TW202124485A - Color material dispersion liquid, dispersant, photosensitive colored resin composition, cured product, color filter and display device - Google Patents

Abstract

Provided is a color material dispersion liquid comprising a color material, a dispersant and a solvent, wherein the dispersant contains at least one of a block copolymer having an A block that includes a constitutional unit represented by the following general formula (I) and a constitutional unit represented by the following general formula (II), and a graft copolymer having a constitutional unit represented by the following general formula (I) and a constitutional unit represented by the following general formula (II):

Description

Color material dispersion, dispersant, photosensitive color resin composition, cured product, color filter, display device

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has continued to increase. The penetration rate of mobile displays (mobile phones, smart phones, and tablet PCs (personal computers, personal computers)) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, organic light-emitting display devices such as organic EL (Electroluminescence) displays, which have high visibility through self-luminescence, are also attracting attention as next-generation image display devices. Regarding the performance of these image display devices, there is a strong desire for further enhancement of image quality or reduction of power consumption, such as improvement of contrast and color reproducibility.

Color filters are used in these liquid crystal display devices or organic light emitting display devices. For example, regarding the formation of a color image in a liquid crystal display device, light passing through a color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. As the light source at this time, in addition to the previous cold cathode tube, a white light-emitting organic light-emitting element or a white light-emitting inorganic light-emitting element is sometimes used. In addition, in organic light emitting display devices, color filters are used for color adjustment and the like. Based on this situation, the requirements for color filters are constantly increasing, such as higher brightness or higher contrast, and improved color reproducibility.

Here, the color filter generally has: a transparent substrate; a colored layer, which is formed on the transparent substrate and includes colored patterns of the three primary colors of red, green, and blue; and a light-shielding portion, which is formed on the transparent substrate in a manner of dividing each colored pattern superior.

Among the methods for forming pixels in color filters, the pigment dispersion method, which has excellent characteristics on average, is the most widely used in terms of spectral characteristics, durability, pattern shape, and accuracy. Regarding color filters with pixels formed using the pigment dispersion method, the miniaturization of pigments has been studied in order to achieve higher brightness or higher contrast. The industry believes that by miniaturizing the pigment, the scattering of light through the color filter caused by the pigment particles will be reduced, thereby achieving high brightness or high contrast. However, the micronized pigment particles tend to agglomerate, so there is a problem of decreased dispersibility or dispersion stability.

As a method for improving the dispersibility of finely divided pigments, it is known that the use of dispersants is more effective. For example, in Patent Document 1, in order to prevent the aggregation of the pigment to obtain a fine pigment dispersion in a good state, a pigment dispersion is disclosed, which is formed by dispersing the pigment by an AB block copolymer. The AB block The characteristic of the copolymer is that the monomer unit constituting the polymer substantially contains a (meth)acrylate-based monomer, and the polymer block constituting the A chain of the copolymer contains (methyl) having a carboxyl group The acrylate monomer unit has an acid value of 50-250 mgKOH/g, and the polymer block constituting the B chain of the copolymer contains (meth)acrylate acetoxyethyl ester as the monomer unit.

On the other hand, in Patent Document 2, it is described that in order to provide a photosensitive resin composition with excellent balance of properties such as solubility and photosensitivity, it contains a binder resin having a carboxyl group and/or a hydroxyl group, and photopolymerization In the photopolymerizable composition composed of a monomer and a photopolymerization initiator, the binder resin having a carboxyl group and/or a hydroxyl group is a copolymer containing a repeating unit represented by the specific formula (I), and the carboxyl group Or at least a part of the hydroxyl group forms a structure with an ethylenically unsaturated group at the end, and the repeating unit represented by the above-mentioned specific formula (I) is derived from the addition of acid (anhydride) to hydroxyalkyl (meth)acrylate The monomer. Previous technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2011-241259 Patent Document 2: Japanese Patent Laid-Open No. 2000-227655

[The problem to be solved by the invention]

As mentioned above, in recent years, in color filters, due to the requirements of high brightness and high contrast, the particle size of the pigments used has been gradually reduced. The micronized pigments tend to agglomerate due to the increased specific surface area, so a dispersant with higher dispersibility is required. In addition, in accordance with requirements for high color gamut or thinning, the demand for high concentration of the color material in the photosensitive resin composition has increased. If the color material ratio in the photosensitive resin composition is increased, the binder component will be relatively reduced. The reduction of the components related to the curability of the coating film such as multifunctional monomers or photoinitiators in the adhesive component will result in insufficient curing, which will lead to a decrease in the crosslinking density of the coating film, and make the substrate of the coating film adhere tightly. Sexual decline. Similarly, in the photosensitive resin composition, the ratio of color materials that are difficult to dissolve in solvents increases, and the relative reduction of binder components that are easily soluble in solvents results in poor solvent resolubility. Therefore, in order to achieve the requirement of increasing the concentration of the color material in the photosensitive resin composition, it is necessary to simultaneously solve the problems caused by the insufficient components of the binder. Furthermore, the substrate adhesion is an indicator of the adhesion between the formed resist pattern (patterned cured product of the photosensitive resin composition) and the substrate. If the substrate adhesion is poor, the following problems will occur, namely, The pattern peeling occurs due to the physical impact in the step after the resist pattern is formed, resulting in display failure. In addition, the solvent re-solubility refers to the property that the solid component of the colored resin composition that has been dried once is re-dissolved in the solvent. For example, if the photosensitive colored resin composition adheres to the tip of the die lip during coating by a die nozzle coater, a cured product will be generated due to drying, and the cured product will not easily dissolve in the photosensitive coloring when coating is restarted. For the resin composition, a part of the cured product on the die lip is easily peeled off and adheres to the colored layer of, for example, a color filter, causing foreign matter defects. Especially when the color material concentration of the colored resin composition is increased, the solvent resolubility tends to become insufficient, and the problem of lower yield due to the above-mentioned foreign matter generated in the manufacturing step of the color filter arises.

The present invention was completed in view of the above-mentioned actual situation, and its first object is to provide a color material dispersion liquid capable of producing a photosensitive colored resin composition that satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion at the same time. And dispersant. In addition, the first object of the present invention is to provide a photosensitive colored resin composition that satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion at the same time. Moreover, the first object of the present invention is to provide a color filter and a display device formed using the photosensitive colored resin composition.

In addition, the second object of the present invention is to provide a color material dispersion liquid capable of producing a photosensitive colored resin composition that simultaneously satisfies excellent substrate adhesion and developability (shortening of the development speed), as a solution to the problem of adhesive components. The technology for the problems caused by the inadequacy. In addition, the second object of the present invention is to provide a photosensitive colored resin composition that satisfies excellent substrate adhesion and developability at the same time, a color filter formed using the photosensitive colored resin composition, and a display device.

In addition, as a technology to solve the problem caused by insufficient binder components, it is also sought to suppress the following phenomenon (notch resistance): the cured product of the photosensitive resin composition is excessively corroded by the developer used for alkaline development, or the developer is caused by the development water. The physical impact caused by pressure peels off from the substrate. However, there has been a problem that the storage stability of the composition will deteriorate if the problem of notch resistance is to be solved. Therefore, the third object of the present invention is to provide a photosensitive colored resin composition having good notch resistance and good storage stability, a color filter formed using the photosensitive colored resin composition, and a display device. [Technical means to solve the problem]

The color material dispersion liquid of the first invention used to achieve the above-mentioned first object contains a color material, a dispersant, and a solvent, and the above-mentioned dispersant contains at least one of a graft copolymer and a block copolymer. The copolymer has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the block copolymer has a structural unit represented by the following general formula (I) and the following The A block of the structural unit represented by the general formula (II).

(通式(I)中，R¹ 表示氫原子或甲基， 通式(II)中，R^1' 表示氫原子或甲基，R² 表示可含有氧原子之脂肪族烴基，R³ 表示脂肪族烴基)[化1]

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, in the general formula (II), R ^1'represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group that may contain an oxygen atom, and R ³ represents a fat Group Hydrocarbyl)

At least one of the dispersant-based graft copolymer and block copolymer of the first invention for achieving the above-mentioned first object, the graft copolymer having the structural unit represented by the above-mentioned general formula (I) and the above-mentioned general The structural unit represented by the formula (II), and the block copolymer has an A block containing the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).

The photosensitive colored resin composition of the first invention for achieving the first object described above contains a color material, the dispersant of the first invention described above, a polyfunctional monomer, a photoinitiator, and a solvent.

The color material dispersion liquid of the second invention used to achieve the above-mentioned second object contains color materials, dispersants and solvents, and the above-mentioned dispersants contain structural units derived from carboxyl-containing ethylenically unsaturated monomers and the following The structural unit represented by the general formula (III), the polymer chain in the structural unit represented by the general formula (III) contains at least one of a graft copolymer and a block copolymer, and the graft copolymer includes selected from At least one structural unit in the group consisting of the structural unit represented by the following general formula (V) and the structural unit represented by the following general formula (V'), the block copolymer has: A block, which Contains a structural unit derived from an ethylenically unsaturated monomer containing a carboxyl group; and B block, which includes a structural unit selected from the following general formula (V) and a structure represented by the following general formula (V') At least one structural unit in the group consisting of the unit.

(通式(III)中，R^1'' 表示氫原子或甲基，A¹ 表示直接鍵結或2價連結基，Polymer表示聚合物鏈)[化2]

(In the general formula (III), R ^1'' represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain)

(通式(V)中，R^11' 係氫原子或甲基，A^2' 係2價連結基，R⁵ 係伸乙基或伸丙基，R⁶ 係氫原子或烴基，m表示2以上80以下之數；  通式(V')中，R^11'' 係氫原子或甲基，A^2'' 係2價連結基，R⁷ 係碳數為1～10之伸烷基，R⁸ 係碳數為3～7之伸烷基，R⁹ 係氫原子或烴基，n表示1以上40以下之數)[化3]

(Formula (V) in, R ^{11 'based} hydrogen atom or a methyl group, A ^2' based divalent linking group, R ⁵ or extension line extending ethyl propyl, R ⁶ a hydrogen atom or a hydrocarbon-based, m represents 2 or more A number below 80; In the general formula (V'), R ^11" is a hydrogen atom or a methyl group, A ^2" is a divalent linking group, R ⁷ is an alkylene group with 1 to 10 carbon atoms, and R ⁸ It is an alkylene group having 3 to 7 carbon atoms, R ⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number from 1 to 40)

The photosensitive colored resin composition of the second invention for achieving the above-mentioned second object contains a color material, a dispersant, a multifunctional monomer, a photoinitiator, and a solvent, and The dispersant has a structural unit derived from an ethylenically unsaturated monomer containing a carboxyl group and a structural unit represented by the general formula (III), and the polymer chain in the structural unit represented by the general formula (III) contains grafts At least one of a copolymer and a block copolymer. The graft copolymer includes a group selected from the group consisting of a structural unit represented by the general formula (V) and a structural unit represented by the general formula (V') At least one structural unit, and the block copolymer has: A block, which includes a structural unit derived from a carboxyl-containing ethylenically unsaturated monomer; and B block, which includes a block selected from the above general formula (V) At least one structural unit in the group consisting of the structural unit represented and the structural unit represented by the general formula (V').

The photosensitive colored resin composition of the third invention for achieving the above-mentioned third object contains a color material, a dispersant, a polyfunctional monomer, a photoinitiator, a solvent, and a polyfunctional thiol compound, and the dispersant contains a source At least one of graft copolymers and block copolymers from structural units of carboxyl-containing ethylenically unsaturated monomers.

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

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

According to the first invention, it is possible to provide a color material dispersion liquid and a dispersant capable of producing a photosensitive colored resin composition that satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion at the same time. Furthermore, according to the present invention, it is possible to provide a photosensitive colored resin composition that simultaneously satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion. Furthermore, according to the present invention, it is possible to provide a color filter and a display device formed using the photosensitive colored resin composition. According to the second invention, it is possible to provide a color material dispersion and a dispersant capable of producing a photosensitive colored resin composition satisfying excellent substrate adhesion and developability at the same time. Furthermore, according to the second invention, it is possible to provide a photosensitive colored resin composition that satisfies excellent substrate adhesion and developability at the same time, a color filter formed using the photosensitive colored resin composition, and a display device. According to the third invention, it is possible to provide a photosensitive colored resin composition having good notch resistance and good storage stability, a color filter formed using the photosensitive colored resin composition, and a display device.

Hereinafter, the color material dispersion liquid, the dispersant, the photosensitive colored resin composition, the color filter, and the display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible light region and the non-visible light region, and further radiation. The radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, the so-called (meth)acryloyl group means each of an acryloyl group and a methacryloyl group, and the so-called (meth)acrylic acid means each of acrylic acid and methacrylic acid, so-called (meth)acrylic acid Acrylate means each of acrylate and methacrylate. In this manual, unless otherwise specified, the chromaticity coordinates x and y are the coordinates in the XYZ color system of JIS Z8701: 1999 for color measurement using C light source. In addition, in this specification, "~" indicating a numerical range is used to include the numerical values described before and after it as the lower limit and the upper limit.

I. The first invention I-1. The first color material dispersion of the present invention The color material dispersion liquid of the first invention contains a color material, a dispersant, and a solvent, and the dispersant contains at least one of a graft copolymer and a block copolymer, and the graft copolymer has the following general formula ( The structural unit represented by I) and the structural unit represented by the following general formula (II), and the block copolymer has a structural unit represented by the following general formula (I) and represented by the following general formula (II) The A block of the structural unit.

(通式(I)中，R¹ 表示氫原子或甲基， 通式(II)中，R^1' 表示氫原子或甲基，R² 表示可含有氧原子之脂肪族烴基，R³ 表示脂肪族烴基)[化4]

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, in the general formula (II), R ^1'represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group that may contain an oxygen atom, and R ³ represents a fat Group Hydrocarbyl)

The color material dispersion liquid of the first invention uses an acidic dispersant as at least one of a graft copolymer and a block copolymer as a dispersant, and the graft copolymer contains the above-mentioned two specific structural units containing acidic groups. (The structural unit represented by the general formula (I) and the structural unit represented by the general formula (II)), the block copolymer has an A block containing the two specific acidic group-containing structural units. Regarding the above-mentioned graft copolymer and block copolymer used in the first invention, it is estimated as follows: By combining the structural unit represented by the general formula (I) with a rigid structure (hereinafter, sometimes referred to as "structural unit (I) )”) and the structural unit represented by the general formula (II) with a soft structure (hereinafter sometimes referred to as "structural unit (II)") as the adsorption site of the color material, and the use of structural unit (I) alone or Compared with the case of (II), it can be compared to the surface of the color material in various states such as steric hindrance or polarity, on the surface of the structural unit (I) that is more suitable for adsorption, and the surface of the structural unit (II) is more suitable for both. Adsorption with higher efficiency, so the dispersion stability is improved. As shown in the following comparative examples, the dispersant having an acidic group tends to have the following tendency: the acidic gene of the dispersant that cannot be adsorbed to the color material comes into contact with the solvent, and the solvent resolubility deteriorates. Furthermore, regarding the dispersant with an acidic group, the following assumptions are made: if the adsorption power to the color material is low, the dispersant is free in the solvent and cannot be adsorbed on the surface of the color material, so that the solvent affinity part of the dispersant is relative to The surface area of the color material surface is reduced, and the contact amount of the acidic group of the dispersant and the solvent is increased. The above-mentioned effects complement each other and cause the resolubility of the solvent to be significantly deteriorated. In contrast, with regard to the graft copolymers and block copolymers used in the first invention, it is estimated that the structural units (I) and (II) as the adsorption site of the dispersant efficiently It is adsorbed on the surface of the color material to cover the color material, whereby the solvent affinity part of the dispersant becomes larger relative to the surface area of the color material surface, and the acidic group of the dispersant is not easy to contact with the solvent, thereby improving the re-solubility of the solvent. In addition, it can be inferred that by the interaction between the structural units (I) and (II) as the adsorption site of the dispersant and the polar groups such as the glass surface as the substrate, the adhesion of the coating film to the substrate is improved. It can be inferred that by combining the structural unit (I) with a rigid structure and the structural unit (II) with a soft structure, compared with the case of using the structural unit (I) or (II) alone, it can also be compared with the structure of the substrate surface. The surface of the unit (I) more suitable for adsorption and the surface of the structural unit (II) more suitable for interacting with each other with higher efficiency, so that the adhesion of the coating film to the substrate is improved.

The first color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, each component of the color material dispersion liquid of the first invention will be described in detail starting from the dispersant of the first invention.

<The dispersant of the first invention> In the first invention, at least one of a graft copolymer and a block copolymer is used as a dispersant. The graft copolymer has the structural unit represented by the general formula (I) and the structure represented by the general formula (II). As the structural unit represented, the block copolymer has an A block containing the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).

[Graft Copolymer] The graft copolymer used in the first invention is a copolymer having a structural unit represented by the above general formula (I) and the above general formula (II) functioning as an adsorption site with respect to the color material in the main chain The structural unit shown has a graft polymer chain that functions as a solvent affinity site in the side chain.

(The structural unit represented by the general formula (I), the structural unit represented by the general formula (II)) The structural unit represented by the general formula (I) is a structural unit derived from (meth)acrylic acid. In the structural unit represented by the general formula (II), R ² represents an aliphatic hydrocarbon group that may contain an oxygen atom. The aliphatic hydrocarbon group may, for example, be a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group. As the aliphatic hydrocarbon group, for example, a methylene group, a dimethylene group (ethylene group), a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a Straight-chain alkylene such as methylene; branched alkylene such as methylmethylene, methylethylene, 1-methylpentylene, 1,4-dimethylbutylene, etc.; ring extension Cyclic alkylene groups such as pentyl and cyclohexylene. The carbon number of the aliphatic hydrocarbon group of R ² may, for example, be 1-20. In terms of dispersion stability, it is preferably 1-16, more preferably 1-12, and still more preferably 2-8. The aliphatic hydrocarbon group containing an oxygen atom in R ² has a structure in which the carbon atom in the aliphatic hydrocarbon group is substituted with an oxygen atom, or the hydrogen atom in the aliphatic hydrocarbon group is substituted with an oxygen atom-containing substituent structure. As an aliphatic hydrocarbon group which may contain an oxygen atom, for example, a structure containing a linking group such as -O-, -COO-, -OCO- in the carbon chain of the hydrocarbon group can be exemplified. As an aliphatic hydrocarbon group containing an oxygen atom, specifically, for example, -R ²⁰ -(OR ²¹ )j- (here, R ²⁰ and R ²¹ each independently represent an aliphatic hydrocarbon group, and j represents 1 to 80 Number), -R ²² -(OCO-R ²³ )k- (here, R ²² and R ²³ each independently represent an aliphatic hydrocarbon group, and k represents a number from 1 to 40). The aliphatic hydrocarbon groups of R ²⁰ , R ²¹ , R ²² and R ²³ may be the same as the above-mentioned aliphatic hydrocarbon groups. In terms of dispersion stability, R ^{20 is} preferably an alkylene having 1 to 20 carbons, R ^{21 is} preferably an alkylene having 1 to 20 carbons, and j is preferably a number of 1 to 40. , More preferably, it is the number of 2-25, More preferably, it is the number of 2-10. In terms of dispersion stability, R ^{22 is} preferably an alkylene having 1 to 20 carbons, R ^{23 is} preferably an alkylene having 1 to 20 carbons, and k is preferably 1 to 30. The number is more preferably a number of 1-20, and still more preferably a number of 1-10. The above-mentioned R ²⁰ and the above-mentioned R ²² are each independently preferably an alkylene group having 1 to 12 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. The above-mentioned R ^{21 is} preferably an alkylene group having 2 to 8 carbon atoms, more preferably an ethylene group or a propylene group. The above-mentioned R ^{23 is} preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 3 to 7 carbon atoms. Moreover, as a substituent containing an oxygen atom, a hydroxyl group, an alkoxy group, etc. are mentioned, for example. In the structural unit represented by the general formula (II), as R ² , in terms of solvent resolubility, it may be an aliphatic hydrocarbon group, and may be an aliphatic hydrocarbon group having 1 to 20 carbon atoms.

