer having an acidic group.

The carboxyl group-containing block copolymer may be an AB block copolymer or a BAB block copolymer. When the block copolymer is a BAB block copolymer, the content ratio of the two B blocks is preferably adjusted to the range of 50:50 to 70:30 in terms of mass ratio from the viewpoint of dispersibility Inside.

From the viewpoint of dispersibility, the acid value of the carboxyl group-containing block copolymer is preferably within a range of not less than 30 mgKOH/g and not more than 250 mgKOH/g, preferably the acid value of the block copolymer. In this way, a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer is included in the A block. The acid value is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The acid value is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

From the viewpoint of dispersibility, the weight average molecular weight of the carboxyl group-containing block copolymer is preferably 5,000 or more and 100,000 or less. The weight average molecular weight of the carboxyl group-containing block copolymer is more preferably 8,000 or more, more preferably 10,000 or more, and on the other hand, 80,000 or less, and still more preferably 70,000 or less.

The molecular weight distribution of the carboxyl group-containing block copolymer is preferably less than 2, more preferably less than 1.5, and further preferably less than 1.3. Furthermore, in the present invention, the molecular weight distribution refers to what is calculated according to "weight average molecular weight (Mw))/(number average molecular weight (Mn)". The larger the molecular weight distribution, the more molecular weight than the designed polymer will be included The smaller or larger the molecular weight, the worse the dispersibility of the colorant, so it is preferable to have a smaller molecular weight distribution.

As the manufacturing method of the said carboxyl group-containing block copolymer, the manufacturing method of the block copolymer known previously can be suitably selected and used. From the viewpoint of easy production of a polymer having a uniform composition, a living polymerization method is preferably used. group transfer polymerization) method), a method using a transition metal catalyst (ATRP (Atom transfer radical polymerization, atom transfer radical polymerization) method), a method using a sulfur-based reversible chain transfer agent (RAFT (Reversible addition-fragmentation chain transfer) , reversible addition and fragmentation chain transfer) method), the method using organic tellurium compounds (TERP (Living radical polymerization, living radical polymerization) method) and other methods.

In the colorant dispersion liquid, the content of the dispersant may be appropriately adjusted, but from the viewpoint of dispersibility and storage stability, it is preferably 5 parts by mass or more and 80 parts by mass relative to 100 parts by mass of the colorant Below, it is more preferable to set it as 20 mass parts or more and 70 mass parts or less.

[other ingredients] In the color material dispersion liquid, as long as the effect of the present invention is not impaired, a dispersing auxiliary resin and other components can be further prepared as necessary. As a dispersion auxiliary resin, an alkali-soluble resin is mentioned, for example. Since the colorant particles are not easily brought into contact with each other due to the steric hindrance of the alkali-soluble resin, the dispersion of the colorant may be stabilized, or the effect of reducing the amount of the dispersant by the dispersion stabilization effect may be obtained. Moreover, as other components, surfactant for improving wettability, silane coupling agent for improving adhesiveness, defoaming agent, anti-cratering agent, decoagulation agent, ultraviolet absorber etc. are mentioned, for example.

[solvent] As the solvent contained in the colorant dispersion liquid, the same solvent as the solvent contained in the photosensitive colored resin composition of the present invention can be used. The amount of the solvent is generally preferably within the range of 55% by mass to 95% by mass, preferably within the range of 65% by mass to 90% by mass, and more preferably within the range of 70% by mass relative to the total amount of the colorant dispersion. Within the range of more than 88% by mass or less. When the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. In addition, when the solvent is too large, the concentration of the colorant decreases, and it may be difficult to achieve the target chromaticity coordinates.

[Manufacturing method of pigment dispersion] The method for producing the color material dispersion liquid is not particularly limited as long as it is a method for obtaining a color material dispersion liquid obtained by dispersing the color material in a solvent with a dispersant. For example, the following production method can be applied, which includes: a step of preparing a colorant; a step of preparing a dispersant; and a step of dispersing the above-mentioned colorant in a solvent in the presence of the above-mentioned dispersant. In the solvent, in the presence of a dispersant, two or more color materials can be co-dispersed, or more than one color material can be dispersed or co-dispersed, and then two or more color material dispersions can be mixed. When dispersing the colorant, a previously known disperser can be used. Specific examples of the dispersing machine 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 type bead mills, and bead mills such as continuous ring bead mills. machine. As a preferable dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03 mm or more and 3.0 mm or less, more preferably 0.05 mm or more and 2.0 mm or less.

III. Cured product of photosensitive colored resin composition Since the photosensitive colored resin composition of this invention contains the monomer which is a photopolymerizable compound as a photocurable component, the hardened|cured material of this invention can be obtained by carrying out photopolymerization reaction of the photosensitive colored resin composition of this invention. For example, after forming a coating film of the photosensitive colored resin composition of the present invention, drying the coating film, exposing the coating film, and developing the coating film as necessary, the cured product of the present invention can be obtained. As the method of forming, exposing, and developing the coating film, for example, the same method as the method used for forming the colored layer included in the color filter of the present invention described below can be adopted. In preferable embodiment of the photosensitive colored resin composition of this invention, binder resin, such as the copolymer containing a hydroxyalkyl (meth)acrylate unit, also has a polymerizable functional group. The hardened product of the photosensitive colored resin composition of the present invention in such a preferred embodiment dissolves or disperses a colorant containing at least one selected from the group consisting of dyes and lake colorants in the following matrix The hardened product is formed by photopolymerization of a binder resin containing a copolymer containing a hydroxyalkyl (meth)acrylate unit, and a monomer. The cured product of the present invention is obtained by dissolving or dispersing a colorant containing at least one selected from the group consisting of dyes and lake colorants in a matrix containing the following binder resin, the binder resin containing ( As a copolymer of hydroxyalkyl meth)acrylate units, the cured product of the present invention has high brightness and excellent flatness, and the generation of development residues is suppressed in the case of development, so it is suitable for use as a color filter. Shading layer.

IV. Color Filters The color filter of the present invention includes at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition of the present invention. At least one of the above-mentioned colored layers of the color filter of the present invention is formed by using a cured product that dissolves or dissolves a colorant including at least one selected from the group consisting of dyes and lake colorants. Dispersed in a matrix containing the following binder resin, the binder resin contains a copolymer containing hydroxyalkyl (meth)acrylate units, so the color filter of the present invention has high brightness and is flat A coloring layer with excellent properties and suppressed development residues.

FIG. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. The color filter 10 of the present invention shown in FIG. 1 includes a transparent substrate 1 , a light shielding portion 2 , and a red coloring layer 3R, a green coloring layer 3G, and a blue coloring layer 3B as the coloring layers 3 . In the color filter of the present invention, the colored layer is usually formed on the opening of the light-shielding portion on the transparent substrate described below, and includes colored patterns of three or more colors. In the example of FIG. 3, the red coloring layer 3R, the green coloring layer 3G, and the blue coloring layer 3B are formed, and are arranged in a predetermined order. The coloring layers of each color are formed in the order of the red coloring layer 3R, the green coloring layer 3G, and the blue coloring layer 3B. The arrangement of the coloring layers is not particularly limited, and for example, a common arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type can be used. In addition, the width, area, etc. of the colored layer can be arbitrarily set. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the colored resin composition, and the like, and is usually preferably in the range of 1 μm or more and 5 μm or less.

The colored layers of the respective colors can be formed by the steps described below. First, using coating methods such as spray coating, dip coating, bar coating, roll coating, spin coating, etc., the photosensitive colored resin composition is coated on a transparent preliminarily formed light-shielding portion. A wet coating film is formed on the substrate. Next, after drying this wet coating film using a hot plate, an oven, etc., it exposes via a photomask of a predetermined pattern, and photopolymerizes a binder resin, a monomer, etc., and sets it as a photosensitive coating film. As a light source used at the time of exposure, an ultraviolet-ray, an electron beam, etc., such as a low-pressure mercury-vapor lamp, a high-pressure mercury-vapor lamp, and a metal halide lamp, are mentioned, for example. The exposure amount is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, heat treatment can also be performed after exposure to promote the polymerization reaction. The heating conditions are appropriately selected according to the mixing ratio of each component in the coloring resin composition used, the thickness of the coating film, and the like.

Next, a development process is performed using a developing solution, and the unexposed part is dissolved and removed, whereby a coating film is formed in a desired pattern. As a developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. In the alkaline solution, an appropriate amount of surfactant and the like may be added. In addition, a general method can be used as a developing method. After the development treatment, usually, washing of the developer solution and drying of the cured coating film of the colored resin composition are performed to form a colored layer. Furthermore, heat treatment may be performed after the development treatment so that the coating film can be sufficiently cured. It does not specifically limit as a heating condition, According to the application of a coating film, it can select suitably.

[shading part] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate, and can be the same as the light-shielding portion in a general color filter. It does not specifically limit as a pattern shape of this light-shielding part, For example, shapes, such as a stripe shape and a matrix shape, are mentioned. The light-shielding portion may be a metal thin film such as chromium formed by sputtering, vacuum deposition, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are methods such as: a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of patterning a photosensitive resist A method of thermal transfer using etchant. The film thickness of the light-shielding portion is set to 0.2 μm or more and about 0.4 μm or less in the case of a metal thin film, and about 0.5 μm or more and 2 μm or less in the case of dispersing or dissolving a black pigment in a binder resin. .

[Transparent substrate] The transparent substrate is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent rigid materials that do not have flexibility, such as quartz glass, alkali-free glass, and synthetic quartz plate, or transparent flexible materials that have flexibility or flexibility, such as transparent resin films, optical resin plates, and flexible glass, can be used. Material. Such transparent substrates for color filters usually have polar groups on the surface. From the viewpoint of improving the substrate adhesion of the photosensitive colored resin composition of the present invention, the transparent substrate is preferably a substrate containing silica such as quartz glass, alkali-free glass, and synthetic quartz plate. The thickness of the transparent substrate is not particularly limited. According to the application of the color filter, for example, a thickness of 50 μm or more and 1 mm or less can be used. Furthermore, the color filter of the present invention may be formed with, for example, an overcoat layer or a transparent electrode layer, an alignment film for aligning the liquid crystal material, or a columnar shape in addition to the above-mentioned transparent substrate, light shielding portion and coloring layer. Spacers etc. The color filter of the present invention is not limited to the above-exemplified structure, and a well-known structure generally used in color filters can be appropriately selected and used.

V. 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, for example, a liquid crystal display device, an organic light-emitting display device, and the like.

[Liquid crystal display device] The liquid crystal display device of the present invention is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device to which the display device of the present invention belongs. As shown in FIG. 2 , the liquid crystal display device 40 of the present invention includes a color filter 10 , a counter substrate 20 including a thin-film transistor (TFT) array substrate, etc., and the color filter 10 formed on the above-mentioned color filter 10 . The liquid crystal layer 30 between the above-mentioned opposite substrate 20 . In addition, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and can be a known structure adopted by a liquid crystal display device using a color filter in general.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be used. Examples of such a driving method include a TN (Twisted Nematic) method, an IPS (In Plane Switching) method, an OCB (Optically Compensated Bend) method, and an MVA (Multi- domain Vertal Alignment, multi-domain vertical alignment) method, etc. In the present invention, any of these can be preferably used. Moreover, as a counter board|substrate, it can select suitably according to the drive method etc. of the liquid crystal display device of this invention, and can be used. As a formation method of a liquid crystal layer, the method generally used as a manufacturing method of a liquid crystal cell can be used, for example, a vacuum injection method, a liquid crystal dropping method, etc. are mentioned.

[Organic Light Emitting Display Device] The organic light-emitting display device of the present invention is characterized by having the above-mentioned color filter of the present invention and an organic light-emitting body. FIG. 3 is a schematic diagram showing an example of an organic light-emitting display device to which the display device of the present invention belongs. As shown in FIG. 3 , the organic light-emitting display device 100 of the present invention includes a color filter 10 and an organic light-emitting body 80 . Between the color filter 10 and the organic light-emitting body 80 , an organic protective layer 50 and an inorganic oxide film 60 may be provided.

As a method for laminating the organic light-emitting body 80, for example, a method such as forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, and an electron injection layer on the upper surface of the color filter in this order 75, and the method of the cathode 76; or the method of attaching the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60. For other structures of the organic light-emitting body 80, such as the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76, known ones are suitably used. The organic light-emitting display device 100 thus obtained can be applied to, for example, both passively driven organic EL displays and actively driven organic EL displays. Furthermore, the organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3 , and can be a well-known structure generally used in organic light emitting display devices using color filters. 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) is determined as a standard polystyrene-equivalent value by GPC (gel permeation chromatography) in accordance with the above-mentioned measuring method of the present invention. An acid value and a hydroxyl value were calculated|required by the method based on JISK0070:1992. The viscosity of the binder resin produced in each production example was obtained by applying the obtained binder resin solution (solid content 40% by mass) under the conditions of a pressure of 20 to 30 hPa and a temperature of 80°C. ) was dried under reduced pressure and concentrated until the solid content concentration reached 60% by mass, then the cyclic heating was performed in a 90° C. hot water bath, and the viscosity was determined using a Brookfield viscometer.

(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 (product 1) represented by the following chemical formula (a) was obtained rate 87%). From the following analysis results, it was confirmed that the obtained compound was the target compound. ・MS(ESI) (m/z): 677(+), bivalent ・Elemental analysis value: CHN measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%, 7.36%, 5.90%)

[Chem. 17] Chemical formula (a)

(2) Synthesis of Lake Color Material 1 2.59 g (0.76 mmol) of dodeca-tungstophosphoric acid-n-hydrate manufactured by Kanto Chemical Co., Ltd. was heated and dissolved in a mixed solution of 40 mL of methanol and 40 mL of water, and the above-mentioned intermediate 11.6 was added. g (1.19 mmol) and stirred for 1 hour. The precipitate was removed by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain a lake color material 1 represented by the following chemical formula (b) (yield 95%). From the following analysis results, it was confirmed that the obtained compound was the target compound.・31P NMR (d-dmso, ppm)δ-15.15 ・MS (MALDI) (m/z): 1355 (M ⁺ ), 2879 (MH ₂ ^- ) ・Elemental analysis value: CHN found (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 18] Chemical formula (b)

(Synthesis Example 2: Synthesis of Dibenzopyran-based Dye 1) To a 500 ml four-necked flask were added 40.2 parts by mass of a sulfofluoran compound represented by the following chemical formula (c), 312 parts by mass of methanol, 6.8 parts by mass of 2,6-xylidine, and N-methyl-o-toluidine 6.0 parts by mass, refluxed for 30 hours. After filtering this reaction liquid at 60 degreeC to remove insoluble components, the solvent was removed under reduced pressure until the reaction liquid reached about 70 ml, and poured into 200 parts by mass of 6% hydrochloric acid. Next, 600 parts by mass of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake was suspended in 100 parts by mass of water, stirred at 60°C for 2 hours, then filtered out again, washed with hot water at 60°C, and dried to obtain 27.4 parts by mass of the following Dibenzopyran-based dye 1 represented by the chemical formula.

[Chem. 19] Chemical formula (c)

[Chem. 20] Dibenzopyran-based dye 1

(Synthesis Example 3: Synthesis of Dibenzopyran-based Dye 2) 18.0 parts by mass of the sulfofluoran compound represented by the above chemical formula (c), 312 parts by mass of methanol, 5.4 parts by mass of 2,6-xylidine, and 4.8 parts by mass of o-toluidine were added to a 500 ml four-necked flask, and refluxed. 30 hours. After filtering this reaction liquid at 60 degreeC to remove insoluble components, the solvent was removed under reduced pressure until the reaction liquid reached about 70 ml, and poured into 200 parts by mass of 6% hydrochloric acid. Next, 600 parts by mass of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake was suspended in 100 parts by mass of water, stirred at 60°C for 2 hours, then filtered out again, washed with hot water at 60°C, and dried to obtain 21.9 parts by mass or less. Intermediate I-1 represented by the chemical formula.