In the structural unit represented by the general formula (II), R ³ represents an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may, for example, be a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group. As the aliphatic hydrocarbon group, for example, a methylene group, a dimethylene group (ethylene group), a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a Straight-chain alkylene such as methylene; branched alkylene such as methylmethylene, methylethylene, 1-methylpentylene, 1,4-dimethylbutylene, etc.; ring extension Cyclic alkylene groups such as pentyl and cyclohexylene; unsaturated alkylene groups such as -CH=CH- group. The carbon number of the aliphatic hydrocarbon group of R ³ may, for example, be 1-20. In terms of dispersion stability, it is preferably 1-16, more preferably 2-12, and still more preferably 2-6.

The structural unit represented by the general formula (II) can be derived from, for example, a monomer as an addition reaction product of a (meth)acrylate having a hydroxyl group and an aliphatic dicarboxylic acid or an aliphatic dicarboxylic anhydride. As the (meth)acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 4-hydroxybutyl meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (poly)ethylene glycol mono(meth)acrylate, (poly)propylene glycol mono(meth)acrylate, unsaturated fatty acid Hydroxyalkyl esters modify ε-caprolactone and the like. In addition, examples of aliphatic dicarboxylic acids or aliphatic dicarboxylic acid anhydrides include malonic acid, succinic acid, glutaric acid, adipic acid, 1,6-hexanedicarboxylic acid, and hexahydrophthalic acid. Formic acid, succinic anhydride, adipic anhydride, hexahydrophthalic anhydride, maleic anhydride, etc.

In the graft copolymer, the structural unit represented by the general formula (I) may include one type or two or more types of structural units. In addition, the structural unit represented by the general formula (II) may include one type or two or more types of structural units.

In terms of dispersion stability, when the total structural unit of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is set to 100 parts by mass, the general formula (I) The content ratio of the structural unit shown is preferably 35 parts by mass or more, more preferably 50 parts by mass or more, and preferably 95 parts by mass or less, and more preferably 85 parts by mass or less.

(Structural unit with grafted polymer chain) The above-mentioned graft copolymer has a graft polymer chain that functions as a solvent affinity site in the side chain. The above-mentioned polymer chain preferably has a solubility of 20 (g/100 g solvent) or more relative to the organic solvent used in combination at 23° C. as a standard. The solubility of the polymer chain can be based on the above-mentioned solubility of the raw material introduced into the polymer chain when preparing the graft copolymer. For example, in order to introduce a polymer chain into a graft copolymer, when using a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at its end, as long as The polymerizable oligomer may have the above-mentioned solubility. In addition, after forming a copolymer from a monomer having a group containing an ethylenically unsaturated double bond, a polymer chain containing a reactive group that can react with the reactive group contained in the copolymer is used to introduce the polymer In the case of a chain, it is sufficient that the polymer chain containing the reactive group has the above-mentioned solubility.

The graft copolymer used in the first invention preferably has a structural unit represented by the following general formula (III), which has the general formula (I) in the main chain that functions as an adsorption site for the color material The structural unit represented by) and the structural unit represented by the above general formula (II) further have a polymer chain functioning as a solvent affinity site in the side chain.

(通式(III)中，R^1'' 表示氫原子或甲基，A¹ 表示直接鍵結或2價連結基，Polymer表示聚合物鏈)[化5]

(In the general formula (III), R ^1'' represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain)

In the above general formula (III), A ¹ is a direct bond or a divalent linking group. The ^{divalent linking group in A 1} is not particularly limited, as long as it can link the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. The divalent linking group may, for example, be a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- Group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof. Furthermore, in the present invention, the orientation of the bond of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, -CO may be the carbon atom side of the main chain and -NH may be the nitrogen atom side of the side chain, or on the contrary, -NH may be the carbon atom of the main chain Side and -CO is the nitrogen atom side of the side chain. Among them, in terms of dispersibility, A ¹ in the general formula (III) is preferably a divalent linking group containing -CONH- group or -COO- group, and more preferably contains -CONH- group or -COO- A divalent linking group of a group and an alkylene group having 1 to 10 carbon atoms.

In terms of the dispersibility and dispersion stability of the color material, the polymer chain preferably includes at least one structural unit represented by the following general formula (IV).

(通式(IV)中，R¹¹ 係氫原子或甲基，A² 係2價連結基，R⁴ 係可具有取代基且可含有雜原子之烴基)[化6]

(In the general formula (IV), R ¹¹ is a hydrogen atom or a methyl group, A ² is a divalent linking group, and R ⁴ is a hydrocarbon group that may have a substituent and may contain a hetero atom)

In the general formula (IV), A ² is a divalent linking group. As the divalent linking group in ^{A 2} , for example, the same group as the divalent linking group in ^{A 1 described above can be mentioned.} Among them, in terms of the dispersibility and dispersion stability of the color material, A ² in the general formula (IV) is preferably a divalent linking group containing -CONH- group or -COO- group, more preferably -CONH -Based or -COO-based.

The hydrocarbon group in the hydrocarbon group that may contain a hetero atom in R ⁴ may, for example, be an alkyl group with 1 to 18 carbons, an alkenyl group with 2 to 18 carbons, an aryl group, an aralkyl group or an alkyl substituted aryl group, etc. The combination of these. The above-mentioned C1-C18 alkyl group may be any of linear, branched, and cyclic, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonane Group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, 𦯉 group, iso𦯉 group, dicyclopentyl group, adamantyl group, lower alkyl substituted adamantyl group, etc. The number of carbon atoms in the alkyl group is preferably 1-12, and more preferably 1-6. The above-mentioned alkenyl group having 2 to 18 carbon atoms may be any of linear, branched, and 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, and in terms of the reactivity of the obtained polymer, it is preferable to have a double bond at the end of the alkenyl group. The carbon number of the alkenyl group is preferably 2-12, more preferably 2-8. The aryl group may, for example, be a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The carbon number of the aryl group is preferably 6-24, more preferably 6-12. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group etc. may be mentioned, and it may have a substituent further. The carbon number of the aralkyl group is preferably 7-20, and more preferably 7-14. In addition, a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded as a substituent to an aromatic ring such as the above-mentioned aryl group or aralkyl group.

As ^{the hydrocarbon group in R 4} , in terms of dispersion stability, it is preferably selected from alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms that may be substituted with alkyl groups, and One or more of the alkyl-substituted C7-14 aralkyl groups are preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-nonyl , N-lauryl, n-stearyl, alkyl-substituted phenyl, and benzyl at least one of the group consisting of.

The ^{heteroatom-containing hydrocarbyl group in R 4} has a structure in which the carbon atom in the hydrocarbyl group is substituted with a heteroatom, or has a structure in which the hydrogen atom in the hydrocarbyl group is substituted with a heteroatom-containing substituent. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. As the hydrocarbon group which may contain a hetero atom, for example, the carbon chain of the hydrocarbon group contains -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO- , -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O- The structure of NH- and other linking groups. In addition, the hydrocarbon group may have a substituent within a range that does not interfere with the dispersibility of the graft copolymer. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, a nitro group, and a cyano group. , Epoxy, isocyanate, thiol, etc.

Moreover, as ^{the hydrocarbon group which may contain a hetero atom in R 4} , the structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a hetero atom may also be used. For example, the structural unit represented by the general formula (IV) may also be a structure obtained by reacting glycidyl (meth)acrylate with a structural unit derived from (meth)acrylic acid. ^{That is, the structure of -A 2} -R ^{4 in} the general formula (IV) can also be -COO-CH ₂ CH(OH)CH ₂ -OCO-CR=CH ₂ (here, R is a hydrogen atom or a methyl group). Represents the structure. In addition, the structural unit represented by the general formula (IV) may also be a structure obtained by reacting 2-isocyanatoalkyl (meth)acrylate with a structural unit derived from hydroxyalkyl (meth)acrylate . ^{That is, R 4} in the general formula (IV) may also be -R'-OCONH-R''-OCO-CR=CH ₂ (here, R'and R'' are each independently an alkylene group, and R is Hydrogen atom or methyl).

As a monomer that can derive the structural unit represented by the general formula (IV), it is preferable to have a structural unit derived from, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl) Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid 2-Ethoxyethyl, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, iso(meth)acrylate, dicyclopentyl (meth)acrylate , Adamantyl (meth)acrylate, (meth)acrylic acid, 2-methacryloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate Ester, methoxy polyethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate, phenoxy glycol (meth) acrylate, unsaturated fatty acid hydroxyalkyl ester modified ε- Caprolactone and so on. However, it is not limited to these.

In the present invention, as the above-mentioned R ⁴ , it is preferable to use one having excellent solubility with the following organic solvent, as long as it is appropriately selected according to the organic solvent used in the color material dispersion liquid. Specifically, for example, when the above-mentioned organic solvent uses an organic solvent such as ether alcohol acetate, ether, ester, alcohol, etc., which are generally used as organic solvents for color material dispersions, methyl, Ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxypolyethylene glycol, Methoxy polypropylene glycol base, polyethylene glycol base, etc.

In the above polymer chain, the structural unit represented by the above general formula (IV) may be one type alone, or two or more types may be mixed. In terms of the dispersibility and dispersion stability of the color material, in the polymer chain, when the total structural unit of the polymer chain is set to 100% by mass, the structural unit represented by the general formula (IV) The total ratio may also be 100% by mass. In terms of the dispersibility and dispersion stability of the color material, in the polymer chain, when the total structural unit of the polymer chain is set to 100% by mass, the structural unit represented by the general formula (IV) Aggregate ratio It is preferably 40% by mass or more, and more preferably 70% by mass or more.

In addition, the polymer chain of the macromonomer includes a structure represented by the following general formula (V) and a structure represented by the following general formula (V') selected from among the structural units represented by the above general formula (IV) The condition of at least one structural unit in the group composed of the unit improves the adhesion of the substrate, shortens the development time, and makes the cross-sectional shape of the resist pattern easy to become a forward cone shape, which is preferable. If the cross-sectional shape of the resist pattern becomes an inverted cone shape, the ITO (Indium Tin Oxides) film formed on the resist pattern may break, which may cause display failure.

(通式(V)中，R^11' 係氫原子或甲基，A^2' 係2價連結基，R⁵ 係伸乙基或伸丙基，R⁶ 係氫原子或烴基，m表示2以上80以下之數；  通式(V')中，R^11'' 係氫原子或甲基，A^2'' 係2價連結基，R⁷ 係碳數為1～10之伸烷基，R⁸ 係碳數為3～7之伸烷基，R⁹ 係氫原子或烴基，n表示1以上40以下之數)[化7]

(Formula (V) in, R ^{11 'based} hydrogen atom or a methyl group, A ^2' based divalent linking group, R ⁵ or extension line extending ethyl propyl, R ⁶ a hydrogen atom or a hydrocarbon-based, m represents 2 or more A number below 80; In the general formula (V'), R ^11" is a hydrogen atom or a methyl group, A ^2" is a divalent linking group, R ⁷ is an alkylene group with 1 to 10 carbon atoms, and R ⁸ It is an alkylene group having 3 to 7 carbon atoms, R ⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number from 1 to 40)

In the structural unit represented by the above general formula (V) and the structural unit represented by the general formula (V'), A ^2'and A ^2" are each independently a divalent linking group. As A ^{2 'and} A ^2''in the divalent linking group, and examples include A ² in the above-described divalent linking group of the same group. Among them, in terms of solubility in terms of a color filter for use of the organic solvent, A ^{2 'and} A ^2''are each independently preferably comprises a divalent group -CONH- or -COO- group of links Group, more preferably -CONH- group or -COO- group.

The above m in the above general formula (V) represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 2 or more. Among them, in terms of substrate adhesion, it is preferably 3 or more , And more preferably 4 or more. On the other hand, the upper limit of m is 80 or less, and it is preferably 50 or less in terms of solubility in organic solvents used for color filter applications.

R ⁶ is a hydrogen atom or a hydrocarbon group. ^{Examples of the hydrocarbon group in R 6} include an alkyl group having 1 to 18 carbons, an alkenyl group having 2 to 18 carbons, an aryl group, and an aralkyl or alkyl substituted aromatic group. The combination of the base and so on. As the hydrocarbon group in the above-mentioned R ⁶ , the same groups as the hydrocarbon group in the ^{above-mentioned R 4 can be exemplified.} The hydrocarbon group in R ⁶ is preferably selected from the group consisting of alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms that may be substituted by alkyl groups, and aryl groups that may be substituted by alkyl groups in terms of dispersion stability. One or more of the alkyl-substituted C7-14 aralkyl groups are preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-nonyl , N-lauryl, n-stearyl, alkyl-substituted phenyl, and benzyl at least one of the group consisting of.

In the above general formula (V'), R ⁷ is an alkylene group having 1 to 10 carbon atoms, and among them, an alkylene group having 2 to 8 carbon atoms is preferred in terms of solvent resolubility. R ⁸ is an alkylene having 3 to 7 carbon atoms, and in terms of substrate adhesion, it is preferably an alkylene having 3 to 5 carbon atoms, and more preferably an alkylene having 5 carbon atoms. alkyl. R ⁹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group in the ^{above R 9} may be the same as the hydrocarbon group in the ^{above R 6.}

The aforementioned n in the aforementioned general formula (V') represents the number of repeating units of the lactone chain, and represents a number of 1 or more, and among them, it is preferably 2 or more, and more preferably 3 or more. On the other hand, the upper limit of n is 40 or less, and it is preferably 20 or less in terms of solubility in organic solvents used for color filter applications.

In the above-mentioned polymer chain, at least one structural unit selected from the group consisting of the structural unit represented by the above general formula (V) and the structural unit represented by the above general formula (V') may be one kind alone, Two or more types can also be mixed. In order to improve the adhesion of the substrate, shorten the development time, and to make the cross-sectional shape of the resist pattern easy to become a positive cone shape, the total structural unit of the polymer chain in the macromonomer of the graft copolymer is set When it is 100% by mass, the total ratio of at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V') is preferably 5 Mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more. In terms of solvent resolubility, when the total structural unit of the polymer chain is 100% by mass, it is selected from the structural unit represented by the general formula (V) and the general formula (V'). The total ratio of at least one structural unit in the group consisting of the structural unit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

Among the structural units of the polymer chain in the structural unit represented by the general formula (III) of the graft copolymer, except for the structural unit selected from the structural unit represented by the general formula (V) and the general formula (V') In addition to the structural unit represented by the above-mentioned general formula (IV) of at least one structural unit in the group consisting of the structural unit represented, other structural units may be contained. As the other structural unit, a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with the ethylenically unsaturated monomer that derives the structural unit represented by the general formula (IV) can be exemplified. Examples of monomers from which other structural units are derived include styrene such as styrene and α-methylstyrene; vinyl ethers such as phenyl vinyl ether and the like.

In terms of the effect of the present invention, in the polymer chain in the structural unit represented by the general formula (III) of the graft copolymer, when the total structural unit of the polymer chain is set to 100% by mass , The total ratio of other structural units is preferably 30% by mass or less, more preferably 10% by mass or less.

Also, in terms of the dispersibility and dispersion stability of the color material, the mass average molecular weight Mw of the polymer chain is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, and even more preferably 15000 Hereinafter, it is more preferably 12,000 or less. With the mass average molecular weight Mw of the polymer chain in the above range, the sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity part of the dispersant can be increased as described above. The effect becomes good. The mass average molecular weight Mw of the polymer chain can be measured in the same manner as the following dispersant for the polymerizable oligomer or the polymer chain containing the reactive group.

In addition, the above-mentioned polymer chain includes the structural unit represented by the above-mentioned general formula (IV), and the glass transition temperature of the polymer chain is 85°C or less, which will improve the development time delay and improve the coating suitability, so it is preferred . In order to improve production efficiency, it is required to increase the coating speed of the photosensitive colored resin composition. If the coating suitability is excellent, uneven streaks will not easily occur during high-speed coating. Here, the glass transition temperature (Tg) of the above-mentioned polymer chain of the graft copolymer in the present invention can be calculated by the following formula. 1/Tg=Σ(Xi/Tgi) Here, the polymer is assumed to be copolymerized with n monomer components of i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, Σ is the sum of i=1 to n. Furthermore, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be the value of the Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

Furthermore, in terms of dispersion stability, the acid value of the polymer chain is preferably 10 mgKOH/g or less, and more preferably 0 mgKOH/g or less. Here, as for the acid value, the above-mentioned polymerizable oligomer or the above-mentioned reactive group-containing polymer chain can be measured in the same manner as the acid value of the following dispersant. The polymer chain may also contain at least one structural unit selected from the group consisting of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), etc., a structure containing an acidic group, etc. As long as the unit does not impair the effect of the present invention, in terms of dispersion stability, when the total structural unit of the polymer chain is 100% by mass, the total ratio of structural units containing acidic groups is preferable It is 5% by mass or less, more preferably 0% by mass.

In addition, in terms of dispersion stability and stability over time when the polyfunctional thiol compound is mixed, the amine value of the polymer chain is preferably 10 mgKOH/g or less, and more preferably 0 mgKOH/g or less. Here, the amine value of the polymer chain means the amount of hydrochloric acid required to neutralize 1 g of the solid content of the polymerizable oligomer or the polymer chain containing reactive groups as the equivalent of potassium hydroxide. The mass (mg) is the value measured by the method described in JIS K 7237:1995. The above-mentioned polymer chain may also contain a structural unit containing a nitrogen atom, as long as the effect of the present invention is not impaired. In terms of dispersion stability and stability over time when the polyfunctional thiol compound is mixed, the above-mentioned When the total structural units of the polymer chain are set to 100% by mass, the total ratio of the structural units containing nitrogen atoms is preferably 3% by mass or less, and more preferably 0% by mass.