[Chem. 21] Intermediate I-1

Next, a mixture of 20 parts by mass of the intermediate I-1, 135.3 parts by mass of 1-methyl-2-pyrrolidone, 7.8 parts by mass of potassium carbonate, and 16.2 parts by mass of methyl iodide was stirred at 80° C. for 2 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10°C, followed by stirring for 1 hour. Then, the precipitate was collected by filtration, and the residue was dried at 60° C. for 24 hours to obtain 20.4 parts by mass of crystals. 20 parts by mass of the obtained crystals and 106 parts by mass of phosphonium chloride were put into a flask, and stirred at 60° C. for 2 hours. The obtained reaction solution was left to cool to room temperature, and the reaction solution was added dropwise to 1500 parts by mass of ice water, followed by stirring for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried over 10 hours. 7 parts by mass of the crystals and 1.8 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, 1.55 parts by mass of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the obtained reaction solution, washed with water, and then the organic layer was separated. The organic layer was dried and purified with sodium sulfate, and concentrated under reduced pressure to obtain 6.8 parts by mass of dibenzopyran-based dye 2 represented by the following chemical formula (yield: 80%).

[Chem. 22] Dibenzopyran-based dye 2

(Synthesis Example 4: Synthesis of Dibenzopyran-based Metal Lake Color Material 3) 5.0 parts by mass of Acid Red 289 was added to 500 ml of water, and dissolved at 80°C to prepare a dye solution. 3.85 parts by mass of polyaluminum chloride ("trade name: Takibaine #1500" manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5 mass %, 23.5 mass % in terms of alumina amount) was added to water 200 ml was stirred at 80°C to prepare an aqueous polyaluminum chloride solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the above dye solution at 80°C over 15 minutes, and further stirred at 80°C for 1 hour. The resulting precipitate was collected by filtration and washed with water. The obtained filter cake was dried to obtain 6.30 parts by mass of dibenzopyran-based metallic lake coloring material 3 (yield 96.2%) as a metallic lake coloring material for dibenzopyran-based dyes.

(Synthesis Example 5: Synthesis of PB15:6 by Alkaline Treatment) 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added to the reaction container, and after completely dissolving, 24 parts by mass of thionyl chloride was added, the temperature was gradually raised, and the reaction was carried out at 101° C. for 3 hours. The reaction solution was poured into 9000 parts by mass of ice water, and after stirring, filtration and water washing were performed. After slurrying the obtained press cake with 300 parts by mass of water, 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, and the mixture was stirred at 65° C. for 4 hours. Filter, wash with water, and dry to obtain Blue Color Derivative 1 with Basic Sites for Surface Treatment. The obtained blue colorant derivative 1 having a basic moiety was confirmed to be the structure of the following chemical formula (d). ・TOF-MS: 768.35

[Chem. 23] Chemical formula (d)

100 parts by mass of commercially available C.I. Pigment Blue 15:6 (ε-type copper phthalocyanine pigment, FASTOGEN BLUE A510 manufactured by DIC Corporation) and 5 parts by mass of the above-mentioned blue pigment derivative 1 having an alkaline moiety were mixed with a grinder. Parts were dry pulverized at 60°C for 1.5 hours. This pulverized product was further mixed with 5 parts by mass of the above-mentioned blue colorant derivative 1 having an alkaline moiety, thereby obtaining an alkaline-treated PB15:6 which is an alkaline-treated C.I. Pigment Blue 15:6.

(Synthesis example 6: Synthesis of acidic dispersant A1 (polymer having a structural unit represented by the above general formula (I))) (1) Synthesis of giant monomer MM-1 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added to a reactor equipped with a condenser, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and the mixture was heated to the temperature while stirring under a nitrogen stream. 90°C. 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, α, α' were added dropwise over 1.5 hours - A mixed solution of 1.0 mass part of azobisisobutyronitrile (abbreviated as AIBN) was further 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 Co., Ltd.), 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. part, and stirred for 3 hours, thereby obtaining a 49.5% by mass solution of the macromonomer MM-1. As a result of GPC measurement of the obtained macromonomer MM-1, the 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 mass parts of PGMEAs were added to the reactor equipped with the condenser, the funnel for addition, the inlet for nitrogen, the mechanical stirrer, and the digital thermometer, and it heated to the temperature of 90 degreeC, stirring under nitrogen flow. 67.34 parts by mass of the above-mentioned macromonomer MM-1 solution (33.33 parts by mass of solid content), 16.67 parts by mass of glycidyl methacrylate (referred to as GMA), 1.24 parts by mass of n-dodecanethiol, and 25.0 parts by mass of PGMEA were added dropwise over 1.5 hours. The mixed solution of 0.5 parts by mass of AIBN and 0.5 parts by mass of AIBN was heated and stirred for 3 hours, then the mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and then aged at the current temperature for 1 hour to obtain grafts 25.0 mass % solution of copolymer A1. As a result of GPC measurement of the obtained graft copolymer A1, 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) Manufacture of the polymer (acidic dispersant A1) having the structural unit represented by the general formula (I) PGMEA was added to the reactor equipped with a condenser tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer 27.80 parts by mass and 9.27 parts by mass of phenylphosphonic acid (product name "PPA" manufactured by Nissan Chemical Co., Ltd.) were heated to a temperature of 90° C. while stirring under nitrogen flow. 100.0 parts by mass of the above graft copolymer A1 was added dropwise over 30 minutes, heated and stirred for 2 hours, thereby obtaining a polymer (acidic dispersant A1) solution (solid matter) having the structural unit represented by the above general formula (I). ingredient 25.0 mass %). The progress of the esterification reaction of GMA and PPA of the obtained acidic dispersant A1 was confirmed by acid value measurement and ¹ H-NMR measurement (it was confirmed that the peak derived from the epoxy group disappeared). The acid value of the obtained acidic dispersant A1 was 98 mgKOH/g.

(Synthesis Example 7: Acidic dispersant B1 (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) block copolymer) synthesis) With reference to Example 1 described in International Publication No. 2016/132863, the following triblock copolymer was synthesized, the triblock copolymer having 20 parts by mass of methyl methacrylate (MMA), n-butyl methacrylate (BMA) 40 mass parts of blocks, methacrylic acid (MAA) 20 mass parts, BMA 20 mass parts blocks, and MMA 20 mass parts, BMA 40 mass parts blocks. The weight average molecular weight (Mw) of the obtained block copolymer was 11,000, the molecular weight distribution (Mw/Mn) was 1.50, and the acid value was 130 mgKOH/g.

(Synthesis Example 8: Synthesis of Alkali-Soluble Resin A) 150 parts by mass of PGMEA was added to the polymerization tank, and the temperature was raised to 100° C. under a nitrogen atmosphere, and then 22 parts by mass of methacrylic acid (MAA) and 64 parts by mass of cyclohexyl methacrylate (CHMA) were continuously added dropwise over 1.5 hours. , and 6 parts by mass of PERBUTYL O (manufactured by NOF Corporation) as a photoinitiator, and 2 parts by mass of a chain transfer agent (n-dodecanethiol). Then, the reaction was continued while maintaining at 100°C, and 2 hours after the completion of the dropwise addition of the main chain-forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound while blowing in air, and after the temperature was raised to 110° C., 0.8 part by mass of triethylamine was added, and the mixture was carried out at 110° C. for 15 hours. The addition reaction was performed to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 9,000, acid value 90 mgKOH/g, solid content 40 mass %).

(Synthesis Example 9: Synthesis of Lake Color Material 4) (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 1.90 g of MoO ₄ ·2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) was dissolved in 230 g of purified water, and 64.9 g of 85% phosphoric acid was added dropwise to the solution using a dropping funnel while stirring. The obtained solution was heated to reflux for 8 hours. The reaction solution was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added while stirring. After further stirring for 1 hour, the precipitate was separated by filtration. The obtained solid was dried at 90°C, whereby 29.4 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) were obtained. (2) Synthesis of Lake Color Material 4 5.30 g of CI Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into 350 ml of purified water, and stirred and dissolved at 40° C. to prepare BB7 solution. Separately, 10.0 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) prepared in (1) above was dissolved in 40 ml of purified water. The K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution was put into the BB7 solution, and the solution was stirred at 40° C. for 1 hour as it was. Then, the internal temperature was raised to 80° C., and the mixture was further stirred for 1 hour to form a lake. After cooling, it was filtered and washed three times with 300 ml of purified water. The obtained solid was dried at 90°C, thereby obtaining 10.4 g of a black-blue solid with an average primary particle size of 40 nm as a lake color of a triarylmethane-based dye and a polyacid anion lake color. Material 4.

(Production Example 1: Production of Binder Resin 1) 150 parts by mass of PGMEA was added to the polymerization tank, and the temperature was raised to 100° C. under a nitrogen atmosphere, and then 26.9 parts by mass of methacrylic acid (MAA), 38.9 parts by mass of benzyl methacrylate (BzMA), 5 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 1.4 parts by mass of PERBUTYL O (manufactured by NOF Corporation) as a photoinitiator, and 2.5 parts by mass of a chain transfer agent (n-dodecanethiol). Then, the reaction was continued while maintaining at 100°C, and 2 hours after the completion of the dropwise addition of the main chain-forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, while blowing in air, 29.2 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added, and the mixture was carried out at 110°C for 15 hours. The addition reaction was performed to obtain a binder resin 1 solution (weight average molecular weight (Mw) 14,900, acid value 67 mgKOH/g, hydroxyl value 129 mgKOH/g, solid content 40 mass %).

(Production Examples 2 to 9, Comparative Production Examples 1 to 9: Production of Binder Resins 2 to 9 and Comparative Binder Resins C1 to C9) In Production Example 1, the binders of Production Examples 2 to 9 were obtained in the same manner as in Production Example 1, except that the addition amounts of the monomer, photoinitiator and chain transfer agent were changed according to Table 1. The solutions of resins 2 to 9 and the comparative binder resins C1 to C9 solutions of Comparative Production Examples 1 to 9 (each binder resin solution is 40 mass % of solid content).

(Comparative Production Example 10: Production of Comparative Binder Resin C10) 150 parts by mass of PGMEA was added to the polymerization tank, and the temperature was raised to 110° C. under a nitrogen atmosphere, and then 81.5 parts by mass of tert-butylcyclohexyl methacrylate (t-BuCHMA), 15.0 parts by mass of methacrylic acid (MAA), 3.5 parts by mass of 2-hydroxyethyl methacrylate (HEMA) and 3.0 parts by mass of AIBN as a photoinitiator were continuously added dropwise over 1.5 hours, respectively. Then, it stirred for 2 hours while maintaining 110 degreeC, and obtained the comparative binder resin C10 solution (solid content 40 mass %).

[Table 1] Table 1 adhesive resin Monomer (parts by mass) Photoinitiator (parts by mass) Chain transfer agent (parts by mass) Numbering Mw Acid value (mgKOH/q) Hydroxyl value (mgKOH/q) Resin viscosity (mPa・s) HEMA BzMA MAA GMA t-BuCHMA Manufacturing Example 1 1 14900 67 129 1108 5 38.9 26.9 29.2 - 1.4 2.5 Manufacturing example 2 2 17500 67 129 2799 5 38.9 26.9 29.2 - 1.4 2.0 Manufacturing Example 3 3 16200 90 114 3826 5 42.1 26.9 26.0 - 1.4 2.0 Manufacturing Example 4 4 18300 86 135 6935 10 37.1 26.9 26.0 - 1.4 2.0 Manufacturing Example 5 5 11000 71 172 794 15 27.9 26.9 30.2 - 1.4 5.0 Manufacturing Example 6 6 13700 70 172 2641 15 27.9 26.9 30.2 - 1.4 3.8 Manufacturing Example 7 7 11500 73 194 926 20 22.9 26.9 30.2 - 1.4 5.5 Manufacturing Example 8 8 12000 110 87 3954 5 49.8 26.9 18.3 - 1.4 2.4 Production Example 9 9 12000 125 72 5235 5 53.9 26.9 14.2 - 1.4 3.3 Comparative Production Example 1 C1 14800 108 79 4090 - 50.9 26.9 22.2 - 1.4 2.0 Comparative Production Example 2 C2 12700 124 66 7130 - 54.6 26.9 18.5 - 1.4 2.4 Comparative Production Example 3 C3 13700 127 66 8088 - 54.6 26.9 18.5 - 1.4 2.0 Comparative Production Example 4 C4 10800 147 36 7570 - 62.0 28.0 10.0 - 1.4 3.3 Comparative Production Example 5 C5 10700 76 104 324 - 43.9 26.9 29.2 - 1.4 3.6 Comparative Production Example 6 C6 10000 70 129 453 5 38.9 26.9 29.2 - 1.4 3.8 Comparative Production Example 7 C7 8300 65 129 238 5 38.9 26.9 29.2 - 1.4 5.5 Comparative Production Example 8 C8 8800 73 150 275 10 32.9 26.9 30.2 - 1.4 5.5 Comparative Production Example 9 C9 7800 80 166 434 20 34.0 23.6 22.4 - 2.0 6.5 Comparative Production Example 10 C10 10000 100 15 343 3.5 - 15.0 - 81.5 3.0 -

(Preparation Example 1: Preparation of Lake Color Material 1 Dispersion) 110 parts by mass of the lake color material of Synthesis Example 1, 20 parts by mass of the acidic dispersant A1 solution of Synthesis Example 6 (5.0 parts by mass of effective solid content), and 7.5 parts by mass of the solution of alkali-soluble resin A of Synthesis Example 8 (effective solid content) 3.0 parts by mass of the chemical composition) and 62.5 parts by mass of PGMEA were mixed, and pre-dispersed with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works) for 1 hour, and further, 0.1 mm zirconia beads were used for 4 hours of pre-dispersion. The dispersion liquid of Lake Color Material 1 was obtained by dispersion.

(Preparation Example 2: Preparation of Dibenzopyran-based Metal Lake Color Material 3 Dispersion) 10 parts by mass of dibenzopyran-based metal lake colorant 3 of Synthesis Example 4, 16.7 parts by mass of the acidic dispersant B1 solution of Synthesis Example 7 (5.0 parts by mass of effective solid content), and alkali-soluble resin of Synthesis Example 8 7.5 parts by mass of solution A (3.0 parts by mass of effective solid content) and 65.8 parts by mass of PGMEA were mixed, and pre-dispersed with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works) for 1 hour, and further 0.1 The mm zirconia beads were formally dispersed for 4 hours to obtain the dibenzopyran-based metal lake color material 3 dispersion liquid.

(Preparation Example 3: Preparation of Dibenzopyran-based Dye 1 Solution) 5.0 parts by mass of dibenzopyran-based dye 1 of Synthesis Example 2 was dissolved in 45 parts by mass of diacetone alcohol to obtain a solution of dibenzopyran-based dye 1.

(Preparation Example 4: Preparation of Dibenzopyran-based Dye 2 Solution) 5.0 parts by mass of dibenzopyran-based dye 2 of Synthesis Example 3 was dissolved in 45 parts by mass of diacetone alcohol to obtain a dibenzopyran-based dye 2 solution.