In the graft copolymer, the total content ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is preferably 3% by mass to 60% by mass, more preferably 6 Mass% to 45% by mass, more preferably 9% to 35% by mass. If the total content ratio of the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) in the graft copolymer is within the above range, the affinity of the graft copolymer with the color material The ratio of the sex parts becomes appropriate, and the decrease in solubility to organic solvents can be suppressed, so the adsorption to color materials becomes good, and excellent dispersibility, dispersion stability and solvent resolubility can be obtained. On the other hand, in the graft copolymer, the total content of the structural unit including the graft polymer chain or the structural unit represented by the general formula (III) is preferably 40% by mass to 97% by mass, more preferably It is 55% by mass to 94% by mass, and more preferably 65% by mass to 91% by mass. If the total content ratio of the structural units of the graft polymer chain or the structural units represented by the general formula (III) in the graft copolymer is within the above range, the ratio of the solvent affinity portion in the graft copolymer When it becomes appropriate, the sufficient steric repulsion effect as a dispersant can be maintained, and the effect on the above effect exerted by the increase in the specific surface area of the solvent affinity part of the dispersant can be improved. Furthermore, the content ratio of the above-mentioned structural unit is based on the structural unit represented by the above-mentioned general formula (I), the structural unit represented by the above-mentioned general formula (II), and the above-mentioned general formula (III) when the graft copolymer is synthesized. Calculate the added amount of monomers such as structural units.

The above-mentioned graft copolymer used in the first invention may also be within a range that does not impair the effect of the invention, except for having the structural unit represented by the above general formula (I) and the structure represented by the above general formula (II) In addition to the unit and the structural unit represented by the general formula (III), it has other structural units. Regarding other structural units, an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer that derives the structural unit represented by the general formula (I) and the like can be appropriately selected for copolymerization, and other structural units can be introduced. As another structural unit copolymerized in the main chain with the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II), for example, the structure represented by the above general formula (IV) can be exemplified Unit etc. In addition, a structural unit containing an acidic group different from the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) may be included as another structural unit. The structural unit containing an acidic group may, for example, be a structural unit derived from an acidic group-containing ethylenically unsaturated monomer, and the acidic group may, for example, be a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As carboxyl group-containing ethylenically unsaturated monomers, for example, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, methylene succinic acid, butylene Addition reaction products of monomers having hydroxyl groups such as enoic acid, cinnamic acid, acrylic acid dimer, 2-hydroxyethyl (meth)acrylate, and anhydrides having aromatic rings such as phthalic acid. As a phosphoric acid group-containing ethylenically unsaturated monomer, 2-propylene oxyethyl acid phosphate etc. are mentioned. The sulfonic acid group-containing ethylenically unsaturated monomer may, for example, be acryloxyethyl sulfonic acid. In the above-mentioned graft copolymer, the total content ratio of other structural units copolymerized in the main chain is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass.

(Manufacturing method of graft copolymer) In the first invention, the method for producing the graft copolymer is not particularly limited, as long as it can produce the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) The method of graft copolymer is sufficient. In the case of producing a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II), for example, the following method can be exemplified: containing (meth)acrylic acid, The monomer represented by the general formula (IIa), and a polymerizable oligomer (macromonomer) containing the above-mentioned polymer chain and a group having an ethylenically unsaturated double bond at the end thereof as a copolymerization component and the like Copolymerization to produce graft copolymers. If necessary, other monomers can also be used, and the graft copolymer can be produced using a known polymerization method.

(通式(IIa)中，R^1' 、R² 及R³ 與通式(II)中之情形相同)[化8]

(In the general formula (IIa), R ^1' , R ² and R ³ are the same as in the general formula (II))

In addition, in the case of producing a graft copolymer having the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II), (meth)acrylic acid and the above general formula ( After the monomer represented by IIa) and other ethylenically unsaturated monomers are addition polymerized to form a copolymer, a polymer chain containing a reactive group that can react with the reactive group contained in the copolymer is used to introduce the polymer chain . Specifically, for example, after synthesizing a copolymer having substituents such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, and a hydrogen bond forming group, the copolymer may be combined with the The polymer chain of the functional group where the substituent reacts reacts and is introduced into the polymer chain. For example, a polymer chain having a carboxyl group at the end can be reacted with a copolymer having a glycidyl group at the side chain, or a polymer chain having a hydroxyl group at the end can be reacted with a copolymer having an isocyanate group at the side chain, and Introduce polymer chains. Furthermore, in the above polymerization, additives generally used in polymerization, such as polymerization initiators, dispersion stabilizers, chain transfer agents, etc., may also be used.

[Block copolymer] The block copolymer used in the first invention has an A block functioning as an adsorption site for color materials, and the A block includes the structural unit represented by the above general formula (I) and the above general formula (II). Indicates the structural unit. The block copolymer used in the first invention preferably further has a B block functioning as a solvent affinity site.

(A block) The structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) in the A block may be the same as those described in the graft copolymer, so the description is omitted here. In the A block, the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) can also be copolymerized in block, but if you want to be able to resist the color of various states such as steric hindrance or polarity On the surface of the material, both the surface where the structural unit (I) is more suitable for adsorption and the surface where the structural unit (II) is more suitable for adsorption with higher efficiency, preferably random copolymerization.

In the A block, the structural unit represented by the general formula (I) may include one type or two or more types of structural units. In addition, the structural unit represented by the general formula (II) may include one type or two or more types of structural units. In terms of dispersion stability, when the total structural unit of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is set to 100 parts by mass, the general formula (I) The content ratio of the structural unit shown is preferably 35 parts by mass or more, more preferably 50 parts by mass or more, and preferably 95 parts by mass or less, and more preferably 85 parts by mass or less.

In the A block, within a range that does not impair the effect of the present invention, in addition to the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II), there may be other Structural units. Regarding other structural units, an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer that derives the structural unit represented by the general formula (I) and the like can be appropriately selected for copolymerization, and other structural units can be introduced. As other structural units contained in the A block in the range not impairing the effects of the present invention, for example, structural units represented by the above-mentioned general formula (IV) and the like can be exemplified. In addition, a structural unit containing an acidic group different from the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) may be included as another structural unit. Regarding the structural unit represented by the above general formula (IV), and the structural unit containing an acidic group that is different from the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II), it can be combined with The description in the branch copolymer is the same, so the description is omitted here. The total content ratio of other structural units contained in the A block is not particularly limited, as long as it is within a range that does not impair the effects of the present invention, but in terms of dispersibility and dispersion stability, it is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass.

That is, in terms of dispersibility and dispersion stability, the total content ratio of the structural unit represented by the general formula (I) contained in the A block and the structural unit represented by the general formula (II) is preferably 80 Mass% or more, more preferably 90% by mass or more, and may be 100% by mass.

(B block) In the block copolymer used in the first invention, the B block is a block that functions as a solvent affinity site. The B block is preferably an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer that derives the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). In the body, it is appropriately selected and used according to the solvent so as to have solvent affinity. Preferably, the B block is introduced in such a way that the solubility of the block copolymer with respect to the solvent used in combination at 23° C. is 20 (g/100 g solvent) or more as a standard.

In the block copolymer used in the first invention, in order to make the solvent affinity good and the dispersibility and dispersion stability of the color material good, the B block that functions as a solvent affinity site is better. It is preferable to include at least one structural unit represented by the above-mentioned general formula (IV). The structural unit represented by the above general formula (IV) contained in the B block may be the same as that described in the graft copolymer, so the description is omitted here.

In the above-mentioned B block, the structural unit represented by the above-mentioned general formula (IV) may be one type alone, or two or more types may be mixed. In terms of the dispersibility and dispersion stability of the color material, in the above B block, when the total structural unit of the B block is set to 100% by mass, the structural unit represented by the above general formula (IV) The total ratio may also be 100% by mass. In terms of the dispersibility and dispersion stability of the color material, in the above B block, when the total structural unit of the B block is set to 100% by mass, the structural unit represented by the above general formula (IV) Aggregate ratio It is preferably 40% by mass or more, and more preferably 70% by mass or more.

In addition, the B block includes a group selected from the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V') among the structural units represented by the general formula (IV) At least one of the structural units will improve the adhesion of the substrate, shorten the development time, and make the cross-sectional shape of the resist pattern easy to become a forward cone shape, which is preferable. As at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V') contained in the B block, it may be combined with The description in the branch copolymer is the same, so the description is omitted here.

In the above-mentioned B block, at least one structural unit selected from the group consisting of the structural unit represented by the above-mentioned general formula (V) and the structural unit represented by the above-mentioned general formula (V') may be one kind alone, Two or more types can also be mixed. In order to improve the adhesion of the substrate, shorten the development time, and to make the cross-sectional shape of the resist pattern easy to become a positive cone shape, when the total structural unit of the above B block is set to 100% by mass, select from the above general formula The total ratio of at least one structural unit in the group consisting of the structural unit represented by (V) and the structural unit represented by the general formula (V') is preferably 5% by mass or more, more preferably 10% by mass or more , And more preferably 15% by mass or more. In terms of solvent resolubility, when the total structural unit of the above B block is set to 100% by mass, it is selected from the structural unit represented by the above general formula (V) and the above general formula (V') The total ratio of at least one structural unit in the group consisting of the structural unit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

In the above-mentioned B block, except for the above-mentioned general formula containing at least one structural unit selected from the group consisting of the structural unit represented by the above-mentioned general formula (V) and the structural unit represented by the above-mentioned general formula (V') In addition to the structural unit shown in (IV), other structural units may be contained. As another structural unit, the structural unit of the ethylenically unsaturated monomer which can copolymerize with the ethylenic unsaturated monomer which derives the structural unit represented by the said general formula (IV) etc. is mentioned. Examples of monomers from which other structural units are derived include styrenes such as styrene and α-methylstyrene; vinyl ethers such as phenyl vinyl ether and the like.

In terms of the effect of the present invention, in the above-mentioned B block, when the total structural unit of the polymer chain is 100% by mass, the total ratio of other structural units is preferably 30% by mass or less, more preferably 10% by mass or less.

In terms of the dispersibility and dispersion stability of the color material, the mass average molecular weight Mw of the above-mentioned B block is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, and more preferably 15000 or less, More preferably, it is 12,000 or less. With the mass average molecular weight Mw of the B block in the above range, sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity part of the dispersant can be increased as described above The effect becomes good. Regarding the mass average molecular weight Mw of only the above-mentioned B block, it can be measured in the same manner as the following dispersant for a polymer having only the B block.

In addition, the B block contains the structural unit represented by the general formula (IV), and the glass transition temperature of the B block is 85°C or less, which will improve the development time delay and improve the coating suitability, so it is preferred . Here, the glass transition temperature (Tg) of the polymer chain of the B block in the present invention can be calculated by the following formula. 1/Tg=Σ(Xi/Tgi) Here, the polymer is assumed to be copolymerized with n monomer components of i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, Σ is the sum of i=1 to n. Furthermore, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be the value of the Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

Furthermore, in terms of dispersion stability, the acid value of the above-mentioned B block is preferably 10 mgKOH/g or less, and more preferably 0 mgKOH/g. Here, the acid value can be measured in the same manner as the acid value of the following dispersant for a polymer having only the B block. The above B block may also contain at least one structural unit selected from the group consisting of the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II), etc., a structural unit containing an acidic group, etc. As long as the effect of the present invention is not impaired, in terms of dispersion stability, when the total structural units of the above-mentioned B block are set to 100% by mass, the total ratio of structural units containing acidic groups is preferably 5% by mass or less, more preferably 0% by mass.

Furthermore, in terms of dispersion stability, the amine value of the above-mentioned B block is preferably 10 mgKOH/g or less, and more preferably 0 mgKOH/g. Here, the amine value of the B block can be measured in the same manner as the amine value of the above-mentioned polymer chain for a polymer having only the B block. The above-mentioned B block may also contain a structural unit containing a nitrogen atom, as long as the effect of the present invention is not impaired. In terms of dispersion stability and stability over time when the polyfunctional thiol compound is mixed, the above-mentioned When the total structural units of the B block are set to 100% by mass, the total ratio of the structural units containing nitrogen atoms is preferably 3% by mass or less, and more preferably 0% by mass.

Moreover, the said B block should just be selected so that it may function as a solvent affinity site, and a structural unit may contain 1 type, and may mix 2 or more types. When the above-mentioned B block contains two or more types of structural units, two or more types of structural units may be randomly copolymerized in the B block.

The bonding sequence of the block copolymer is not particularly limited, as long as the color material can be stably dispersed, but the bonding sequence in which the A block is bonded to one end of the block copolymer is the same as that of the color material. The interaction is excellent and the dispersants can effectively inhibit the aggregation of each other. The AB block copolymer or the ABA block copolymer is preferred, and the AB block copolymer is preferred.

In the block copolymer, the total content ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is preferably 3% by mass to 60% by mass, more preferably 6 Mass% to 45% by mass, more preferably 9% to 35% by mass. If the total content ratio of the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) in the block copolymer is within the above range, the affinity of the block copolymer with the color material The ratio of the sex parts becomes appropriate, and the decrease in solubility to organic solvents can be suppressed, so the adsorption to color materials becomes good, and excellent dispersibility, dispersion stability and solvent resolubility can be obtained.

On the other hand, in the above-mentioned block copolymer, the total content ratio of the B block is preferably 40% by mass to 97% by mass, more preferably 55% to 94% by mass, and still more preferably 65% by mass to 91% by mass. quality%. If the total content ratio of the B block in the block copolymer is within the above range, the ratio of the solvent affinity portion in the block copolymer becomes appropriate, the sufficient steric repulsion effect as a dispersant can be maintained, and the The effect of increasing the specific surface area of the solvent affinity part of the dispersant on the above effect becomes good. Furthermore, the content ratio of the above-mentioned structural unit is based on the structural unit represented by the above-mentioned general formula (I), the structural unit represented by the above-mentioned general formula (II), and the one represented by the above-mentioned general formula (IV) when the block copolymer is synthesized. Calculate the added amount of monomers such as structural units.

(Method of manufacturing block copolymer) The manufacturing method of the said block copolymer is not specifically limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method. The reason is that it is possible to produce copolymers with uniform molecular weight that are not easy to cause chain transfer or loss of activity, and the dispersibility can be improved. As the living polymerization method, living anionic polymerization methods such as living radical polymerization method and group transfer polymerization method, living cationic polymerization method, etc. may be mentioned. By using these methods to sequentially polymerize monomers, copolymers can be produced. For example, by first manufacturing the A block and then polymerizing the structural unit constituting the B block with the A block, a block copolymer can be manufactured. In addition, the polymerization order of the A block and the B block in the above-mentioned production method may be reversed. In addition, the A block and the B block may be produced separately, and thereafter, the A block and the B block may be coupled.

[Characteristics of dispersant] Also, in terms of dispersibility and dispersion stability, the mass average molecular weight Mw of at least one of the graft copolymer and the block copolymer is preferably 4000 or more, more preferably 5000 or more, and still more preferably 6000 or more. On the other hand, in terms of solvent resolubility, it is preferably 50,000 or less, and more preferably 30,000 or less. Also, in terms of dispersion stability, the ratio of the mass average molecular weight Mw to the number average molecular weight Mn (Mw/Mn) of the dispersant used as the graft copolymer is preferably 4.0 or less, more preferably 3.5 or less, and more Preferably, it is 3.0 or less. Also, in terms of dispersion stability, the ratio of the mass average molecular weight Mw to the number average molecular weight Mn (Mw/Mn) of the dispersant used as the block copolymer is preferably 1.8 or less, more preferably 1.6 or less, and more Preferably, it is 1.4 or less. Furthermore, in the present invention, the mass average molecular weight Mw and the number average molecular weight Mn are values measured by GPC (Gel Permeation Chromatography). The measurement system uses HLC-8120GPC manufactured by Tosoh Corporation. The elution solvent is N-methylpyrrolidone added with 0.01 mol/L lithium bromide, and the polystyrene standard for the calibration curve is set to Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation) and the measurement column is set to TSK-GEL ALPHA-M× 2 (manufactured by Tosoh Corporation).

In the present invention, in terms of dispersion stability, the acid value of at least one of the graft copolymer and the block copolymer is preferably 30 mgKOH/g or more, more preferably 35 mgKOH/g or more, More preferably, it is 40 mgKOH/g or more. On the other hand, in terms of solvent resolubility, the acid value of at least one of the graft copolymer and the block copolymer is preferably 180 mgKOH/g or less, more preferably 160 mgKOH/g or less, More preferably, it is 140 mgKOH/g or less. The acid value of the dispersant represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid component of the copolymer, and is based on the method described in JIS K 0070: 1992 The measured value.

In the present invention, the content ratio or structure of each structural unit of the dispersant can be determined by various mass analysis, NMR (nuclear magnetic resonance, nuclear magnetic resonance), etc. In addition, the dispersant may be decomposed by pyrolysis if necessary, and the obtained decomposed product may be decomposed by high performance liquid chromatography, gas chromatography mass spectrometer, NMR, elemental analysis, XPS (X-ray photoelectron spectrometer) , X-ray photoelectron spectrometer)/ESCA (electrospectroscopy for chemical analysis, electronic spectrometer for chemical analysis) and TOF-SIMS (time of flight secondary ion mass spectrometry, time of flight secondary ion mass spectrometry).

At least one of a dispersant-based graft copolymer and a block copolymer of the first invention, the graft copolymer having the structural unit represented by the general formula (I) and the structure represented by the general formula (II) The unit, the block copolymer has an A block containing the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). In the color material dispersion liquid of the first invention, as a dispersant, at least one of a graft copolymer and a block copolymer is contained, and the graft copolymer has the structural unit represented by the general formula (I) and the The structural unit represented by the general formula (II), the block copolymer has an A block containing the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), but may also contain Other well-known dispersants may be used as long as they do not impair the effect of the present invention. In the dispersant used in the color material dispersion liquid of the first invention, the total content ratio of at least one of the graft copolymer and the block copolymer is preferably 60% by mass or more, more preferably 70% by mass Above, it is more preferably 80% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass.

In the color material dispersion of the first invention, at least one of the above-mentioned graft copolymer and block copolymer is used as a dispersant, and the content depends on the type of color material used, and the following photosensitive color resin The concentration of solid components in the composition, etc. are appropriately selected. The content of the dispersant is preferably in the range of 3 parts by mass to 60 parts by mass, and more preferably in the range of 5 parts by mass to 45 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion liquid. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of a photosensitive colored resin composition will be more excellent. Moreover, if it is less than the said upper limit, development residue will become favorable. Furthermore, in the present invention, the solid components are all components other than the above-mentioned solvents, and also include monomers dissolved in the solvents.

＜Color material＞ In the present invention, the color material is not particularly limited, as long as it can emit the desired color when forming the coloring layer of the color filter. Various organic pigments, inorganic pigments, dispersible dyes, and dyes can be made. The salt compound etc. are used individually or in mixture of 2 or more types. Among them, organic pigments can be preferably used due to their higher color rendering properties and higher heat resistance. As an organic pigment, for example, a compound classified as a pigment in the Dyestuff Index (CI; issued by The Society of Dyers and Colourists) can be exemplified. Specifically, a compound marked with the following dye index (CI) number can be exemplified Compound.

CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35:1 , 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62: 1, 63, 65, 71, 73, 74, 75, 81 , 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 126, 127, 127 : 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163 , 164, 165, 166, 167, 168, 173, 175, 185, 194, 211, 214, 215, 231, and CI Pigment Yellow 150 derivative pigments; C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32 , 37, 38, 40, 41, 42, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 53 : 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60, 60: 1, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81:1 , 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 150, 151, 166, 168 , 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209 , 210, 214, 215, 216, 220, 221, 224, 226, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253 , 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291; C.I. Pigment Blue 1, 15, 15:1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, 61, 79, 80; CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 ； C.I. Pigment Brown 23, 25; C.I. Pigment Black 1, 7.

In addition, specific examples of the above-mentioned inorganic pigments include: titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow plum, zinc yellow, iron plum (red iron oxide (III)), cadmium red, ultramarine blue , Iron blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc.

For example, when the color material dispersion of the present invention is used as the following photosensitive colored resin composition to form a pattern of a light-shielding layer on the substrate of a color filter, a black pigment with higher light-shielding properties is blended into the ink. As black pigments with high light-shielding properties, for example, inorganic pigments such as carbon black or ferroferric oxide; or organic pigments such as cyanine black can be used.

As the above-mentioned dispersible dye, a dispersible dye can be exemplified by imparting various substituents to the dye or using it in combination with a solvent with low solubility. The salt-forming compound of the dye refers to the compound formed by the formation of a salt between the dye and the counter ion. For example, a salt-forming compound of a basic dye and an acid, a salt-forming compound of an acid dye and a base can be mentioned, and it also includes the use of the well-known lake The salting method is a lake pigment made by making the dye that is soluble in the solvent insoluble in the solvent. In the present invention, the dispersibility or dispersion stability of the color material can be improved by using a color material containing at least one selected from the group consisting of dyes and dye salt-forming compounds and the above-mentioned dispersant of the present invention.

染料、香豆素染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 再者，標準上只要相對於10 g之溶劑(或混合溶劑)，染料之溶解量為10 mg以下，便可判定為該染料可分散於該溶劑(或混合溶劑)中。As the above-mentioned dye, it can be suitably selected from previously known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, and

Dyes, coumarin dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. Furthermore, as long as the dissolved amount of the dye is 10 mg or less relative to 10 g of solvent (or mixed solvent), it can be judged that the dye can be dispersed in the solvent (or mixed solvent).

Among them, the color material contains selected from the group consisting of diketopyrrolopyrrole pigments, anthraquinone pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, bis-㗁𠯤 pigments, triarylmethane dyes, quinone When at least one of the group consisting of phthalone dyes, coumarin dyes, phthalocyanine dyes, and salt-forming compounds of these dyes, by using the above-mentioned dispersing agent, a high-brightness colored layer can be formed. good. In addition, as the above-mentioned color material, it is preferable to contain a diketopyrrolopyrrole pigment, a quinophthalone pigment, a copper phthalocyanine pigment, a zinc phthalocyanine pigment, a diacetyl pigment, a triarylmethane dye, and a quinophthalone dye. And at least one of the group consisting of the salt-forming compounds of the dyes.

As diketopyrrolopyrrole pigments, for example, CI Pigment Red 254, 255, 264, 272, 291 and the diketopyrrolopyrrole pigments represented by the following general formula (i) can be mentioned, of which, preferably selected from CI Pigment Reds 254, 272, 291 and at least one of diketopyrrolopyrrole pigments in ^{which R 21} and R ^{22 in the following general formula (i) are each 4-bromophenyl.}

(通式(i)中，R²¹ 及R²² 分別獨立地為4-氯苯基或4-溴苯基)[化9] General formula (i)

(In the general formula (i), R ²¹ and R ²² are each independently 4-chlorophenyl or 4-bromophenyl)

As an anthraquinone pigment, C.I. Pigment Red 177 etc. are mentioned, for example. As the quinophthalone pigment, for example, C.I. Pigment Yellow 138 may, for example, be mentioned. Examples of copper phthalocyanine pigments include: CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6; CI Pigment Green 7, 36, etc.; among them, Preferably, it is CI Pigment Blue 15:6. As the zinc phthalocyanine pigment, for example, C.I. Pigment Green 58, 59 and the like can be mentioned. As an aluminum phthalocyanine pigment, C.I. Pigment Green 62, 63, etc. are mentioned, for example. As the second pigment, C.I. Pigment Violet 23 and the like can be mentioned. As the quinophthalone dye, for example, C.I. Disperse Yellow 54, 64, 67, 134, 149, 160; C.I. Solvent Yellow 114, 157, etc.; among them, C.I. Disperse Yellow 54 is preferred. Examples of triarylmethane dyes include: C.I. Basic Red 9; C.I. Basic Blue 1, 7, and the like. The phthalocyanine dye may, for example, be C.I. Basic Blue 140.

The average primary particle size of the color material used in the present invention is not particularly limited, as long as it can emit the desired color when the coloring layer of the color filter is made, and it also depends on the type of color material used. The difference is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle size of the color material is within the above range, a display device equipped with a color filter manufactured using the color material dispersion of the present invention can be turned into a high-contrast and high-quality display device.

In addition, the average dispersed particle size of the color material in the color material dispersion liquid varies according to the type of color material used, preferably in the range of 10 nm to 100 nm, more preferably in the range of 15 nm to 60 nm Inside. The average dispersed particle diameter of the color material in the color material dispersion is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured with a laser light scattering particle size distribution meter. For the measurement of particle size by using a laser light scattering particle size distribution meter, the color material dispersion liquid can be appropriately diluted (for example, 1000 times, etc.) with the solvent used for the color material dispersion liquid to a concentration that can be measured by the laser light scattering particle size distribution meter , And use a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.) by dynamic light scattering method at 23°C for measurement. The average distribution particle size here is the volume average particle size.

The color material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt milling method. In addition, commercially available color materials can also be used after being refined.

In the color material dispersion of the present invention, the content of the color material is not particularly limited. In terms of dispersibility and dispersion stability, the content of the color material relative to 100 parts by mass of the total solid content in the color material dispersion, for example, is preferably in the range of 5 parts by mass to 80 parts by mass, more preferably Within the range of 8 parts by mass to 70 parts by mass. Especially in the case of forming a coating film or a colored layer with a high color material concentration, the content of the color material relative to 100 parts by mass of the total solid content in the color material dispersion is preferably 30 to 80 parts by mass Within the range, it is more preferably within the range of 40 parts by mass to 75 parts by mass.

＜Solvent＞ The solvent used in the present invention is not particularly limited, as long as it is an organic solvent that does not react with each component in the color material dispersion liquid and can dissolve or disperse them. The solvent can be used alone or in combination of two or more kinds. Specific examples of solvents include, for example, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxy Carbitol 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, 2-heptanone, etc.; methoxy ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butane acetate Ester, 3-methoxybutyl acetate, ethoxyethyl acetate and other glycol ether acetate solvents; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl card Carbitol acetate solvents such as BCA; Diacetate such as propylene glycol diacetate and 1,3-butanediol diacetate; Ethylene glycol monomethyl ether and ethylene diacetate Glycol ether solvents such as alcohol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; Aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; tetrahydrofuran, etc. Cyclic ether solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are suitably used in terms of solubility of other components. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetic acid in terms of solubility or coating suitability of other components. Ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate More than species.

In the color material dispersion liquid of the present invention, the solvent as described above is generally preferably 55% to 95% by mass, more preferably 65% to 90% by mass relative to the total amount of the color material dispersion containing the solvent , More preferably, it is in the range of 70% by mass to 88% by mass. If the solvent is too small, the viscosity tends to increase, and the dispersibility tends to decrease. In addition, if the solvent is too much, the color material concentration may decrease, making it difficult to achieve the target chromaticity coordinates.

＜Other ingredients＞ In the color material dispersion of the present invention, a dispersion auxiliary resin and other components may be further formulated as needed, as long as the effect of the present invention is not impaired. As the dispersion auxiliary resin, for example, the alkali-soluble resin exemplified in the following photosensitive colored resin composition may be mentioned. Due to the steric hindrance of the alkali-soluble resin, the color material particles are not easily in contact with each other, so there are cases where the dispersion is stabilized, or the dispersion stabilization effect has the effect of reducing the dispersant. In addition, as other ingredients, for example, surfactants to improve wettability, silane coupling agents to improve adhesion, defoamers, anti-shrinking agents, antioxidants, anti-cohesion agents, ultraviolet absorbers, etc. Wait.

The color material dispersion of the present invention is used as a preliminary preparation for preparing the following photosensitive colored resin composition. That is, the so-called color material dispersion liquid is prepared in advance in the stage before the preparation of the following photosensitive colored resin composition (mass of color material components in the composition)/(mass of solid components other than the color material components in the composition) A relatively high color material dispersion. Specifically, the ratio of (mass of color material components in the composition)/(mass of solid components other than the color material components in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid with the following components, a photosensitive colored resin composition having excellent dispersibility can be prepared.

<Method of manufacturing color material dispersion> In the present invention, the method for producing the color material dispersion is not particularly limited, as long as the color material dispersion is obtained by dispersing the color material in a solvent by the dispersant. In order to make the color material excellent in dispersibility and dispersion stability, as the method for producing the color material dispersion of the present invention, a method having the following steps can be exemplified: preparing the above-mentioned dispersant; and coloring in the presence of the above-mentioned dispersant The material is dispersed in the solvent.

In the above-mentioned manufacturing method, the color material can be dispersed using a previously known dispersing machine. Specific examples of the dispersing machine include: roller mills such as two-roll mills and three-roll mills, ball mills such as ball mills, vibrating ball mills, paint conditioners, continuous disc type bead mills, continuous ring type bead mills, etc. Bead mill. As a preferable dispersion condition for the bead mill, the particle size of the beads used is preferably 0.03 mm to 3.0 mm, more preferably 0.05 mm to 2.0 mm.

Specifically, the following method can be exemplified: pre-dispersing by 2.0 mm zirconia beads with a relatively large bead size, and then formal dispersion by using 0.1 mm zirconia beads with a relatively small bead size. Furthermore, after dispersion, it is preferable to filter with a filter of 0.5 μm to 2 μm.

＜Use＞ The color material dispersion and dispersant of the first invention are suitable for use as a color filter because they can produce a photosensitive colored resin composition that satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion at the same time. . In addition, the color material dispersion and dispersant of the first invention can also be used for coloring resin compositions or thermosetting coloring resin compositions that do not require photosensitive components. The first color material dispersion and dispersant of the present invention are used for various applications that require excellent dispersion stability of fine color materials, and are also used in inkjet inks or printing inks, recording tools, cosmetics, etc.

I-2. The photosensitive colored resin composition of the first invention The photosensitive colored resin composition of the first invention is characterized by containing a color material, the dispersant of the first invention described above, a polyfunctional monomer, a photoinitiator, and a solvent. Since the photosensitive colored resin composition of the first invention contains the dispersant, color material, and solvent of the first invention described above, it can be the same as the content described in the color material dispersion liquid of the first invention described above, while satisfying Excellent dispersion stability, solvent re-solubility and substrate adhesion.

The photosensitive colored resin composition of the first invention contains at least a color material, a dispersant, a polyfunctional monomer, a photoinitiator, and a solvent, and may further contain other components within a range that does not impair the effects of the invention. Hereinafter, each component contained in the photosensitive colored resin composition of the first invention will be described, but the dispersant, color material, and solvent are the same as those described in the color material dispersion liquid of the first invention. , So the description is omitted here.

＜Multifunctional monomer＞ The polyfunctional monomer used in the photosensitive colored resin composition is not particularly limited, as long as it can be polymerized by the following photoinitiator. Usually, a compound having two or more ethylenically unsaturated double bonds is used, especially It is preferably a multifunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups. As such a polyfunctional (meth)acrylate, what is necessary is just to select it suitably from a conventionally well-known thing, and use. As a specific example, for example, the one described in JP 2013-029832 A, etc. may be mentioned.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the photosensitive colored resin composition of the present invention requires excellent photocuring properties (high sensitivity), the multifunctional monomer preferably has 3 (trifunctional) or more polymerizable double bonds, preferably Poly(meth)acrylates of trivalent or higher polyols or their dicarboxylic acid-modified products are specifically preferably: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(methyl) Acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Modified succinic acid of penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. The content of the above-mentioned polyfunctional monomer used in the photosensitive colored resin composition is not particularly limited, and it is preferably in the range of, for example, 5 to 60% by mass relative to the total solid content of the photosensitive colored resin composition. , More preferably in the range of 10% by mass to 40% by mass. If the content of the multifunctional monomer is less than the above-mentioned lower limit, the photocuring may not proceed sufficiently and the exposed part may be eluted during development. If the content of the multifunctional monomer is more than the above upper limit, there may be an alkali Possibility of decline in sexual development.

等。作為光起始劑之具體例，可例舉：二苯甲酮、4,4'-雙二乙基胺基二苯甲酮、4-甲氧基-4'-二甲基胺基二苯甲酮等芳香族酮類、安息香甲醚等安息香醚類、乙基安息香等安息香、2-(鄰氯苯基)-4,5-苯基咪唑二聚物等聯咪唑類、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-㗁二唑等鹵甲基㗁二唑化合物、2-(4-丁氧基-萘-1-基)-4,6-雙-三氯甲基-S-三𠯤等鹵甲基-S-三𠯤系化合物、2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙酮、1,2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1,1-羥基-環己基-苯基酮、苄基、苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯硫醚、聯苯醯縮二甲醇、二甲胺基苯甲酸酯、對二甲胺基苯甲酸異戊酯、2-正丁氧基乙基-4-二甲胺基苯甲酸酯、2-氯9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、異丙基9-氧硫𠮿

、4-苯甲醯基-甲基二苯硫醚、1-羥基-環己基-苯基酮、2-苄基-2-(二甲基胺基)-1-[4-(4-嗎啉基)苯基]-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯基雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-(4-嗎啉基)-1-丙酮等。 其中，較佳為使用2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-(二甲基胺基)-1-(4-嗎啉基苯基)-1-丁酮、4,4'-雙(二乙基胺基)二苯甲酮、二乙基9-氧硫𠮿

。將如2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮之α-胺基苯乙酮系起始劑與如二乙基9-氧硫𠮿

之9-氧硫𠮿

系起始劑組合之情況因調整感度，抑制水斑，使顯影耐性提昇，故進而較佳。 使用α-胺基苯乙酮系起始劑及9-氧硫𠮿

]系起始劑之情形時該等之合計含量相對於感光性著色樹脂組合物之固形物成分總量，較佳為5質量%～15質量%。若起始劑量為15質量%以下，則製程中之昇華物減少故而較佳。若起始劑量為5質量%以上，則水斑等顯影耐性改善。<Photoinitiator> The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and it can be used alone or in combination of two or more from various previously known initiators. Examples of photoinitiators include aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α-amino ketones, biimidazoles, N,N-dimethylamino benzophenone , Halomethyl-S-tris series compounds, 9-oxysulfur

Wait. Specific examples of the photoinitiator include: benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone Aromatic ketones such as methyl ketone, benzoin ethers such as benzoin methyl ether, benzoin such as ethyl benzoin, biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-trichloro Halomethyl oxadiazole compounds such as methyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2-(4-butoxy-naphthalene-1-yl)-4 ,6-Bis-trichloromethyl-S-tris and other halomethyl-S-tris series compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzyl benzoic acid, methyl benzyl benzoate, 4-benzyl-4'-methyl diphenyl sulfide , Biphenyl dimethyl acetal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2- Chlorine 9-oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, Isopropyl 9-oxysulfur 𠮿

, 4-Benzyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-? (Alkolinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene Yl)-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzyl) phosphine oxide, 2-methyl-1 -[4-(Methylthio)phenyl]-2-(4-morpholinyl)-1-acetone and the like. Among them, it is preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-(dimethylamino) -1-(4-morpholinylphenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, diethyl 9-oxothio𠮿

. Combine the α-aminoacetophenone-based initiator such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one and diethyl 9- Oxysulfur 𠮿

Of 9-oxysulfur 𠮿

In the case of a combination of initiators, the sensitivity is adjusted, the water spot is suppressed, and the development resistance is improved, so it is more preferable. Use α-aminoacetophenone-based initiator and 9-oxysulfur 𠮿

] In the case of the initiator, the total content of these is preferably 5 to 15% by mass relative to the total solid content of the photosensitive colored resin composition. If the starting dose is 15% by mass or less, the sublimation in the process is reduced, so it is better. If the starting dose is 5% by mass or more, the development resistance such as water spots is improved.

In the present invention, in order to improve the sensitivity, the photoinitiator preferably contains an oxime ester-based photoinitiator. In addition, by using the oxime ester-based photoinitiator, it is easy to suppress the unevenness of the line width in the plane when the thin line pattern is formed. Furthermore, by using an oxime ester-based photoinitiator, there is a tendency that the residual film rate is increased and the effect of suppressing the generation of water spots is improved. Furthermore, the so-called water spots refer to the phenomenon that, if a component that improves alkaline developability is used, after alkaline developing is rinsed with pure water, a phenomenon such as water permeation marks is produced. This kind of water spots disappear after post-baking, so there is no problem as a product, but in the appearance inspection of the patterned surface after development, it will be detected as uneven and abnormal, resulting in the inability to distinguish between normal and abnormal products The problem. Therefore, if the inspection sensitivity of the inspection device decreases during the appearance inspection, the result will cause a decrease in the yield of the final color filter product, which may cause problems. As the oxime ester-based photoinitiator, in order to reduce the contamination of the photosensitive colored resin composition or the contamination of the device caused by the decomposition product, the one having an aromatic ring is preferred, and the condensed ring containing the aromatic ring is more preferred. Furthermore, it is more preferable to have a condensed ring containing a benzene ring and a heterocyclic ring. As the oxime ester-based photoinitiator, it can be selected from 1,2-octanedione-1-[4-(phenylthio)-,2-(phthaloyl oxime)], 1-[9-ethyl -6-(2-Methylbenzyl)-9H-carbazol-3-yl)-ethanone 1-(o-acetoxime), Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open The oxime ester-based photoinitiators described in 2001-233842, Japanese Patent Publication 2010-527339, Japanese Patent Publication 2010-527338, Japanese Patent Publication 2013-041153, etc. are appropriately selected. As commercially available products, IRGACURE OXE-01, Adeka Arkles NCI-930 with a diphenyl sulfide skeleton, TR-PBG-345, TR-PBG-304 with a carbazole skeleton, and TR-PBG with a pyridine skeleton can also be used -365, TR-PBG-3057 with a diphenyl sulfide skeleton (the above are manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), etc. Especially in terms of brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a sulphur skeleton. In addition, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton because of its high sensitivity. In addition, the combined use of two or more oxime ester-based photoinitiators is preferable because it is easy to improve the brightness, the residual film rate, and the effect of suppressing the generation of water spots is high. In particular, when two types of oxime ester-based photoinitiators having a diphenyl sulfide skeleton are used in combination, or an oxime ester-based photoinitiator having a diphenyl sulfide skeleton and an oxime ester-based photoinitiator having a diphenyl sulfide skeleton are used in combination , It is better because of higher brightness and higher heat resistance. In addition, the combination of an oxime ester-based photoinitiator having a carbazole skeleton and an oxime ester-based photoinitiator having a pyridine skeleton or an oxime ester-based photoinitiator having a diphenyl sulfide is excellent in sensitivity and brightness. Better.