(Preparation Example 5: Preparation of PB15:6 Dispersion) Alkaline treatment PB15 of Synthesis Example 5: 6 10 parts by mass, 16.7 parts by mass of the acidic dispersant B1 solution of Synthesis Example 7 (5.0 parts by mass of effective solid content), and 7.5 parts by mass of the alkali-soluble resin A solution of Synthesis Example 8 ( Effective solid content 3.0 parts by mass) and 65.8 parts by mass of PGMEA were mixed, and pre-dispersed for 1 hour with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works), and further for 6 hours with 0.1 mm zirconia beads. PB15:6 dispersion liquid was obtained by the main dispersion in 15 hours.

(Preparation Example 6: Preparation of PV23 Dispersion) Into a 30 ml mayonnaise bottle were placed 10 parts by weight of commercially available C.I. Pigment Violet 23 (PV23), 16.7 parts by mass of the acid dispersant B1 solution of Synthesis Example 7 (5.0 parts by mass of effective solid content), and the alkali of Synthesis Example 8 7.5 parts by mass of soluble resin A solution (3.0 parts by mass of effective solid content), 65.8 parts by weight of PGMEA, and 30 parts by weight of zirconia beads with a diameter of 2 mm were preliminarily prepared in a paint shaker (manufactured by Asada Steel Co., Ltd.) for 1 hour. After crushing, the mixture was transferred to another 30 ml mayonnaise bottle, 30 parts by weight of zirconia beads with a diameter of 0.1 mm were added, and the mixture was shaken in a paint shaker for 5 hours to obtain a PV23 dispersion.

(Preparation Example 7: Preparation of Lake Color Material 4 Dispersion) In Preparation Example 1, 10 parts by mass of the lake color material 4 of Synthesis Example 6 was used instead of 10 parts by mass of the lake color material 1 of Synthesis Example 1 as the color material. A dispersion of Lake Color 4 was prepared.

系光起始劑，2,4-二乙基9-氧硫𠮿

)0.39質量份、作為抗氧化劑之IRGANOX1010(BASF公司製造)0.78質量份、PGMEA 44.1質量份而獲得感光性黏合劑成分1。 (Preparation Example I: Preparation of Photosensitive Adhesive Component 1) Dipentaerythritol hexaacrylate ( DPHA) (ARONIX M402 (manufactured by Toagosei Co., Ltd.)) 24.7 parts by mass, Irgacure 907 (manufactured by BASF, α-amino ketone-based photoinitiator) as a photoinitiator 3.53 mass parts, kayacure DETX-S (Japan Manufactured by the chemical company, 9-oxysulfur 𠮿

It is a photoinitiator, 2,4-diethyl 9-oxothiol

) 0.39 parts by mass, 0.78 parts by mass of IRGANOX1010 (manufactured by BASF Corporation) as antioxidants, and 44.1 parts by mass of PGMEA to obtain photosensitive adhesive component 1.

(Preparation Examples II to IX, Comparative Preparation Examples I to X: Preparation of Photosensitive Adhesive Components 2 to 9 and Comparative Photosensitive Adhesive Components 1 to 10) In the preparation of the photosensitive adhesive component 1 of the preparation example I, in the preparation examples II to IX, the solutions of the binder resins 2 to 9 of the preparation examples 2 to 9 were used to replace the solution of the binder resin 1 of the preparation example 1. In Examples I to X, the solutions of the comparative binder resins C1 to C10 of the comparative production examples C1 to C10 were used instead of the solution of the binder resin 1 of the production example 1. Photosensitive adhesive components 2 to 9 were obtained in ~IX, and comparative photosensitive adhesive components C1 to C10 were obtained in Comparative Preparation Examples I to X.

(Example 1) 23.2 parts by mass of dispersion liquid of Lake Colorant 1 of Preparation Example 1, 32.1 parts by mass of photosensitive adhesive component 1 of Preparation Example 1, 0.03 parts by mass of surfactant MEGAFAC R08MH (manufactured by DIC Corporation), and 44.7 parts by mass of PGMEA were mixed And the photosensitive colored resin composition of Example 1 was obtained.

(Examples 2 to 9, Comparative Examples 1 to 10) In the preparation of the photosensitive colored resin composition of Example 1, in Examples 2 to 9, the photosensitive adhesive components 2 to 9 were used instead of the photosensitive adhesive component 1, and in Comparative Examples 1 to 10, the comparative photosensitivity was used. The photosensitive colored resin compositions of Examples 2 to 9 and Comparative Examples 1 to 10 were obtained in the same manner as in Example 1, except that the adhesive components C1 to C10 were used instead of the photosensitive adhesive component 1.

(Comparative Examples 11 to 12) In the preparation of the photosensitive colored resin composition of Example 1, PB15:6 dispersion liquid 25.5 was used so that the mass ratio of alkali-treated PB15:6 and PV23 (alkaline-treated PB15:6:PV23) became 86.4:13.6 parts by mass, and 4.0 parts by mass of PV23 dispersion liquid instead of 23.2 parts by mass of dispersion liquid of lake colorant 1, and in Comparative Example 11, 29.2 parts by mass of photosensitive adhesive component 2 were used instead of 32.1 parts by mass of photosensitive adhesive component 1, and In Comparative Example 12, 29.2 parts by mass of the comparative photosensitive binder component C5 was used instead of 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 41.3 parts by mass. In the same manner as in Example 1, the photosensitive colored resin compositions of Comparative Examples 11 to 12 were obtained.

(Example 10, Comparative Examples 13 to 15) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake color material 1 and the dibenzopyran-based metal lake color material 3 (lake color material 1: dibenzopyran-based Metal lake color material 3) 17.6 parts by mass of dispersion liquid of lake color material 1 and 1.32 parts by mass of dispersion liquid of dibenzopyran-based metal lake color material 3 are used in place of lake color material 1 so as to be 93.0:7.0 In addition, in Example 10, 34.0 parts by mass of the photosensitive adhesive component 2 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 34.0 parts by mass of the comparative photosensitive adhesive component C1 was used in Comparative Example 13 instead of the photosensitive adhesive component. 1 32.1 parts by mass of the photosensitive adhesive component, in Comparative Example 14, 34.0 parts by mass of the comparative photosensitive adhesive component C4 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 34.0 parts by mass of the comparative photosensitive adhesive component C6 was used in the comparative example 15 Example 10 and Comparative Example were obtained in the same manner as in Example 1, except that parts by mass were replaced by 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 47.1 parts by mass The photosensitive coloring resin composition of 13-15.

(Example 11, Comparative Examples 16 to 18) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake colorant 1 and the dibenzopyran-based dye 1 (lake colorant 1: dibenzopyran-based dye 1) became 94.2: 17.3 parts by mass of lake color material 1 dispersion liquid and 1.06 mass parts of dibenzopyran-based dye 1 solution were used instead of 23.2 mass parts of lake color material 1 dispersion liquid in Example 11. In Comparative Example 16, 34.4 parts by mass of Comparative Photosensitive Adhesive Component C1 was used instead of 32.1 parts by mass of Photosensitive Adhesive Component 1. In Comparative Example 17 In Comparative Example 18, 34.4 parts by mass of comparative photosensitive adhesive component C4 was used instead of 32.1 parts by mass of photosensitive adhesive component 1, and 34.4 parts by mass of comparative photosensitive adhesive component C6 was used in place of 32.1 parts by mass of photosensitive adhesive component 1, And except having changed the addition amount of PGMEA from 44.7 mass parts to 47.2 mass parts, it carried out similarly to Example 1, and obtained the photosensitive colored resin composition of Example 11 and Comparative Examples 16-18.

(Example 12, Comparative Examples 19 to 21) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake colorant 1 and the dibenzopyran-based dye 2 (lake colorant 1: dibenzopyran-based dye 2) became 94.2: 17.3 parts by mass of Lake Colorant 1 Dispersion Liquid and 1.06 parts by mass of Dibenzopyran-based Dye 2 Solution in place of 23.2 parts by mass of Lake Colorant 1 Dispersion Liquid in Example 12 34.4 parts by mass of photosensitive adhesive component 2 instead of 32.1 parts by mass of photosensitive adhesive component 1, in Comparative Example 19, 34.4 parts by mass of comparative photosensitive adhesive component C1 was used instead of 32.1 parts by mass of photosensitive adhesive component 1, in Comparative Example 20 In Comparative Example 21, 34.4 parts by mass of the comparative photosensitive adhesive component C4 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 34.4 parts by mass of the comparative photosensitive adhesive component C6 was used in place of 32.1 parts by mass of the photosensitive adhesive component 1, And except having changed the addition amount of PGMEA from 44.7 mass parts to 47.2 mass parts, it carried out similarly to Example 1, and obtained the photosensitive colored resin composition of Example 12 and Comparative Examples 19-21.

(Comparative Examples 22 to 23) In the preparation of the photosensitive colored resin composition of Example 1, PB15:6 dispersion liquid 17.4 was used so that the mass ratio of alkali-treated PB15:6 and PV23 (alkaline-treated PB15:6:PV23) became 76.5:23.5 Parts by mass, and 5.35 parts by mass of PV23 dispersion liquid instead of 23.2 parts by mass of dispersion liquid of Lake Colorant 1, and in Comparative Example 22, 32.2 parts by mass of photosensitive adhesive component 2 were used instead of 32.1 parts by mass of photosensitive adhesive component 1, and In Comparative Example 23, 32.2 parts by mass of the comparative photosensitive adhesive component C5 was used in place of 32.1 parts by mass of the photosensitive adhesive component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 44.9 parts by mass. In the same manner as in Example 1, the photosensitive colored resin compositions of Comparative Examples 22 to 23 were obtained.

(Example 13, Comparative Examples 24 to 26) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake colorant 1 and the alkaline treatment PB15:6 (the lake colorant 1: the alkaline treatment PB15:6) was 59.6:40.4. Instead of 23.2 parts by mass of dispersion liquid of lake color material 1, 18.3 parts by mass of dispersion liquid of lake color material 1 and 12.4 parts by mass of dispersion liquid of PB15:6 were used, and 28.7 parts by mass of photosensitive adhesive component 2 were used in Example 13. In place of 1 32.1 parts by mass of the photosensitive binder component, in Comparative Example 24, 28.7 parts by mass of the comparative photosensitive binder component C1 was used in place of 32.1 parts by mass of the photosensitive binder component 1, and in the comparative example 25, the comparative photosensitive binder component was used 28.7 parts by mass of C4 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 28.7 parts by mass of the comparative photosensitive adhesive component C6 was used in Comparative Example 26 instead of 32.1 parts by mass of the photosensitive adhesive component 1, and the addition amount of PGMEA was adjusted from 44.7 Except having changed the mass part to 40.6 mass parts, it carried out similarly to Example 1, and obtained the photosensitive colored resin composition of Example 13 and Comparative Examples 24-26.

(Comparative Examples 27 to 28) In the preparation of the photosensitive colored resin composition of Example 1, PB15:6 dispersion liquid 34.8 was used so that the mass ratio of alkali-treated PB15:6 and PV23 (alkaline-treated PB15:6:PV23) became 92.5:7.5 Parts by mass, and 2.82 parts by mass of PV23 dispersion liquid instead of 23.2 parts by mass of dispersion liquid of Lake Colorant 1, and in Comparative Example 27, 25.6 parts by mass of photosensitive adhesive component 2 were used instead of 32.1 parts by mass of photosensitive adhesive component 1, and In Comparative Example 28, 25.6 parts by mass of the comparative photosensitive binder component C5 was used instead of 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 36.8 parts by mass. In the same manner as in Example 1, the photosensitive colored resin compositions of Comparative Examples 27 to 28 were obtained.

(Examples 1-2 to 9-2, Comparative Examples 1-2 to 10-2) In the preparation of the photosensitive colored resin compositions of Examples 1 to 9 and Comparative Examples 1 to 10, the dispersion liquid of Lake Color Material 4 of Preparation Example 7 was used instead of the dispersion liquid of Lake Color Material 1 of Preparation Example 1, except that Other than that, the photosensitive colored resin compositions of Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 were obtained in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 10.

[Evaluation method] <Shape of colored layer> The photosensitive colored resin composition of Example 1 was coated on a glass substrate with a thickness of 0.7 mm (NH TECHNO GLASS Co., Ltd. product, "NA35") was applied, followed by heating and drying at 80° C. for 3 minutes using a hot plate. Then, using an ultra-high pressure mercury lamp to irradiate ultraviolet rays of 60 mJ/cm ² through a photomask for forming a line & space of 60 μm, and using a 0.05 mass % potassium hydroxide aqueous solution as an alkaline developer, 60 seconds spray development. Then, post-baking was performed in a clean oven at 230° C. for 30 minutes, thereby producing a pattern-forming substrate in which a coloring layer was formed on a glass substrate with a line and space pattern of 60 μm. The photosensitive colored resin composition of each Example and each Comparative Example was coated on the pattern-forming substrate prepared as described above using a spin coater so that the film thickness after post-baking was 2.5 μm, and then used. The hot plate was heated and dried at 90°C for 3 minutes. Then, after irradiating ultraviolet rays of 60 mJ/cm ² with an ultra-high pressure mercury lamp without the use of a light shield, post-baking was performed in a clean oven at 230° C. for 30 minutes, thereby forming patterns of 60 μm between the examples as the examples. Or the colored layer of the cured film of the photosensitive colored resin composition of each comparative example. After the colored layer was formed, the pattern profile was measured using a film thickness meter of a stylus profiler "P-17" manufactured by KLA-Tencor Corporation. Using the center of the base pattern as a reference, the difference in film thickness between a portion 15 μm from the center and the center portion was obtained, and the evaluation was performed according to the following evaluation criteria. (Criteria for evaluating the shape of the colored layer) A: The difference in film thickness is less than 0.05 μm B: The difference in film thickness is 0.05 μm or more and less than 0.1 μm C: The difference in film thickness is 0.1 μm or more

<Development Residue Evaluation> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater, respectively, and then coated on a 60-degree heating plate. It was dried at ℃ for 3 minutes, thereby forming a coloring layer with a thickness of 2.5 μm. About the glass plate in which the said coloring layer was formed, using 0.05 mass % potassium hydroxide aqueous solution as an alkaline developing solution, the shower image development was performed for 60 seconds. After the formation of the above-mentioned colored layer after the development was visually observed, it was sufficiently wiped with a lens-wiping cloth containing ethanol (manufactured by TORAY, trade name Toraysee MK Clean Cloth), and the degree of coloration of the lens-wiping cloth was visually observed, and the following evaluation was performed. benchmark for evaluation. (Development Residue Evaluation Criteria) A: No development residue was visually confirmed, and the lens cloth was not colored at all. B: The development residue was not confirmed visually, and the lens wiping cloth was confirmed to be slightly colored. C: A little development residue was observed visually, and the coloring of the lens wiping cloth was confirmed. D: Development residue was observed visually, and coloring of the lens wiping cloth was confirmed.