系起始劑與肟酯系光起始劑組合會調整感度、抑制水斑且使顯影耐性提昇，故而較佳，將2種以上肟酯系光起始劑與9-氧硫𠮿

系起始劑組合會使亮度、殘膜率提昇、容易調整感度、抑制產生水斑之抑制效果較高且使顯影耐性提昇，故而較佳。In addition, a combination of a photoinitiator having a tertiary amine structure and an oxime ester-based photoinitiator can suppress water spots and increase sensitivity, which is preferable. The reason is that the photoinitiator with a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, so the free radicals generated from the initiator are not likely to lose activity due to oxygen, and the sensitivity can be improved. As a commercially available product of the photoinitiator having a tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one ( For example, IRGACURE 907; manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone (for example, IRGACURE 369; manufactured by BASF), 4,4'-bis(diethylamino)benzophenone (for example, Hicure ABP; manufactured by Kawaguchi Pharmaceutical Co., Ltd.) and the like. Also, put 9-oxysulfur 𠮿

The combination of an oxime ester-based photoinitiator and an oxime ester-based photoinitiator can adjust the sensitivity, suppress water spots, and improve the development resistance. Therefore, it is better to combine two or more oxime ester-based photoinitiators and 9-oxysulfur.

The combination of initiators can improve brightness, residual film rate, easy adjustment of sensitivity, high suppression effect of suppressing water spots, and improvement of development resistance, so it is preferable.

The content of the photoinitiator used in the photosensitive colored resin composition of the present invention is usually 0.01 parts by mass to 100 parts by mass, preferably 5 parts by mass to 60 parts by mass relative to 100 parts by mass of the above-mentioned polyfunctional monomer. share. If the content is more than the above lower limit, the photohardening progresses sufficiently to suppress the elution of the exposed part during development. On the other hand, if the content is less than the above upper limit, the yellowing of the obtained colored layer becomes weak, which can suppress The brightness drops. In addition, the total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is in the range of 0.1% by mass to 12.0% by mass relative to the total solid content of the photosensitive colored resin composition. Preferably, it is in the range of 1.0% by mass to 8.0% by mass.

＜Other ingredients＞ The photosensitive colored resin composition of the present invention may optionally contain a polyfunctional thiol compound, an alkali-soluble resin, an antioxidant, and various additives. (Multifunctional thiol compound) When the photosensitive resin composition of the present invention further contains a multifunctional thiol compound, the notch resistance is improved and the storage stability is good, so it is preferable. Here, the so-called notch resistance refers to the property that easily suppresses the following phenomena: the hardened product of the photosensitive resin composition is excessively corroded by the developer used in alkaline development, or due to the physical impact caused by the development water pressure. The material is peeling off. The multifunctional thiol compound generates sulfur-containing free radicals by free radicals generated from the photoinitiator during exposure. It is presumed that the unsaturated bond of the sulfur-containing free gene polyfunctional monomer undergoes a thiol-ene reaction, whereby crosslinking is performed to improve the curability of the coating film, and as a result, the notch resistance is improved. Furthermore, when an amine-based dispersant is used as a dispersant, etc., when there is a Michael addition catalyst such as a tertiary amine, the unsaturated bond between the multifunctional thiol compound and the multifunctional monomer causes the Michael Into a reaction. Therefore, if a polyfunctional thiol compound is used in a photosensitive resin composition containing an amine-based dispersant, a mico addition reaction will proceed during the storage process, and the stability will tend to deteriorate over time. In contrast, as described above, since the photosensitive resin composition of the present invention uses an acid-based dispersant, even if it contains a polyfunctional thiol compound, the storage stability is good.

The multifunctional thiol compound used in the present invention is a compound having two or more thiol groups in one molecule. The polyfunctional thiol compound can be appropriately selected and used from known compounds having two or more thiol groups in one molecule. In the photosensitive resin composition of this invention, a polyfunctional thiol compound may be used individually by 1 type, or may be used in combination of 2 or more types. Specific examples of the polyfunctional thiol compound include, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, and 1,6-hexanedithiol , 1,8-octanedithiol, 1,2-cyclohexanedithiol, decanedithiol, ethylene glycol bismercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol Dimercaptoacetate, 1,4-butanediol bismercaptoacetate, 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trimethylol Tris(3-mercaptopropionate), pentaerythritol tetramercaptoacetate, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionic acid) Ester); In addition, examples can also include: esters of various polyols and thiol-containing carboxylic acids such as thioglycolic acid and mercaptopropionic acid, trimercaptopropionic acid tris(2-hydroxyethyl) isocyanurate, 1 ,4-Dimethylmercaptobenzene, 2,4,6-trimercapto symmetrical trisulfide, 2-(N,N-dibutylamino)-4,6-dimercapto symmetrical trisulfide, etc.

The multifunctional thiol compound may be a multifunctional thiol compound having a substituent on the carbon atom at the α-position and/or β-position with respect to the thiol group. As such specific examples, for example, 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis(1-mercaptoethyl)benzene, phthalic acid bis(1- Mercaptoethyl), bis(2-mercaptopropyl) phthalate, bis(3-mercaptobutyl) phthalate, bis(3-mercaptoisobutyl), etc.

Also, exemplified: ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate) Butyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3- Mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2 -Mercaptopropionate), octanediol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), pentaerythritol tetra(2-mercaptopropionate), dipentaerythritol hexa( 2-mercaptopropionate), ethylene glycol bis(3-mercaptoisobutyrate), propylene glycol bis(3-mercaptoisobutyrate), diethylene glycol bis(3-mercaptoisobutyrate), butyl Diol bis(3-mercaptoisobutyrate), octanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), pentaerythritol tetra(3-mercaptoisobutyrate) Butyrate), dipentaerythritol hexa(3-mercaptoisobutyrate), ethylene glycol bis(2-mercaptoisobutyrate), propylene glycol bis(2-mercaptoisobutyrate), diethylene glycol bis( 2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolpropane tris(2-mercaptoisobutyrate) Ester), pentaerythritol tetra(2-mercaptoisobutyrate), dipentaerythritol hexa(2-mercaptoisobutyrate), ethylene glycol bis(4-mercaptovalerate), propylene glycol bis(4-mercaptoisovalerate) Ester), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylolpropane tri( 4-mercaptovalerate), pentaerythritol tetra(4-mercaptovalerate), dipentaerythritol hexa(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate), propylene glycol bis(3-mercapto Valerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), trimethylolpropane Tris(3-mercaptovalerate), pentaerythritol tetra(3-mercaptovalerate), dipentaerythritol hexa(3-mercaptovalerate) and the like.

In the present invention, the multifunctional thiol compound is preferably a multifunctional secondary thiol compound having a secondary thiol group in which the carbon atom to which the thiol group is bonded is a secondary carbon atom. The reason is that the secondary thiol has lower reactivity than the primary thiol, so it is difficult to react with each component in the photosensitive resin composition, and the storage stability of the photosensitive resin composition is excellent.

In addition, when the above-mentioned polyfunctional thiol compound is a polyfunctional thiol compound represented by the following general formula (A), the notch resistance is improved and the storage stability is good, which is preferable.

(通式(A)中，R^a 表示氫原子或碳數1～6之烷基，R^b 表示碳數1～6之伸烷基，Q表示羥基數2～6之多元醇之殘基，s係2～6之整數)[化10]

In (Formula ^(A), R ^a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms of, R ^b represents 1 to 6 carbon atoms extension of the group, Q represents a residue of the polyol hydroxyl number of 2 to 6, s is an integer from 2 to 6)

In the general formula (A), Ra is ^a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, in terms of storage stability of the photosensitive resin composition of, R ^a is preferably an alkyl group having a carbon number of 1 to 6, more preferably is alkyl of 1 to 3.

The alkyl group having 1 to 6 carbons is a linear, branched or cyclic alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, butyl Group, tertiary butyl group, various pentyl groups, various hexyl groups, cyclopentyl groups, cyclohexyl groups, etc. In addition, the alkylene group having 1 to 6 carbon atoms is a straight-chain or branched alkylene group, and examples thereof include: methylene, ethylene, trimethylene, propylene, various butylenes, and various pentylenes , All kinds of Shen Heji, etc.

In addition, Q is the residue of a polyhydric alcohol that forms an ester with a specific thiol group-containing carboxylic acid. As the polyol used here, ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. can be exemplified, but it is not limited to these. p represents the number of esters of a specific thiol group-containing carboxylic acid and a polyol, and is an integer of 2-6 corresponding to the number of hydroxyl groups in the residue of a polyol with a hydroxyl number of 2-6.

In the polyfunctional thiol compound used in the present invention, the number of thiol groups in one molecule is preferably 3 or more. In order to make the photosensitive resin composition excellent in storage stability and improve notch resistance, it is more It is preferably 3 to 6.

As the multifunctional thiol compound used in the present invention, among them, butanediol bis(3-mercaptopropionate) (BDTP), trimethylolpropane tris(3-mercaptopropionate) (TMTP), pentaerythritol four (3-mercaptopropionate) (PETP), tris (2-hydroxyethyl) isocyanurate tris (3-mercaptopropionate) (THEIC-BMPA), pentaerythritol tetrakis (3-mercaptobutyrate) (PTMP), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolethane tris(3-mercaptobutyrate) (TEMB), pentaerythritol tetra(3-mercaptopropionate) ) (PEMP) and other mercapto alkylate derivatives; ethylene glycol dimercaptoacetate (EGTG), butanediol dimercaptoacetate (BDTG), hexanediol dimercaptoacetate (HDTG), trimethylol Thioglycolic acid derivatives such as trithioglycolate (TMTG) and pentaerythritol tetramercaptoacetate (PETG); 1,4-bis(3-mercaptobutanoyloxy)butane, 1,3,5-tri (3-Mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione is preferred because it improves notch resistance and has good storage stability , But not limited to this.

The content of the polyfunctional thiol compound is preferably in the range of 0.01% by mass to 15.0% by mass, and more preferably in the range of 0.1% by mass to 10.0% by mass relative to the total solid content of the photosensitive colored resin composition. Within the range, more preferably within the range of 0.5% by mass to 5.0% by mass. If it is more than the said lower limit, it will become easy to improve notch resistance. On the other hand, if it is not more than the above upper limit value, it is easy to suppress the generation of development residue.

(Alkali-soluble resin) In the photosensitive colored resin composition of the present invention, since the dispersant has a carboxyl group, it can also function as an alkali-soluble resin. Therefore, an alkali-soluble resin different from the above-mentioned dispersant is not an essential component. In the photosensitive colored resin composition of the present invention, in order to easily adjust the alkali solubility, it is preferable to further contain an alkali-soluble resin different from the above-mentioned dispersant. The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that function as a binder resin and are soluble in the alkali developer used for pattern formation. In the present invention, the so-called alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard. The preferred alkali-soluble resins in the present invention are resins with acidic groups, usually resins with carboxyl groups, and specific examples include acrylic resins such as acrylic copolymers with carboxyl groups and styrene-acrylic copolymers with carboxyl groups , Epoxy (meth)acrylate resin with carboxyl group, etc. Among them, those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferred. The reason is that by containing the photopolymerizable functional group, the film strength of the formed cured film is improved. In addition, acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins can also be used in combination of two or more types.

Acrylic resins such as acrylic copolymers containing structural units with carboxyl groups and styrene-acrylic copolymers with carboxyl groups, for example, are prepared by a well-known method in which ethylenically unsaturated monomers containing carboxyl groups and optionally added Copolymerization of other monomers (co)polymerization and obtained polymer (co)polymer. As the carboxyl group-containing ethylenically unsaturated monomer, for example, (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, ethylene Methylsuccinic acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of monomers with hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride or phthalic anhydride and cyclohexanedicarboxylic anhydride can also be used , Ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, acid anhydride-containing monomers such as maleic anhydride, methylene succinic anhydride, and methyl maleic anhydride may also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

In order to have excellent adhesion of the colored layer, the alkali-soluble resin preferably further has a hydrocarbon ring. Obtained the following insights: by having a hydrocarbon ring as a bulky group in the alkali-soluble resin, the obtained colored layer has good solvent resistance, especially the swelling of the colored layer is suppressed. The effect is not clear, but it is estimated that the inclusion of a large hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer. As a result, the strength of the coating film is increased, thereby suppressing swelling caused by the solvent. Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and combinations of these. The hydrocarbon ring may have a carbonyl group, a carboxyl group, an oxycarbonyl group, and an amido group. And other substituents. Among them, when an aliphatic ring is included, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved. Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cyclopentane, cyclohexane, norethane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) Aliphatic hydrocarbon rings such as, adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and stilbene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, or the following chemical formula ( ii) CARDO structure, etc. as indicated.

[化11] Chemical formula (ii)

When an aliphatic ring is included as a hydrocarbon ring, it is preferable because the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved. In addition, when the CARDO structure represented by the above chemical formula (ii) is included, the curing property of the colored layer is improved, and the solvent resistance (inhibiting the swelling of NMP (N-Methyl pyrrolidone)) is improved. Especially good.

In the alkali-soluble resin used in the present invention, the use of an acrylic copolymer containing the structural unit having the above-mentioned hydrocarbon ring in addition to the structural unit having the carboxyl group makes it easy to adjust the amount of each structural unit, and it is easy to increase the amount of the above-mentioned hydrocarbon The amount of structural unit of the ring improves the function of the structural unit, so it is preferable. The acrylic copolymer containing a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". As the ethylenically unsaturated monomer having the above-mentioned hydrocarbon ring, for example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylic acid may be mentioned. Isopropyl ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., have a greater effect on maintaining the cross-sectional shape of the colored layer after development during heat treatment. Preferred are cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzene Vinyl.

In addition, the alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resin and the dispersant of the present invention can form a cross-linked bond during the curing step of the resin composition when the color filter is manufactured, and the alkali-soluble resin is mutually Or the alkali-soluble resin and the photopolymerizable compound may form a crosslinked bond. Therefore, if an alkali-soluble resin having an ethylenic double bond in the side chain is used in combination with the dispersant of the present invention, the synergistic effect will increase the film strength of the cured film, and therefore the brightness of the colored layer and the ITO film can be improved. The resistance to cracking and, in addition, the development resistance is improved, and the heat shrinkage of the cured film is suppressed, so that the adhesion to the substrate becomes excellent. The method of introducing the ethylenic double bond into the alkali-soluble resin may be appropriately selected from previously known methods. For example, the following method can be exemplified: a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of the alkali-soluble resin to convert the vinyl Introduce a double bond into the side chain; or when a structural unit with a hydroxyl group is introduced into the copolymer, a compound with an isocyanate group and an ethylenic double bond in the molecule is added to introduce the ethylenic double bond to the side Chain.

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

The alkali-soluble resin used in the present invention preferably includes acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having structural units with carboxyl groups and structural units with hydrocarbon rings, and more preferably includes structures having carboxyl groups Acrylic resins such as acrylic copolymers and styrene-acrylic copolymers such as units, structural units having a hydrocarbon ring, and structural units having an ethylenic double bond.

Regarding the alkali-soluble resin, by appropriately adjusting the addition amount of each structural unit, an alkali-soluble resin with required properties can be made.

In order to obtain a good pattern, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, and more preferably 10% by mass or more with respect to the total amount of monomers. On the other hand, in order to suppress film roughness on the surface of the pattern after development, the addition amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and more preferably 40% by mass or less relative to the total amount of monomers. . If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is more than the above lower limit, the obtained coating film has sufficient solubility with respect to the alkaline developer, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is When the value is below the above upper limit, it tends to be less likely to cause the pattern to be formed to fall off from the substrate or the film on the surface of the pattern is rough during development with an alkaline developer.

In addition, it is more preferably used as an alkali-soluble resin in acrylic copolymers containing structural units with ethylenic double bonds and acrylic resins such as styrene-acrylic copolymers, which have both epoxy groups and ethylenic double bonds. The addition amount of the compound relative to the carboxyl group-containing ethylenically unsaturated monomer is preferably 10% by mass to 95% by mass, more preferably 15% by mass to 90% by mass.

The weight average molecular weight (Mw) of the preferred copolymer containing carboxyl groups is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. If it is less than 1,000, the function of the adhesive after curing may be significantly reduced, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer. Furthermore, polystyrene can be used as the standard substance and THF (Tetrahydrofuran) as the eluent, and the weight average molecular weight of the copolymer containing carboxyl group can be determined by using Shodex GPC System-21H (Shodex GPC System-21H). Mw).

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but an epoxy (meth)acrylate obtained by reacting the reactant of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride The compound is more suitable. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected and used from known ones. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, respectively, and may use 2 or more types together.

Regarding the alkali-soluble resin, in terms of the developability (solubility) with respect to the alkaline aqueous solution used in the developer, it is preferable to select and use one having an acid value of 50 mgKOH/g or more. In terms of the developability (solubility) relative to the alkaline aqueous solution used in the developer and the adhesion to the substrate, the acid value of the alkali-soluble resin is preferably 60 mgKOH/g or more and 300 mgKOH/g Hereinafter, among them, it is preferably 70 mgKOH/g or more and 200 mgKOH/g or less. Furthermore, the acid value of the alkali-soluble resin can be measured in accordance with JIS K 0070:1992.

In order to obtain the effects of improving the film strength of the cured film, improving the development resistance, and excellent adhesion to the substrate, the ethylenic unsaturated bond equivalent is preferably 100 when the side chain of the alkali-soluble resin has an ethylenic unsaturated group. Within the range of ~2000, preferably within the range of 140-1500. If the ethylenically unsaturated bond equivalent is 100 or more, the development resistance or adhesiveness is excellent. In addition, if the ethylenically unsaturated bond equivalent is 2000 or less, the ratio of other structural units such as the structural unit having a carboxyl group or the structural unit having a hydrocarbon ring can be relatively increased, so that the developability and heat resistance are excellent. Here, the ethylenically unsaturated bond equivalent is the weight average molecular weight of the ethylenically unsaturated bond in the alkali-soluble resin per 1 mole, and is represented by the following formula (1).

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

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

The alkali-soluble resin used in the photosensitive color resin composition may be used individually by 1 type, and may be used in combination of 2 or more types. The content of the alkali-soluble resin is not particularly limited, but it is preferably in the range of 1% by mass to 60% by mass, and more preferably in the range of 5% by mass to 5% by mass relative to the total solid content of the photosensitive colored resin composition. Within the range of 40% by mass. If the content of the alkali-soluble resin is more than the above lower limit value, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is less than the above upper limit value, film roughness or pattern notch during development can be suppressed.

(Antioxidants) When the photosensitive colored resin composition of the present invention further contains an antioxidant, the heat resistance is improved, the fading of the color material is suppressed, and the brightness is improved, which is preferable. The antioxidant may be appropriately selected from those previously known. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. In terms of heat resistance, preferred are Use hindered phenol antioxidants. It may also be a latent antioxidant as described in International Publication No. 2014/021023.