<Brightness> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on a glass substrate with a thickness of 0.7 mm (NH TECHNO GLASS (NH TECHNO GLASS (NH TECHNO GLASS (NH TECHNO GLASS) stock), "NA35"). Then, it was heated and dried on a heating plate at 80°C for 3 minutes, and an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 60 mJ/cm ² without a light shield, and then baked in a clean oven at 230°C for 30 minutes. This obtains a cured film (colored film). The luminance (Y) of the obtained colored substrate was measured using "microspectroscopy apparatus OSP-SP200" manufactured by Olympus, and evaluated according to the following evaluation criteria. (Brightness evaluation) A: Brightness (Y) is 13.0 or more B: Brightness (Y) is 12.0 or more and less than 13.0 C: Brightness (Y) is less than 12.0

<Heat resistance> After obtaining a cured film (colored film) by the same method as the evaluation of the above-mentioned brightness, the obtained colored film was further baked in a clean oven at 240° C. for 25 minutes, and the coloring film was measured. Chromaticity (L ₀ , a ₀ , b ₀ ), then post-baking in a clean oven at 240° C. for 50 minutes, and measuring the chromaticity (L ₁ , a ₁ , b ₁ ) of the obtained colored film again . The chromaticity change of the coloring film in the period from 25 minutes to 75 minutes at 240°C was evaluated by the following formula. ΔEab={(L ₁ −L ₀ ) ² +(a ₁ −a ₀ ) ² +(b ₁ −b ₀ ) ² } ^1/2 The smaller the value of ΔEab, the better the heat resistance is evaluated. If ΔEab is less than 3.0, it is judged that there is no problem in practice. (Heat resistance evaluation criteria) A: ΔEab is less than 2.0 B: ΔEab is 2.0 or more and less than 3.0 C: ΔEab is 3.0 or more

In the following Tables 2 to 5, metal lake color material 3 means dibenzopyran-based metal lake color material 3 obtained in Synthesis Example 4, and PB15:6 means the base obtained in Synthesis Example 5 Sexual treatment PB15:6, PV23 means commercially available C.I. Pigment Violet 23. In addition, A1 of the dispersant means the acidic dispersant A1 obtained in Synthesis Example 6, and B1 of the dispersant means the acidic dispersant B1 obtained in Synthesis Example 7.

[Table 2] Table 2 Photosensitive adhesive ingredients Pigment dispersion ① Pigment dispersion ② Pigment mass ratio (pigment ①/pigment ②) PGMEA Evaluation results adhesive resin parts by mass Pigment Dispersant parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape development residue brightness Heat-resistant color difference ΔEab Example 1 1 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 B A A A Example 2 2 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 3 3 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 4 4 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 5 5 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 B A A A Example 6 6 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 7 7 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 B A A A Example 8 8 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 9 9 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Comparative Example 1 C1 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A B A B Comparative Example 2 C2 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A B A B Comparative Example 3 C3 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A B A B Comparative Example 4 C4 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A C A B Comparative Example 5 C5 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 6 C6 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 7 C7 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 8 C8 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 9 C9 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 10 C10 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 11 2 29.2 PB15: 6 B1 25.5 PV23 B1 4.0 86.4/13.6 41.3 A A C A Comparative Example 12 C5 29.2 PB15: 6 B1 25.5 PV23 B1 4.0 86.4/13.6 41.3 A A C A

[table 3] table 3 Photosensitive adhesive ingredients Pigment dispersion ① Pigment dispersion ② Pigment mass ratio (pigment ①/pigment ②) PGMEA Evaluation adhesive resin parts by mass Pigment Dispersant parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape Development residue brightness Example 10 2 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 A A A Comparative Example 13 C1 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 A B A Comparative Example 14 C4 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 A C A Comparative Example 15 C6 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 C A A Example 11 2 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 A A A Comparative Example 16 C1 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 A B A Comparative Example 17 C4 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 A C A Comparative Example 18 C6 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 C A A Example 12 2 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 A A A Comparative Example 19 C1 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 A B A Comparative Example 20 C4 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 A C A Comparative Example 21 C6 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 C A A Comparative Example 22 2 32.2 PB15: 6 B1 17.4 PV23 B1 5.35 76.5/23.5 44.9 A A C Comparative Example 23 C5 32.2 PB15: 6 B1 17.4 PV23 B1 5.35 76.5/23.5 44.9 A A C

[Table 4] Table 4 Photosensitive adhesive ingredients Pigment dispersion ① Pigment dispersion ② Pigment mass ratio (pigment ①/pigment ②) PGMEA Evaluation adhesive resin parts by mass Pigment Dispersant parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape Development residue brightness Example 13 2 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 A A A Comparative Example 24 C1 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 A B A Comparative Example 25 C4 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 A C A Comparative Example 26 C6 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 C A A Comparative Example 27 2 25.6 PB15: 6 B1 34.8 PV23 B1 2.82 92.5/7.5 36.8 A A C Comparative Example 28 C5 25.6 PB15: 6 B1 34.8 PV23 B1 2.82 92.5/7.5 36.8 A A C

[table 5] table 5 Photosensitive adhesive ingredients Pigment dispersion PGMEA Evaluation results adhesive resin parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape Development residue brightness Heat-resistant color difference ΔEab Example 1-2 1 32.1 Lake Color 4 A1 23.2 44.7 B A B B Example 2-2 2 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 3-2 3 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 4-2 4 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 5-2 5 32.1 Lake Color 4 A1 23.2 44.7 B A B B Example 6-2 6 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 7-2 7 32.1 Lake Color 4 A1 23.2 44.7 B A B B Example 8-2 8 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 9-2 9 32.1 Lake Color 4 A1 23.2 44.7 A A B B Comparative Example 1-2 C1 32.1 Lake Color 4 A1 23.2 44.7 A B B C Comparative Example 2-2 C2 32.1 Lake Color 4 A1 23.2 44.7 A B B C Comparative Example 3-2 C3 32.1 Lake Color 4 A1 23.2 44.7 A B B C Comparative Example 4-2 C4 32.1 Lake Color 4 A1 23.2 44.7 A C B C Comparative Example 5-2 C5 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 6-2 C6 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 7-2 C7 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 8-2 C8 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 9-2 C9 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 10-2 C10 32.1 Lake Color 4 A1 23.2 44.7 C A B C

[Results Summary] The results in Tables 2 to 5 show that the colored layers formed using the photosensitive colored resin compositions of Examples 1 to 13 and Examples 1-2 to 9-2 have high brightness and are excellent in flatness. , the generation of development residues is suppressed, and the photosensitive coloring resin compositions of Examples 1 to 13 and Examples 1-2 to 9-2 in combination contain: at least one selected from the group consisting of dyes and lake colorants A colorant, and a binder resin comprising the following copolymer (copolymer containing hydroxyalkyl (meth)acrylate units), the copolymer having 5 to 25% by mass represented by the general formula (A) The polymer structure derived from the structural unit of hydroxyalkyl (meth)acrylate, the weight average molecular weight is 11000 or more, and the acid value is 60-130 mgKOH/g. Furthermore, according to the comparison of Examples 1 to 9 and Comparative Examples 1 to 10 shown in Table 2, and the comparison of Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 shown in Table 5 The comparison shows that in the photosensitive colored resin containing the lake color material represented by the above general formula (1), namely the lake color material 1, or the lake color material represented by the above general formula (2), namely the lake color material 4 In the composition, when a copolymer containing a hydroxyalkyl (meth)acrylate unit is used as the binder resin, the heat resistance is improved.

On the other hand, in Comparative Examples 1 to 4, 13 to 14, 16 to 17, 19 to 20, 24 to 25, and 1-2 to 4-2, those containing no hydroxyalkyl (meth)acrylate units were used In comparison with any one of the binder resins C1 to C4, the effect of suppressing the development residue is not good. Among them, Comparative Examples 4, 14, 17, 20, and 25 of Comparative Examples 4, 14, 17, 20, and 25 of Comparative Binder Resin C4 that did not contain hydroxyalkyl (meth)acrylate units, had a weight-average molecular weight of less than 11,000, and had an acid value of more than 130 mgKOH/g were used. And 4-2, the inhibitory effect of the development residue is particularly poor. Furthermore, in Comparative Examples 1 to 4, 13 to 14, 16 to 17, 19 to 20, 24 to 25, and 1-2 to 4-2, although the copolymers used as binder resins did not contain (methyl) Although the hydroxyalkyl acrylate unit is excellent in the flatness of the colored layer, the reason is considered that the acid value of the copolymer is relatively high, ranging from 108 to 147 mgKOH/g. On the other hand, in the photosensitive colored resin composition of the present invention, the copolymer containing a hydroxyalkyl (meth)acrylate unit used as a binder resin contains a hydroxyalkyl (meth)acrylate in the above-mentioned specific amount Therefore, if the acid value is in the range of 60 to 130 mgKOH/g, even if the acid value is relatively high, the generation of development residues can be suppressed. For example, in Examples 8 and 9, although the acid values of the binder resins 8 and 9 used were as high as those of Comparative Examples 1 to 3, the generation of development residues was suppressed. In the photosensitive colored resin composition of the present invention, the copolymer containing a hydroxyalkyl (meth)acrylate unit used as a binder resin contains a hydroxyalkyl (meth)acrylate unit in the above-mentioned specific amount, whereby In the resin composition, the components with low developability other than the binder resin interact with the hydroxyalkyl (meth)acrylate unit and develop together with the components with low developability, so it is considered that the generation of residues can be suppressed. . In the case where the binder resin does not contain enough hydroxyalkyl (meth)acrylate units and has a high acid value, the developability of the binder resin as a single component will become too high, and the discard developability will be low Therefore, it is considered that residues are likely to be generated. In the comparative examples using the comparative binder resins C1 to C3, there is no hydroxyalkyl (meth)acrylate unit, so the generation of the development residue is easily affected by the acid value, so it is considered that the acid value is 108 mgKOH/g or more. developed residues.

In Comparative Examples 5 and 5-2, the comparative adhesive resin C5 which does not contain a hydroxyalkyl (meth)acrylate unit and has a weight average molecular weight of less than 11,000 was used. , 26, and 6-2 to 10-2 used comparative binder resins C6 to C10 with a weight average molecular weight of less than 11,000, so they were inferior in the flatness of the colored layer, respectively. In Comparative Examples 11 to 12, 22 to 23, and 27 to 28, only the pigment was used as the colorant, so the brightness of the colored layer was poor. In addition, in Comparative Examples 12, 23 and 28, although the same comparative adhesive resin C5 as that of Comparative Example 5 was used, the flatness of the colored layer was excellent. From this, it is clear that when a pigment is used as a colorant, the problem that the flatness of the colored layer is not easily damaged.

1: Substrate 2: Shading part 3: Coloring layer 3B: blue tinting layer 3B': blue coating 3G: Green Shading Layer 3R: red tinting layer 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: Light-emitting layer 75: Electron injection layer 76: Cathode 80: organic light emitters 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. 4(a), 4(b), and 4(c) are schematic diagrams showing an example of a conventional method of forming a colored layer of a color filter using a photosensitive colored resin composition containing a pigment. 5(a), 5(b), and 5(c) show an example of a conventional method of forming a coloring layer of a color filter using a photosensitive coloring resin composition containing a dye or lake coloring material. Sketch map.

Claims (9)

A photosensitive colored resin composition for a color filter, which contains a colorant, a binder resin, a monomer, a photoinitiator, and a solvent, and the colorant comprises a group selected from the group consisting of dyes and lake colorants At least one of the above-mentioned binder resins includes a copolymer containing 5 to 25% by mass of a structural unit derived from a hydroxyalkyl (meth)acrylate represented by the following general formula (A) It has a high molecular structure with a weight average molecular weight of 11,000 or more, an acid value of 60 to 130 mgKOH/g, and the general formula (A)

(In the general formula (A), ^RA represents a methyl group or a hydrogen atom, and ^RB represents an alkylene group having 1 to 4 carbon atoms). The photosensitive colored resin composition for color filters according to claim 1, wherein the colorant comprises a lake colorant. The photosensitive colored resin composition for color filters according to claim 1 or 2, wherein the colorant comprises a lake colorant represented by the following general formula (1) or general formula (2), Formula 1)

(In the general formula (1), A is an a-valent organic group that does not have a π bond to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N , or an aromatic group having the aliphatic hydrocarbon group, which may contain heteroatoms in the carbon chain; B ^c- represents a c-valent polyacid anion; R ⁱ to R ^v independently represent a hydrogen atom, 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 can be bonded to form a ring structure; R ^vi and R ^vii independently represent an alkyl group that may have a substituent group, and a group that may have a substituent group. An alkoxy group, a halogen atom or a cyano group; Ar ¹ represents a divalent aromatic group which may have a substituent; R ⁱ to R ^vii and Ar ¹ present in plural may be the same or different respectively; a and c represent 2 or more b and d represent integers greater than or equal to 1; e is 0 or 1, and no bond exists when e is 0; f and g represent integers greater than 0 and less than 4, and f+e and g+e are greater than or equal to 0 and less than 4; e, f and g 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, R ^I and R ^II , R ^III and R ^IV , R ^V It can be bonded with 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 a substituent which may have a substituent The divalent aromatic heterocyclic group, there are plural R ^I to R ^VIII and Ar ² which may be the same or different; E ^m- represents an m-valent polyacid anion; m represents an integer of 2 or more; j is 0 or 1. When j is 0, there is no bond; k and l represent integers between 0 and 4, and k+j and l+j are 0 or more and 4 or less; there are plural j, k and l which may be the same or different respectively). The photosensitive colored resin composition for a color filter according to claim 3, wherein the colorant further comprises a color selected from the group consisting of dibenzopyran-based dyes, and a color represented by the general formula (1) or the general formula (2). At least one of the lake color material of dibenzopyran-based dyes with different lake color materials and the group consisting of C.I. Pigment Blue 15:6. The photosensitive colored resin composition for color filters according to claim 4, wherein the dibenzopyran-based dye is a dibenzopyran-based dye represented by the following general formula (3) or general formula (4) , the lake color material of the above-mentioned dibenzopyran series dye is the metal lake color material of the dibenzopyran series dye represented by the following general formula (5), [Chem. 4] general formula (3)

(In the general formula (3), R ¹ and R ² are each independently an alkyl group or an aryl group, and R ³ and R ⁴ are each independently an aryl group or a heteroaryl group) [Chem. 5] General formula (4)

(In the general formula (4), R ⁵ and R ⁶ are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent, and R ⁷ and R ⁸ are each independently an aromatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent group. Heterocyclic group, and at least one aromatic hydrocarbon group or aromatic heterocyclic group of R ⁷ and R ⁸ is substituted by an aliphatic hydrocarbon group, R ⁷ and R ⁸ are different from each other; L ¹ and L ² are independently a direct bond, - SO ₂ -, or -CO-, R ⁹ is a halogenated aliphatic hydrocarbon group) [Chem. 6] General formula (5)

(In general formula (5), R ^1' , R ^2' , R ^3' and R ^4' each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, R ^{1 '} and R ^{3 '} , R ^2' and R ^4' can be bonded respectively to form a ring structure, R ^1' and the 5th carbon atom of the dibenzopyran ring, R ^3' and the 7th carbon atom of the dibenzopyran ring, R ^2' The 4-position carbon atom of the dibenzopyran ring, or R ^4' and the 2-position carbon atom of the dibenzopyran ring can be respectively bonded to form a ring structure; the hydrogen atom possessed by the above-mentioned aryl or heteroaryl group may be substituted by an acidic group or a salt thereof, or a halogen atom; R ^5' represents an acidic group or a salt thereof, and x is an integer of 0 to 5; wherein, the general formula (5) has at least 2 acidic groups or a salt thereof, and wherein 1 forms the inner salt). The photosensitive colored resin composition for color filters according to claim 1 or 2, which further contains a dispersant. A hardened product, which is a hardened product of the photosensitive colored resin composition for color filters according to any one of claims 1 to 6. A color filter comprising at least a substrate and a colored layer disposed on the substrate, and at least one of the colored layers is a photosensitive colored resin for a color filter according to any one of claims 1 to 6 Hardened product of the composition. A display device having a color filter as claimed in claim 8.

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