Examples of hindered phenol-based antioxidants include: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010; manufactured by BASF Corporation), Isocyanuric acid 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) ester (trade name: IRGANOX3114; manufactured by BASF Corporation), 2,4,6-tris(4- Hydroxy-3,5-di-tertiary butylbenzyl)-1,3,5-trimethylbenzene (trade name: IRGANOX1330; manufactured by BASF), 2,2'-methylene bis(6-tertiary butyl) 4-methylphenol) (trade name: SUMILIZER MDP-S; manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX1081 ; BASF Corporation), 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate (trade name: IRGAMOD195; BASF Corporation) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010; BASF Manufactured by the company).

If the photosensitive colored resin composition composition of the present invention contains the above-mentioned oxime ester-based photoinitiator and antioxidant, the synergistic effect is used to increase brightness, increase residual film rate, and increase linearity when forming fine line patterns or follow the mask. The line width design improves the ability to form fine line patterns, so it is better.

The content of the antioxidant is, for example, preferably 0.1% by mass to 10.0% by mass, and more preferably 0.5% by mass to 5.0% by mass relative to the total amount of solid content of the photosensitive colored resin composition. 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 above upper limit, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

When an antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, as the blending amount of the antioxidant, relative to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator, the antioxidant is preferably 1 part by mass -250 parts by mass, more preferably 3 parts by mass to 80 parts by mass, and still more preferably 5 parts by mass to 45 parts by mass. If it is in the above-mentioned range, the effect of the above-mentioned combination is excellent.

(Various additives) Various additives may be contained in the photosensitive colored resin composition of this invention. As an additive, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, an adhesion promoter, etc. are mentioned, for example. As a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.

Also, as the silane coupling agent, for example, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicones), etc. Among them, in terms of the adhesion of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacrylic group and an acrylic group are preferable.

As the content of the silane coupling agent, relative to 100 parts by mass of the total solid content in the photosensitive colored resin composition, the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass the following. If it is more than the said lower limit and less than the said upper limit, the adhesiveness of a base material will be excellent.

<The blending ratio of the components in the photosensitive colored resin composition> The total content of the color material is preferably in the range of 3% by mass to 65% by mass, and more preferably in the range of 4% by mass to 60% by mass relative to the total solid content of the photosensitive colored resin composition. If it is more than the above lower limit, the coloring layer has sufficient color density when the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm). Moreover, if it is less than the said upper limit, the coloring layer which is excellent in storage stability and has sufficient hardness or adhesion to a substrate can be obtained. Especially in the case of forming a coloring layer with a high color material concentration, the content of the color material relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of, for example, 15% to 75% by mass, and more It is preferably in the range of 25% by mass to 70% by mass. In addition, the content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed, but for example, it is preferably 1% to 40% by mass relative to the total solid content of the photosensitive colored resin composition. Within the range, it is more preferably in the range of 2% by mass to 30% by mass, and still more preferably in the range of 3% by mass to 25% by mass. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of a photosensitive colored resin composition will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a coloring layer with a high color material concentration, the content of the dispersant relative to the total solid content of the photosensitive colored resin composition is preferably in the range of 2% by mass to 25% by mass, and more Preferably, it is in the range of 3% by mass to 20% by mass. In addition, the content of the solvent may be appropriately set within the range where the coloring layer can be formed with high accuracy. The content of the solvent is preferably in the range of 55% to 95% by mass, and more preferably in the range of 65% to 88% by mass relative to the total amount of the photosensitive colored resin composition containing the solvent. When the content of the above-mentioned solvent is within the above-mentioned range, the coatability can be excellent.

<Method for manufacturing photosensitive colored resin composition> The method for producing the photosensitive colored resin composition of the present invention is not particularly limited. For example, it can be achieved by adding a polyfunctional monomer, a photoinitiator, an alkali-soluble resin, if necessary, to the color material dispersion of the present invention. Other ingredients are obtained by mixing using a known mixing method. Alternatively, it can be obtained by adding a color material, the above-mentioned dispersant of the present invention, a multifunctional monomer, a photoinitiator, a solvent, an alkali-soluble resin added as necessary, and other components, and mixing using a known mixing method.

＜Use＞ The photosensitive colored resin composition of the first invention can satisfy excellent dispersion stability, solvent resolubility, and substrate adhesion at the same time, so it is suitable for color filter applications among them. The photosensitive colored resin composition of the first invention is used for various applications requiring excellent dispersion stability of fine color materials, and is also used for inkjet inks or printing inks.

I-3. The first color filter of the present invention The color filter of the first invention includes at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition of the first invention.

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

＜Colored layer＞ The colored layer used in the color filter of the present invention is at least one colored layer of the cured product of the photosensitive colored resin composition of the present invention. The colored layer is usually formed in the opening of the light-shielding portion on the following substrate, and usually contains a colored pattern of more than three colors. In addition, the arrangement of the colored layers is not particularly limited, and it can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type. In addition, the width and area of the colored layer can be arbitrarily set. The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive colored resin composition, etc., and is usually preferably in the range of 1 μm to 5 μm.

This colored layer can be formed by the following method, for example. First, the above-mentioned photosensitive colored resin composition of the present invention is applied to the coating method using spray coating method, dip coating method, bar coating method, roll coating method, spin coating method, die nozzle coating method, etc. A wet coating film was formed on the following substrate. Among them, the spin coating method and the die nozzle coating method can be preferably used. Then, after the wet coating film is dried using a hot plate or oven, etc., the coating film is exposed through a mask of a predetermined pattern, and the alkali-soluble resin and polyfunctional monomer are photopolymerized to make the cured product.涂膜。 Coating. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, can be mentioned, for example. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, in order to promote the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected according to the blending ratio of the components in the photosensitive colored resin composition used, the thickness of the coating film, and the like.

Then, a developing solution is used to perform a development process to dissolve and remove the unexposed part, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. It is also possible to add an appropriate amount of surfactants and the like to the alkaline solution. In addition, general methods can be adopted for the development method. After the development treatment, the developer is usually washed, and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. In addition, after the development treatment, heat treatment may be performed in order to sufficiently harden the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

＜Shading part＞ The light-shielding part in the color filter of the present invention is formed in a pattern on the substrate described below, and can be made the same as the light-shielding part generally used as a light-shielding part for a color filter. The pattern shape of the light-shielding portion is not particularly limited, and for example, a stripe shape, a matrix shape, or the like may be mentioned. The light-shielding part may also be a metal thin film such as chromium obtained by a sputtering method, a vacuum evaporation method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin adhesive. When the resin layer contains light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using inkjet ink containing light-shielding particles, and a photosensitive resist Methods of thermal transfer, etc.

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

＜Substrate＞ As the substrate, the following transparent substrates, silicon substrates, and those having aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the transparent substrate or silicon substrate can be used. Other color filter layers, resin layers, transistors such as TFTs (Thin-film transistors), circuits, etc. can also be formed on these substrates. The transparent substrate in the color filter of the present invention is not particularly limited, as long as it is a substrate that is transparent to visible light, and a transparent substrate used in general color filters can be used. Specific examples include: transparent rigid materials that are not flexible, such as quartz glass, alkali-free glass, and synthetic quartz plates; or transparent and flexible materials such as transparent resin films, optical resin plates, and flexible glass. The thickness of the transparent substrate is not particularly limited. According to the application of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used. Furthermore, the color filter of the present invention may be formed with, for example, an overcoat layer or a transparent electrode layer, in addition to the above-mentioned substrate, light-shielding portion, and coloring layer, and then an alignment film or columnar spacers.

I-4. The first display device of the present invention The display device of the first invention is characterized by having the color filter of the first invention described above. The structure of the display device in the first invention is not particularly limited, and it can be appropriately selected from previously known display devices. For example, a liquid crystal display device or an organic light-emitting display device can be exemplified.

[Liquid crystal display device] As the liquid crystal display device of the present invention, for example, a liquid crystal display device having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate can be exemplified . With reference to the drawings, the liquid crystal display device of the present invention will be described on the other. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and liquid crystal formed between the color filter 10 and the counter substrate 20. Layer 30. In addition, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and may be a structure generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. As such a driving method, for example, a TN (Twisted Nematic, twisted nematic) method, an IPS (In-Plane Switching, lateral electric field effect) method, an OCB (Optically Compensated Birefringence, optically compensated bending arrangement) method, and MVA may be mentioned. (Multi-domain Vertical Alignment, multi-quadrant vertical alignment) method and so on. In the present invention, any of the above-mentioned methods can be suitably used. In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy, and mixtures thereof can be used in accordance with the driving method of the liquid crystal display device of the present invention.

As a method of forming the liquid crystal layer, a method generally used as a method of manufacturing a liquid crystal cell can be used. For example, a vacuum injection method or a liquid crystal dropping method can be mentioned. After the liquid crystal layer is formed by the above-mentioned method, the liquid crystal cell is slowly cooled to normal temperature, so that the enclosed liquid crystal can be aligned.

[Organic Light Emitting Display Device] As the organic light-emitting display device of the present invention, for example, an organic light-emitting display device including the above-mentioned color filter and organic light-emitting body of the present invention can be exemplified. With reference to the drawings, the organic light emitting display device of the present invention will be described on the other. FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. As shown in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. It is also possible to have an organic protective layer 50 or an inorganic oxide film 60 between the color filter 10 and the organic light-emitting body 80.

As a layering method of the organic light-emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode are sequentially formed on the upper surface of the color filter. The method of 76; or the method of attaching the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60, etc. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light-emitting body 80, as well as other structures, can be suitably known. The organic light emitting display device 100 fabricated in this manner can be applied to, for example, an organic EL display in a passive driving mode, and can also be applied to an organic EL display in an active driving mode. Furthermore, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a configuration generally known as a liquid crystal display device using a color filter.

II. The second invention Hereinafter, the color material dispersion liquid, the photosensitive colored resin composition, the color filter, the liquid crystal display device, and the organic light emitting display device of the second invention will be described in detail in order. II-1. The second color material dispersion of the present invention The second color material dispersion of the present invention contains color materials, dispersants and solvents, and the above dispersants have structural units derived from carboxyl-containing ethylenically unsaturated monomers and are represented by the following general formula (III) The polymer chain in the structural unit represented by the general formula (III) contains at least one of a graft copolymer and a block copolymer, and the graft copolymer is selected from the following general formula (V) At least one structural unit in the group consisting of the structural unit represented by the following general formula (V') and the structural unit represented by the following general formula (V'), the block copolymer has: A block, which contains ethylene derived from a carboxyl group The structural unit of a sexually unsaturated monomer; and the B block, which includes a structural unit selected from the group consisting of a structural unit represented by the following general formula (V) and a structural unit represented by the following general formula (V') At least one structural unit.

(通式(III)中，R^1'' 表示氫原子或甲基，A¹ 表示直接鍵結或2價連結基，Polymer表示聚合物鏈)[化12]

(In the general formula (III), R ^1'' represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain)

(通式(V)中，R^11' 係氫原子或甲基，A^2' 係2價連結基，R⁵ 係伸乙基或伸丙基，R⁶ 係氫原子或烴基，m表示2以上80以下之數；  通式(V')中，R^11'' 係氫原子或甲基，A^2'' 係2價連結基，R⁷ 係碳數為1～10之伸烷基，R⁸ 係碳數為3～7之伸烷基，R⁹ 係氫原子或烴基，n表示1以上40以下之數)[化13]

(Formula (V) in, R ^{11 'based} hydrogen atom or a methyl group, A ^2' based divalent linking group, R ⁵ or extension line extending ethyl propyl, R ⁶ a hydrogen atom or a hydrocarbon-based, m represents 2 or more A number below 80; In the general formula (V'), R ^11" is a hydrogen atom or a methyl group, A ^2" is a divalent linking group, R ⁷ is an alkylene group with 1 to 10 carbon atoms, and R ⁸ It is an alkylene group having 3 to 7 carbon atoms, R ⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number from 1 to 40)

The second color material dispersion of the present invention uses the above-mentioned specific graft copolymer or block copolymer as a dispersant, and the above-mentioned specific graft copolymer or block copolymer contains a structure derived from a carboxyl-containing ethylenically unsaturated monomer Unit and at least one structural unit selected from the group consisting of the structural unit represented by the above general formula (V) and the structural unit represented by the above general formula (V'), so that it is possible to produce a substrate that is excellent at the same time Adhesion and developability (shortening of development time) photosensitive colored resin composition. Regarding the above-mentioned specific graft copolymer or block copolymer used in the second invention, it is considered that since it contains a structural unit derived from an ethylenically unsaturated monomer containing a carboxyl group, it is combined with the glass surface as a substrate, etc. The interaction of the polar groups improves the adhesion of the coating film to the base material, and because it contains structural units with polyethylene oxide chains, polypropylene oxide chains or ester chains, the use of polyethylene oxide chains and polycyclic The oxygen atoms contained in the oxypropane chain or the ester chain are hydrogen-bonded with the alkaline developer, and are easily dissolved in the alkaline developer during development, thereby shortening the development time.

The color material dispersion liquid of the second invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, each component of the color material dispersion liquid of this second invention will be described in detail in order from the dispersant which is the characteristic of the second invention.

<The dispersant used in the second invention> The dispersant used in the second invention is the dispersant of the second invention and has a structural unit derived from a carboxyl-containing ethylenically unsaturated monomer and a structural unit represented by the above general formula (III), the general formula ( III) At least one of a polymer chain graft copolymer and a block copolymer in the structural unit represented, the graft copolymer includes a structural unit selected from the structural unit represented by the general formula (V) and the general formula At least one structural unit in the group consisting of the structural unit represented by (V'), the block copolymer has: A block containing a structural unit derived from an ethylenically unsaturated monomer containing a carboxyl group; and The B block includes at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V').

[Graft Copolymer] The graft copolymer used in the second invention has a structural unit derived from a carboxyl-containing ethylenically unsaturated monomer that functions as an adsorption site for color materials in the main chain, and further has a solvent affinity in the side chain. The structural unit represented by the above-mentioned general formula (III) of the grafted polymer chain that functions as the site, in the grafted polymer chain, includes the structural unit selected from the above-mentioned general formula (V) and the above-mentioned general formula (V) At least one structural unit in the group consisting of the structural unit represented by').

The structural unit derived from the carboxyl-containing ethylenically unsaturated monomer in the second invention may be the same as the structural unit derived from the carboxyl-containing ethylenically unsaturated monomer in the first invention, and may be optional At least one of the structural unit represented by the above-mentioned general formula (I) and the structural unit represented by the above-mentioned general formula (II) in the first invention. The structural unit represented by the general formula (I) may be the same as the structural unit represented by the general formula (I) in the first invention, and the structural unit represented by the general formula (II) may be the same as The structural units represented by the general formula (II) in the first invention described above are the same.

The graft copolymer used in the second invention has the structural unit represented by the above general formula (III), and the polymer chain contained in the structural unit represented by the general formula (III) functions as a solvent affinity site. In the graft copolymer used in the second invention, the polymer chain in the structural unit represented by the general formula (III) includes a structural unit selected from the structural unit represented by the general formula (V) and the general formula (V) At least one structural unit in the group consisting of the structural unit represented by').

The structural unit represented by the general formula (III) may be the same as the structural unit represented by the general formula (III) in the first invention, and the structural unit represented by the general formula (V) may be The structural unit represented by the general formula (V) in the first invention described above is the same, and the structural unit represented by the general formula (V') may be the same as the structural unit represented by the general formula (V') in the first invention. The structural units shown are the same.

In the above-mentioned polymer chain, at least one structural unit selected from the group consisting of the structural unit represented by the above general formula (V) and the structural unit represented by the above general formula (V') may be one kind alone, Two or more types can also be mixed. In order to improve the adhesion of the substrate and shorten the development time, when the total structural unit of the polymer chain in the macromonomer of the graft copolymer is set to 100% by mass, it is selected from the general formula (V). The total ratio of at least one structural unit in the group consisting of the structural unit represented and the structural unit represented by the general formula (V') is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably It is 15% by mass or more. In terms of solvent resolubility, when the total structural unit of the polymer chain is 100% by mass, it is selected from the structural unit represented by the general formula (V) and the general formula (V'). The total ratio of at least one structural unit in the group consisting of the structural unit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

Among the structural units of the polymer chain in the structural unit represented by the general formula (III) of the graft copolymer used in the second invention, it is preferred that, in addition to including those selected from those represented by the general formula (V) In addition to at least one structural unit in the group consisting of the structural unit and the structural unit represented by the general formula (V'), it further includes a structural unit selected from the structural unit represented by the general formula (V) and the general formula ( The structural unit represented by the above general formula (IV) in which at least one structural unit is different from the group consisting of the structural unit represented by V'). The structural unit represented by the above general formula (IV) may be the same as the structural unit represented by the above general formula (IV) in the first invention.

In the above-mentioned polymer chain, the above-mentioned general formula is different from at least one structural unit selected from the group consisting of the structural unit represented by the above-mentioned general formula (V) and the structural unit represented by the above-mentioned general formula (V') The structural unit represented by (IV) may be one type alone, or two or more types may be mixed. When the total structural unit of the polymer chain in the macromonomer of the graft copolymer is set to 100% by mass, it is selected from the structural unit represented by the general formula (V) and the general formula (V') The total ratio of the structural units represented by the general formula (IV) in which at least one structural unit is different from the group consisting of the structural units represented is preferably 20% by mass or more in terms of solvent resolubility, It is more preferably 30% by mass or more, and still more preferably 40% by mass or more. In order to improve the adhesion of the substrate and shorten the development time, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

In addition, among the structural units of the polymer chain in the structural unit represented by the general formula (III) of the graft copolymer used in the second invention, except for the structure selected from the structure represented by the general formula (V) In addition to the structural unit represented by the aforementioned general formula (IV), other structural units may be included in at least one structural unit in the group consisting of the unit and the structural unit represented by the aforementioned general formula (V'). As this other structural unit, the structural unit derived from the ethylenic unsaturated monomer which can copolymerize with the ethylenic unsaturated monomer which derives the structural unit represented by the said general formula (IV) etc. is mentioned. Regarding the monomer deriving the other structural unit and the total ratio thereof, it may be the same as the monomer deriving the other structural unit in the first invention described above.

In addition, the mass average molecular weight Mw, glass transition temperature, acid value, and amine value of the polymer chain may be the same as the mass average molecular weight Mw and glass transition of the polymer chain in the graft copolymer used in the first invention. The temperature, acid value, and amine value are the same.

In the graft copolymer used in the second invention, the total content of the structural units derived from the carboxyl group-containing ethylenically unsaturated monomer is preferably 3% by mass to 60% by mass, more preferably 6 Mass% to 45% by mass, more preferably 9% to 35% by mass. If the total content ratio of the above-mentioned carboxyl-containing ethylenically unsaturated monomer-derived structural units in the graft copolymer is within the above range, the ratio of the affinity portion with the color material in the graft copolymer becomes appropriate. And it can suppress the decrease in solubility to organic solvents, so the adsorption to color materials becomes good, and excellent dispersibility, dispersion stability and solvent re-solubility can be obtained. On the other hand, in the graft copolymer, the total content of the structural units represented by the general formula (III) is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and further It is preferably 65% by mass to 91% by mass. If the total content ratio of the structural units represented by the above general formula (III) in the graft copolymer is within the above range, the ratio of the solvent affinity part in the graft copolymer becomes appropriate, and the dispersant can be maintained as a dispersant. Sufficient steric repulsion effect, and the effect of the above effect can be improved by increasing the specific surface area of the solvent affinity part of the dispersant. Furthermore, the content ratio of the above-mentioned structural units is based on the ratio of the above-mentioned structural units derived from the above-mentioned carboxyl-containing ethylenically unsaturated monomers and the above-mentioned structural units represented by the general formula (III). Calculate the addition amount.

The above-mentioned graft copolymer used in the second invention may also be within a range that does not impair the effect of the invention, except for having the above-mentioned structural unit derived from the carboxyl-containing ethylenically unsaturated monomer, and the above-mentioned general formula (III) In addition to the structural unit represented by ), there are other structural units. Regarding other structural units, an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer that derives the structural unit represented by the general formula (III) and the like can be appropriately selected to be copolymerized, and other structural units can be introduced. As another structural unit copolymerized with the structural unit represented by the above-mentioned general formula (III) in the main chain, for example, the structural unit represented by the above-mentioned general formula (IV) and the like can be exemplified. In the above-mentioned graft copolymer, the total content ratio of other structural units copolymerized in the main chain is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass.

[Block copolymer] The block copolymer used in the second invention has: A block, which contains a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer and functions as an adsorption site for color materials; and a B block, It contains at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V'), and functions as a solvent affinity site.

In the A block of the block copolymer used in the second invention, the above-mentioned structural unit derived from the carboxyl-containing ethylenically unsaturated monomer can be combined with the graft copolymer used in the second invention Those recorded are the same. When the A block contains two or more structural units derived from the above-mentioned carboxyl-containing ethylenically unsaturated monomer, the two or more structural units may also be block copolymerized, but it is necessary to prevent the steric hindrance. Or the surface of the color material in various states such as polarity, adsorb on the surface of each structural unit more suitable for adsorption with higher efficiency, preferably random copolymerization.

In the A block of the block copolymer used in the second invention, it may also have the above-mentioned structural unit derived from the carboxyl-containing ethylenically unsaturated monomer within a range that does not impair the effect of the invention. , And then have other structural units. Regarding this other structural unit, an ethylenically unsaturated monomer can be appropriately selected and copolymerized, and other structural units can be introduced. As other structural units included in the A block within a range that does not impair the effect of the present invention, for example, the structural unit represented by the above-mentioned general formula (IV) and the like can be mentioned. The structural unit represented by the above general formula (IV) may be the same as the structural unit represented by the above general formula (IV) in the first invention.

The total content ratio of the above-mentioned carboxyl-containing ethylenically unsaturated monomer-derived structural units contained in the A block is not particularly limited, as long as it is within a range that does not impair the effects of the present invention, but it is dispersible In terms of dispersion stability, it is preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass. The total content ratio of other structural units contained in the A block is not particularly limited, as long as it is within a range that does not impair the effects of the present invention, but in terms of dispersibility and dispersion stability, it is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass.

(B block) In the block copolymer used in the second invention, the B block is a block that functions as a solvent affinity site, and contains a structural unit selected from the above-mentioned general formula (V) and the above-mentioned general formula (V). At least one structural unit in the group consisting of the structural unit represented by'). In the B block of the block copolymer used in the second invention, it is selected from the group consisting of the structural unit represented by the above general formula (V) and the structural unit represented by the above general formula (V') The at least one structural unit may be the same as that described in the graft copolymer used in the second invention.

In the block copolymer used in the second invention, in order to improve the solvent affinity, the dispersibility and dispersion stability of the color material, and the B block that functions as a solvent affinity site It may further include at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V'), which is different from the above-mentioned general formula (IV) Indicates the structural unit. The structural unit represented by the above general formula (IV) contained in the B block may be the same as that described in the above graft copolymer.

In the above-mentioned B block, the above-mentioned general formula ( The structural unit represented by IV) may be one type alone, or two or more types may be mixed. In terms of the dispersibility and dispersion stability of the color material, in the above-mentioned B block, when the total structural unit of the B block is set to 100% by mass, it includes those selected from those represented by the above-mentioned general formula (V) The total ratio of the structural unit represented by the general formula (IV) in the group consisting of the structural unit and the structural unit represented by the general formula (V') may also be 100% by mass. In terms of the dispersibility and dispersion stability of the color material, in the B block, when the total structural unit of the B block is set to 100% by mass, the structural unit represented by the general formula (IV) The total ratio is preferably 40% by mass or more, more preferably 70% by mass or more.

In addition, in the B block, at least one structural unit selected from the group consisting of the structural unit represented by the general formula (V) and the structural unit represented by the general formula (V') may be 1 alone It is possible to mix two or more kinds. In order to improve the adhesion of the substrate and shorten the development time, when the total structural unit of the above-mentioned B block is set to 100% by mass, it is selected from the structural unit represented by the above-mentioned general formula (V) and the above-mentioned general formula (V' The total ratio of at least one structural unit in the group consisting of the structural unit represented by) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. In terms of solvent resolubility, when the total structural unit of the above B block is set to 100% by mass, it is selected from the structural unit represented by the above general formula (V) and the above general formula (V') The total ratio of at least one structural unit in the group consisting of the structural unit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

In addition, in the above-mentioned B block, the above-mentioned structural unit is different from at least one structural unit selected from the group consisting of the structural unit represented by the above-mentioned general formula (V) and the structural unit represented by the above-mentioned general formula (V') The structural unit represented by the general formula (IV) may be one type alone, or two or more types may be mixed. When the total structural unit of the above-mentioned B block is set to 100% by mass, it is selected from the group consisting of the structural unit represented by the above-mentioned general formula (V) and the structural unit represented by the above-mentioned general formula (V') In terms of solvent resolubility, the total ratio of the structural units represented by the general formula (IV) having at least one different structural unit is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably It is 40% by mass or more. In order to improve the adhesion of the substrate and shorten the development time, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

In the above-mentioned B block, except for the above-mentioned general formula containing at least one structural unit selected from the group consisting of the structural unit represented by the above-mentioned general formula (V) and the structural unit represented by the above-mentioned general formula (V') In addition to the structural unit shown in (IV), other structural units may be contained. As this other structural unit, the structural unit derived from the ethylenic unsaturated monomer which can copolymerize with the ethylenic unsaturated monomer which derives the structural unit represented by the said general formula (IV) etc. is mentioned. Regarding the monomer deriving the other structural unit and the total ratio thereof, it may be the same as the monomer deriving the other structural unit in the first invention described above.

In addition, regarding the mass average molecular weight Mw, glass transition temperature, acid value, amine value of the B block, the copolymerization method in the B block, and the bonding sequence, it can be copolymerized with the block used in the first invention. The mass average molecular weight Mw, glass transition temperature, acid value, amine value, copolymerization method and bonding sequence of the above-mentioned B block in the B block are the same.

In the block copolymer, the total content of the structural units derived from the carboxyl group-containing ethylenically unsaturated monomer is preferably 3% by mass to 60% by mass, more preferably 6% to 45% by mass, and further Preferably it is 9 mass%-35 mass %. If the total content ratio of the structural units derived from the carboxyl group-containing ethylenically unsaturated monomer in the block copolymer is within the above range, the ratio of the affinity portion with the color material in the block copolymer becomes appropriate. And it can suppress the decrease in solubility to organic solvents, so the adsorption to color materials becomes good, and excellent dispersibility, dispersion stability and solvent re-solubility can be obtained.

On the other hand, in the above-mentioned block copolymer, the total content ratio of the B block is preferably 40% by mass to 97% by mass, more preferably 55% to 94% by mass, and still more preferably 65% by mass to 91% by mass. quality%. If the total content ratio of the B blocks in the block copolymer is within the above range, the ratio of the solvent affinity part in the block copolymer becomes appropriate, the sufficient steric repulsion effect as a dispersant can be maintained, and the The effect of increasing the specific surface area of the solvent affinity part of the dispersant on the above effect becomes good. Furthermore, the content ratio of the above-mentioned structural unit is based on the structural unit derived from the above-mentioned carboxyl-containing ethylenically unsaturated monomer when synthesizing the block copolymer, and the structural unit selected from the above-mentioned general formula (V) and the above-mentioned general formula. The amount of addition of at least one of the monomers in the group consisting of the structural unit represented by the formula (V') is calculated.

The mass average molecular weight Mw and acid value of at least one of the above-mentioned graft copolymer and the above-mentioned block copolymer used in the second invention may be the same as those of the above-mentioned graft copolymer and the above-mentioned block used in the above-mentioned first invention. At least one of the copolymers has the same mass average molecular weight Mw and acid value.

In the color material dispersion liquid of the second invention, as a dispersant, the graft copolymer and the block copolymer used in the second invention are contained, but other known dispersants may also be contained as long as they do not damage And the effect of the present invention is sufficient. In the dispersant used in the color material dispersion liquid of the second invention, the total content ratio of at least one of the graft copolymer and the block copolymer used in the second invention is preferably 60% by mass Above, it is more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass.

In the color material dispersion liquid of the second invention, at least one of the above-mentioned graft copolymer and block copolymer is used as a dispersant, and its content depends on the type of color material used, and the following photosensitive color resin The concentration of solid components in the composition, etc. are appropriately selected. The content of the dispersant in the color material dispersion liquid may be the same as that of the color material dispersion liquid of the first invention described above.

In the color material dispersion liquid of the second invention, the color material, solvent, and other components may be the same as the color material, solvent, and other components in the color material dispersion liquid of the first invention.

<Preferable form of the color material dispersion liquid of the second invention> In the color material dispersion liquid of the second invention, in the dispersant, the polymer chain in the structural unit represented by the general formula (III) of the graft copolymer further includes and is selected from the general formula (V The structural unit represented by the general formula (V') and the structural unit represented by the general formula (IV) differing in at least one structural unit in the group consisting of the structural unit represented by the general formula (V'), the general formula (III) The glass transition temperature of the polymer chain in the structural unit represented is 85°C or less, and the B block of the block copolymer further includes a structural unit selected from the structural unit represented by the general formula (V) and the general formula (V). ') The structural unit represented by the general formula (IV) in which at least one structural unit in the group consisting of the structural unit represented by is different, the glass transition temperature of the B block is 85°C or less, and the development time is improved due to the above situation It is preferred because it delays and improves coating suitability. In order to improve production efficiency, it is required to increase the coating speed of the photosensitive colored resin composition. If the coating suitability is excellent, uneven streaks will not easily occur during high-speed coating. In the color material dispersion of the second invention, in terms of dispersion stability and solvent resolubility, in the dispersant, the acid value of at least one of the graft copolymer and the block copolymer Preferably, it is 30 mgKOH/g to 180 mgKOH/g.

II-2. The second photosensitive colored resin composition of the present invention The photosensitive colored resin composition of the second invention contains a color material, the dispersant of the second invention described above, a polyfunctional monomer, a photoinitiator, and a solvent.

In the photosensitive colored resin composition of the second invention, the dispersant of the second invention described above may be the same as the dispersant described in the color material dispersion liquid of the second invention. The photosensitive colored resin composition of the second invention, by containing the dispersant, color material, and solvent of the second invention described above, can be the same as the description of the color material dispersion liquid of the second invention described above, and at the same time satisfy the excellent basis Material adhesion and developability.

The photosensitive colored resin composition of the second invention contains at least the color material, the dispersant of the second invention, the polyfunctional monomer, the photoinitiator, and the solvent, and may be within a range that does not impair the effects of the invention. , And further contain other ingredients. In the photosensitive colored resin composition of the second invention, the color material, solvent, multifunctional monomer, photoinitiator, and other components can be combined with the color material, solvent, polyfunctional monomer, photoinitiator, and other components in the photosensitive colored resin composition of the first invention. The solvent, multifunctional monomer, photoinitiator, and other components are the same.

<Preferable form of the photosensitive colored resin composition of the second invention> The case where the photosensitive colored resin composition of the second invention further contains a polyfunctional thiol compound improves the notch resistance and has good storage stability, which is preferable. The multifunctional thiol compound may be the same as the multifunctional thiol compound in the first invention described above. The photosensitive colored resin composition of the second invention contains the polyfunctional thiol compound represented by the general formula (A) in which the notch resistance is improved and the storage stability is good, which is preferable. In the photosensitive colored resin composition of the second invention, the content of the polyfunctional thiol compound relative to 100 parts by mass of the total solid content in the colored resin composition may be, for example, 0.001 parts by mass to 15.0 parts by mass, within 0.01 parts by mass When it is 15.0 parts by mass, the notch resistance can be easily improved and the development residue can be easily suppressed, which is preferable.

＜Use＞ The photosensitive colored resin composition of the second invention can simultaneously satisfy excellent substrate adhesion and developability (shortening of development time), and is therefore suitable for color filter applications.

II-3. The second color filter of the present invention The second color filter of the present invention has at least a substrate and a coloring layer disposed on the substrate, and at least one of the coloring layers is the second The cured product of the photosensitive colored resin composition of the present invention. The color filter of the second invention can be made into a color filter with excellent productivity when at least one of the colored layers is a cured product of the photosensitive colored resin composition of the second invention.

As long as the color filter of the second invention has a colored layer that is a cured product of the photosensitive colored resin composition of the second invention, the other structure may be the same as that described in the color filter of the first invention. .

II-4. Second Display Device of the Invention The second liquid crystal display device of the invention is characterized by having the color filter of the second invention described above. In the second invention, by using the color filter of the second invention described above, a display device with excellent productivity can be provided.

As long as the display device of the second invention includes the color filter of the second invention described above, the other configuration may be the same as that described in the display device of the first invention described above, so the description is omitted here.

According to the second invention, it is possible to provide a color material dispersion and a dispersant capable of producing a photosensitive colored resin composition satisfying excellent substrate adhesion and developability at the same time. Furthermore, according to the second invention, it is possible to provide a photosensitive colored resin composition that satisfies excellent substrate adhesion and developability at the same time, a color filter formed using the photosensitive colored resin composition, and a display device.

III. The third invention III-1. The third photosensitive colored resin composition of the present invention The photosensitive colored resin composition of the third aspect of the present invention contains a color material, a dispersant, a polyfunctional monomer, a photoinitiator, a solvent, and a polyfunctional thiol compound. At least one of graft copolymers and block copolymers of structural units of monomers.

The photosensitive colored resin composition of the third invention contains a polyfunctional thiol compound, and the dispersant contains a graft copolymer and a block copolymer having a structural unit derived from a carboxyl-containing ethylenically unsaturated monomer At least one of them has good notch resistance and good storage stability. It is estimated that according to this combination, the photosensitive colored resin composition has good chipping resistance and good storage stability due to the effects as described in the photosensitive colored resin composition of the first invention.

The photosensitive colored resin composition of the third invention contains at least the color material, the dispersant used in the third invention, the polyfunctional monomer, the photoinitiator, the solvent, and the polyfunctional thiol compound, and it may not be impaired. Within the range of the effects of the present invention, other components are further contained. Hereinafter, each component of the photosensitive colored resin composition of the third invention will be described in detail starting from the dispersant which is the characteristic of the third invention.

<The third dispersant used in the present invention> The dispersant used in the third invention contains at least one of graft copolymers and block copolymers having structural units derived from carboxyl-containing ethylenically unsaturated monomers.

[Graft Copolymer] The graft copolymer used in the third invention has a structural unit derived from a carboxyl-containing ethylenically unsaturated monomer that functions as an adsorption site for color materials in the main chain, and has solvent affinity in the side chain Copolymers of grafted polymer chains with functional sites.

The above-mentioned structural unit derived from the carboxyl-containing ethylenically unsaturated monomer in the third invention can be combined with the structure derived from the carboxyl-containing ethylenically unsaturated monomer in the graft copolymer used in the second invention. The units are the same.

The structural unit having a grafted polymer chain in the third invention may be the same as the structural unit having a grafted polymer chain in the above-mentioned first invention.

In the graft copolymer used in the third invention, the total content ratio of the structural units derived from the carboxyl group-containing ethylenically unsaturated monomer can be the same as that in the graft copolymer used in the first invention. The total content ratio of the structural unit represented by the general formula (I) and the structural unit represented by the above-mentioned general formula (II) is the same. In addition, in the graft copolymer used in the third invention, the content ratio of the structural unit having a graft polymer chain can be comparable to that in the graft copolymer used in the first invention. The content ratio of the structural units is the same.

[Block copolymer] The block copolymer used in the third aspect of the present invention has an A block which contains a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer and functions as an adsorption site for the color material. The block copolymer used in the third invention preferably further has a B block functioning as a solvent affinity site.

Regarding the block copolymer used in the third invention, the A block containing the structural unit derived from the carboxyl-containing ethylenically unsaturated monomer can be the same as the block copolymer used in the second invention described above. The A block of the structural unit derived from the carboxyl-containing ethylenically unsaturated monomer is the same.

The B block functioning as a solvent affinity site of the block copolymer used in the third invention may be the same as the B block in the block copolymer used in the first invention described above.

In the block copolymer used in the third invention, the total content ratio of the structural units derived from the carboxyl group-containing ethylenically unsaturated monomer can be the same as that in the block copolymer used in the first invention. The total content ratio of the structural unit represented by the general formula (I) and the structural unit represented by the above-mentioned general formula (II) is the same. In addition, in the block copolymer used in the third invention, the total content ratio of B blocks may be the same as the total content ratio of B blocks in the block copolymer used in the first invention.

In addition, among the dispersants used in the third invention, in addition to at least one of the graft copolymers and block copolymers used in the third invention, other dispersants can be combined with the dispersants used in the first invention. same.

In the photosensitive colored resin composition of the third invention, the color material, solvent, polyfunctional monomer, photoinitiator, polyfunctional thiol compound and other components can be combined with the photosensitive colored resin composition of the first invention The color materials, solvents, multifunctional monomers, photoinitiators, multifunctional thiol compounds and other components are the same.

<Preferable form of the photosensitive colored resin composition of the third invention> Regarding the photosensitive colored resin composition of the third aspect of the present invention, the case where the polyfunctional thiol compound is a polyfunctional thiol compound represented by the general formula (A) will improve notch resistance and good storage stability. Better. In the photosensitive colored resin composition of the third invention, the content of the above-mentioned polyfunctional thiol compound relative to 100 parts by mass of the total solid content in the colored resin composition may be, for example, 0.001 to 15.0 parts by mass, within 0.01 When it is 15.0 parts by mass, it is easy to improve notch resistance and it is easy to suppress the generation of development residue, which is preferable. The photosensitive colored resin composition of the third invention is in the above-mentioned dispersant, the above-mentioned graft copolymer has the structural unit represented by the above-mentioned general formula (III), and the polymer in the structural unit represented by the above-mentioned general formula (III) The chain contains the structural unit represented by the above general formula (IV), the glass transition temperature of the polymer chain in the structural unit represented by the general formula (III) is 85°C or less, and the block copolymer has the above general formula ( IV) The B block of the structural unit represented by the B block, and the glass transition temperature of the B block is 85° C. or less. The above situation is preferable because it improves the development time delay and improves the coating suitability. In terms of dispersion stability and solvent resolubility, the photosensitive colored resin composition of the third invention is preferably in the above-mentioned dispersant, at least one of the above-mentioned graft copolymer and the above-mentioned block copolymer The acid value is 30 mgKOH/g～180 mgKOH/g.

＜Use＞ The photosensitive colored resin composition of the third aspect of the present invention has good notch resistance and good storage stability, so it is suitable for color filter applications among them.

III-3. The color filter of the third invention The color filter of the third invention has at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is the above-mentioned third one The cured product of the photosensitive colored resin composition of the invention. The color filter of the third invention can be an excellent color filter with suppressed defects because at least one of the colored layers is a cured product of the photosensitive colored resin composition of the third invention.

As long as the color filter of the third invention has a colored layer that is a cured product of the photosensitive colored resin composition of the third invention, the other configurations may be the same as those described in the color filter of the first invention. .

III-4. The display device of the third invention The liquid crystal display device of the third invention is characterized by having the color filter of the third invention described above. In the third aspect of the present invention, by using the color filter of the third aspect of the present invention, it is possible to produce an excellent display device with suppressed defects.

As long as the display device of the third aspect of the invention includes the color filter of the third aspect of the invention, the other configuration may be the same as that described in the display device of the first aspect of the invention, so the description is omitted here.

According to the third invention, it is possible to provide a photosensitive colored resin composition having good notch resistance and good storage stability, a color filter formed using the photosensitive colored resin composition, and a display device. Example

Hereinafter, the present invention will be specifically explained by showing examples. The invention is not limited by these descriptions. The acid value of the graft copolymer and the block copolymer is determined according to the measurement method described in the specification of the present invention. The weight average molecular weight (Mw) and Mw/Mn of graft copolymers and block copolymers are based on the measurement method described in the specification of the present invention and GPC (Gel Permeation Chromatography) is used as the standard polystyrene The conversion value is calculated.

The glass transition temperature (Tg) of the polymer chain of the graft copolymer and the glass transition temperature (Tg) of the B block of the block copolymer can be calculated by the following formula. 1/Tg=Σ(Xi/Tgi) Here, the block copolymer is assumed to be copolymerized with n monomer components of i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, Σ is the sum of i=1 to n. Furthermore, the value of the homopolymer glass transition temperature (Tgi) of each monomer adopts the value of Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)). The values (Tgi) of the homopolymer glass transition temperature (Tgi) of each monomer specifically used in the examples and comparative examples are as follows. Methacrylic acid (MAA): 185°C Butyl methacrylate (BMA): 20°C Benzyl methacrylate (BzMA): 54°C Methyl methacrylate (MMA): 105°C Methoxy polyethylene glycol monomethacrylate (trade name: PME-200; manufactured by NOF Corporation; BLEMMER PME-200; ethylene oxide repeat number = 4): -59°C Unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone (PCL-FM5) (trade name: PLACCEL FM5; manufactured by Daicel Co., Ltd.; caprolactone chain repeat number = 5): -47°C

Example I series: the first invention (Synthesis example 1: Manufacturing of giant monomer m1) Add 30.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) to a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer. While stirring under a nitrogen stream, it is heated to a temperature of 90 ℃. It took 1.5 hours to drop 60.0 parts by mass of methyl methacrylate (MMA), 10.0 parts by mass of butyl methacrylate (BMA), 30.0 parts by mass of benzyl methacrylate (BzMA), 7.0 parts by mass of mercaptopropionic acid, and 1.0 parts by mass. Part of the mixed solution of α,α'-azobisisobutyronitrile (AIBN), and react for a further 3 hours. After cooling, the reaction solution was diluted with 200 parts by mass of tetrahydrofuran (THF), and reprecipitation was performed with 3000 parts by mass of hexane, thereby obtaining 106.0 parts by mass of white powder. Then, to 50.0 parts by mass of the white powder, 50.0 parts by mass of PGMEA, 3.7 parts by mass of glycidyl methacrylate (GMA), 0.15 parts by mass of N,N-dimethyldodecylamine, and 0.1 parts by mass of PGMEA were added Methoxyphenol was stirred at 110°C for 24 hours while air was introduced. After cooling, the reaction solution was reprecipitated with 3000 parts by mass of hexane, thereby obtaining 52.0 parts by mass of macromonomer m1. GPC (Gel Permeation Chromatography) was used to confirm the obtained macromonomer m1 under standard conditions of N-methylpyrrolidone/polystyrene added with 0.01 mol/L lithium bromide, and the result was the weight The average molecular weight (Mw) is 4800, and the molecular weight distribution (Mw/Mn) is 1.6. The calculated value of Tg is 78°C.

(Synthesis examples 2 to 4: manufacture of giant monomers m2 to m4) In the manufacture of the macromonomer m1 of Synthesis Example 1, as shown in Table 1, it was changed to 70.0 parts by mass of MMA and 30.0 parts by mass of methoxy polyethylene glycol monomethacrylate (manufactured by NOF Corporation; product) Name: BLEMMER PME-200; ethylene oxide repeat number = 4) (PME-200) is used instead of 60.0 parts by mass of MMA, 10.0 parts by mass of BMA, and 30.0 parts by mass of BzMA, except for this, the same as Synthesis Example 1 To produce a giant monomer m2. The weight average molecular weight (Mw) of the obtained macromonomer m2 is 6500, and the molecular weight distribution (Mw/Mn) is 1.7. The calculated value of Tg is 34°C. In the production of the macromonomer m1 of Synthesis Example 1, as shown in Table 1, it was changed to 60.0 parts by mass of MMA, 5.0 parts by mass of BzMA, and 35.0 parts by mass of unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone (trade name : PLACCEL FM5; manufactured by Daicel Co., Ltd.; caprolactone chain repeat number = 5) (PCL-FM5) is used instead of 60.0 parts by mass of MMA, 10.0 parts by mass of BMA, and 30.0 parts by mass of BzMA. In addition, with In Synthesis Example 1, the macromonomer m3 was produced in the same manner. The weight average molecular weight (Mw) of the obtained macromonomer m3 is 5200, and the molecular weight distribution (Mw/Mn) is 1.6. The calculated value of Tg is 31°C. In the production of the giant monomer m1 of Synthesis Example 1, as shown in Table 1, 100.0 parts by mass of MMA were used instead of 60.0 parts by mass of MMA, 10.0 parts by mass of BMA, and 30.0 parts by mass of BzMA. In Synthesis Example 1, the macromonomer m4 was produced in the same manner. The weight average molecular weight (Mw) of the obtained macromonomer m2 was 4300, and the molecular weight distribution (Mw/Mn) was 1.6. The calculated value of Tg is 105°C.

(Production Example 1: Production of graft copolymer A) To a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 100.0 parts by mass of PGMEA was added, and while stirring under a nitrogen stream, it was heated to a temperature of 85°C. It took 1.5 hours to drop 92.9 parts by mass of the macromonomer m1 of Synthesis Example 1, 4.2 parts by mass of methacrylic acid (MAA), 2.9 parts by mass of 2-methacryloxyethyl succinate (2-MOES), 1.3 A mixed solution of n-dodecane mercaptan, 50.0 parts by mass PGMEA, and 1.0 part by mass AIBN, heated and stirred for 3 hours, and then added dropwise a mixture of 0.10 parts by mass AIBN and 6.0 parts by mass PGMEA over 10 minutes, and then at the same temperature It is matured for 1 hour. After cooling, the reaction solution was reprecipitated with 3000 parts by mass of hexane, thereby obtaining 99.0 parts by mass of graft copolymer A. The weight average molecular weight (Mw) of the obtained graft copolymer A was 12,500, Mw/Mn was 2.6, and the acid value was 35 mgKOH/g.

(Production Examples 2-11: Production of graft copolymers B-K) In Production Example 1, as shown in Table 1, the types of macromonomers, the macromonomers, the monomers that derive the structural units represented by the general formula (I), and the structural units represented by the general formula (II) were changed Instead of using 92.9 parts by mass of macromonomer m1, 4.2 parts by mass of MAA, and 2.9 parts by mass of 2-MOES, the mass ratio of the monomers was carried out in the same manner as in Production Example 1 to produce graft copolymers B to K. Table 1 shows the weight average molecular weight (Mw), Mw/Mn, and acid value of the graft copolymers B to K obtained. Furthermore, 2-AOEHHP means 2-propenyloxyethylhexahydrophthalic acid derived from the structural unit represented by the above general formula (II).

(Comparative production examples 1 to 2: production of comparative graft copolymers L to M) In Manufacturing Example 1, as shown in Table 1, only the macromonomer and either MAA or 2-MOES were used and the mass ratio was changed, instead of using 92.9 parts by mass of the macromonomer m1, 4.2 parts by mass of MAA, and 2.9 parts by mass Except for the part 2-MOES, the comparative graft copolymers L to M were produced in the same manner as in Production Example 1. Table 1 shows the weight average molecular weight (Mw), Mw/Mn, and acid value of the obtained comparative graft copolymers L to M.

[Table 1] Table 1 Dispersant A B C D E F G H I J K L M Copolymerization graft graft graft graft graft graft graft graft graft graft graft Comparative grafting Comparative grafting Giant cell m1 m1 m2 m1 m3 m1 m4 m1 m1 m1 m1 m1 m1 Giant monomer (mass ratio) MMA 60.0 60.0 70.0 60.0 60.0 60.0 100.0 60.0 60.0 600. 60.0 60.0 60.0 BMA 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 BzMA 30.0 30.0 30.0 5.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 PME-200 30.0 PCL-FM5 35.0 Calculated value of polymer chain Tg(℃) 78 78 34 78 31 78 105 78 78 78 78 78 78 Grafted main chain (mass ratio) Giant cell 92.9 89.8 83.7 82.3 77.5 65.2 83.7 77.5 74.4 71.2 68.1 87.8 67.1 Formula (I): MAA 4.2 6.1 9.9 9.8 13.5 20.8 9.9 6.2 4.4 2.4 0.7 12.2 Formula (II): 2-MOES 2.9 4.2 6.4 9.1 14.0 6.4 16.3 21.3 26.4 31.3 32.9 Formula (II): 2-AOEHHP 7.8 Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 80/20 80/20 80/20 80/20 50/50 35/65 20/80 5/95 100/0 0/100 Copolymer Mw/Mn 2.6 2.6 2.5 2.6 2.8 2.6 2.5 2.4 2.8 2.6 2.6 2.7 2.6 Mw 12500 10900 14,300 18400 12500 16600 12600 17,400 16100 11700 13,500 14000 12200 Acid value 35 50 80 80 110 170 80 80 80 80 80 80 80

(Production Example 12: Production of block copolymer N) Add 150.0 parts by mass of PGMEA, 3.0 parts of iodine, 2,2'-azobis(4-methoxy-2, 4-Dimethylvaleronitrile) (trade name: V-70; manufactured by Wako Pure Chemical Industries, Ltd.), 50.2 parts by mass MMA, 8.4 parts by mass BMA, 25.1 parts by mass BzMA, 0.04 parts by mass succinimide, one side in nitrogen Stir under flow, while stirring at 40°C for 5 hours, to produce a copolymer of B block. The calculated value of Tg of the obtained copolymer was 78°C. Then, 9.9 parts by mass of MAA and 6.4 parts by mass of 2-MOES were added, and the mixture was stirred at 40°C for 5 hours. The solid content was measured and converted based on the non-volatile content. As a result, the polymerization conversion rate was 99%. This reaction solution was reprecipitated with 3000 parts by mass of hexane, thereby obtaining 99.0 parts by mass of AB block copolymer N. The weight average molecular weight (Mw) of the block copolymer N obtained in this way is 8300, Mw/Mn is 1.2, and the acid value is 80 mgKOH/g.

(Production Examples 13-15: Production of block copolymers O-Q) In Production Example 12, as shown in Table 2, the type and mass ratio of the monomers for the B block were changed, instead of using 50.2 parts by mass of methyl methacrylate (MMA) and 8.4 parts by mass of the monomers for the B block. Except for n-butyl acrylate (BMA) and 25.1 parts by mass of benzyl methacrylate (BzMA), the block copolymers O to Q were produced in the same manner as in Production Example 12. Table 2 shows the weight average molecular weight (Mw), Mw/Mn, and acid value of the obtained block copolymers O to Q.

(Comparative Production Examples 3 to 4: Production of Comparative Block Copolymers R to S) In Production Example 12, as shown in Table 2, the mass ratio of the B block monomer was changed, and only one of MAA or 2-MOES was used as the A block monomer and the mass ratio was changed. In the same manner as in Production Example 12, comparative block copolymers R to S were produced. Table 2 shows the weight average molecular weight (Mw), Mw/Mn, and acid value of the obtained comparative block copolymers R to S.

(Comparative Production Example 5: Production of Comparative Random Copolymer T) Using monomers of the same type and the same mass ratio as the monomers for the B block and the monomer for the A block in Production Example 12, a comparative random copolymer T was produced. Specifically, 300 parts by mass of PGMEA was added to a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer. After the temperature was raised to 100°C under a nitrogen atmosphere, the addition was continued for 1.5 hours. 50.2 parts by mass MMA, 8.4 parts by mass BMA, 25.1 parts by mass BzMA, 9.9 parts by mass MAA, 6.4 parts by mass 2-MOES and 6 parts by mass PERBUTYLO (manufactured by NOF Corporation), 2 parts by mass chain transfer agent (positive ten Dithiol). Thereafter, the reaction was continued while maintaining 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 as a polymerization inhibitor was added to stop the polymerization. The reaction solution was re-precipitated with 3000 parts by mass of hexane, thereby producing a comparative random copolymer T. Table 2 shows the weight average molecular weight (Mw), Mw/Mn, and acid value of the obtained comparative random copolymer T.

[Table 2] Table 2 Dispersant N O P Q R S T Copolymerization Block Block Block Block Comparison block Comparison block Relatively random B block MMA 50.2 37.6 33.5 83.7 52.7 40.3 50.2 BMA 8.4 16.7 20.9 8.8 6.7 8.4 BzMA 25.1 12.5 12.5 26.3 20.1 25.1 PME-200 16.7 FLC-FA5 16.7 B block (mass ratio) MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA/PME-200=45/20/15/20 MMA/BMA/BzMA/PCL-FM5=40/25/15/20 MMA=100 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 (Quality ratio) Calculated value of B block Tg(℃) 78 33 34 105 78 78 - B block (total mass) 83.7 83.7 83.7 83.7 87.8 67.1 - A block Formula (I): MAA 9.9 9.9 9.9 9.9 12.2 9.9 Formula (II): 2-MOES 6.4 6.4 6.4 6.4 32.9 6.4 Formula (II): 2-AOEHHP (Quality ratio) Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 80/20 100/0 0/100 80/20 Copolymer Mw/Mn 1.2 1.2 1.2 1.2 1.2 1.2 1.6 Mw 8300 9500 10100 8900 8500 9600 9500 Acid value 80 80 80 80 80 80 80

(Preparation Example 1: Preparation of Alkali-soluble Resin α) Add 300 parts by mass of PGMEA to a reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer. After the temperature is raised to 100°C in a nitrogen atmosphere, 90 parts by mass of Amethyst are continuously added dropwise over 1.5 hours 2-phenoxyethyl acrylate (PhEMA), 54 parts by mass MMA, 36 parts by mass methacrylic acid (MAA), 6 parts by mass PERBUTYLO (manufactured by NOF Corporation), 2 parts by mass chain transfer agent (positive Dodecanethiol). Thereafter, the reaction was continued while maintaining 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 as a polymerization inhibitor was added to stop the polymerization. Then, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added. After the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added and the addition was carried out at 110°C. The reaction was completed for 15 hours to obtain an alkali-soluble resin α solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass).

(Example 1) (1) Manufacturing of color material dispersion R-1 The graft copolymer A of Production Example 1 as dispersant A was 6.5 parts by mass, CI Pigment Red 177 (PR177) 6.5 parts by mass, CI Pigment Red 291 (PR291) 6.5 parts by mass, PGMEA 80.5 parts by mass, 100 parts by mass of zirconia beads with a particle size of 2.0 mm are put into a mayonnaise bottle, shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-compression, and then the zirconia with a particle size of 2.0 mm is taken out To the beads, 200 parts by mass of zirconia beads with a particle diameter of 0.1 mm were added, and the beads were dispersed in a paint shaker for 4 hours as the main crush to obtain a color material dispersion liquid R-1.

(2) Production of photosensitive colored resin composition R-1 Add 8.71 parts by mass of the color material dispersion R-1 obtained in (1) above, 0.33 parts by mass of the alkali-soluble resin α solution obtained in Preparation Example 1, and a multifunctional monomer (trade name ARONIX M-403; East Asia Synthetic Co., Ltd. manufacture) 1.19 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (photoinitiator: trade name IRGACURE 907; BASF Co., Ltd. of Japan) Co., Ltd.) 0.06 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE 369; Japanese BASF Company manufacture) 0.06 parts by mass, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzyl oxime)] (photoinitiator: trade name IRGACURE OXE01; Japan BASF Co., Ltd.) 0.03 parts by mass, fluorine-based surfactant (trade name MEGAFAC R-08MH; manufactured by DIC Co., Ltd.) 0.07 parts by mass, and PGMEA 9.95 parts by mass, to obtain photosensitive colored resin composition R-1.

(Examples 2-15) (1) Manufacturing of color material dispersion R-2～R-15 In (1) of Example 1, as shown in Table 3 and Table 4, dispersants B, C, D, E, F, G, H, I, J, K, N, O, P and Q were used respectively Except for replacing the dispersant A, the color material dispersion liquids R-2 to R-15 were produced in the same manner as in Example 1. (2) Manufacture of photosensitive colored resin composition R-2～R-15 In Example 1 (2), except that the above-mentioned color material dispersion liquids R-2 to R-15 were used instead of the color material dispersion liquid R-1, the photosensitivity was obtained in the same manner as in Example 1 (2). Colored resin composition R-2 to R-15.

(Comparative Examples 1 to 5) (1) Manufacture of comparative color material dispersion liquid CR-1～CR-5 In (1) of Example 1, as shown in Tables 3 and 4, comparative graft copolymers L and M, comparative block copolymers R and S, and comparative random copolymer T were used instead of dispersant A, respectively. Except for this, in the same manner as in Example 1, comparative color material dispersion liquids CR-1 to CR-5 were obtained. (2) Comparison of the production of photosensitive colored resin compositions CR-1～CR-5 In Example 1 (2), the above-mentioned comparative color material dispersions CR-1 to CR-5 were used instead of the color material dispersion R-1, except that the comparison was obtained in the same manner as in Example 1 (2). Photosensitive colored resin composition CR-1 to CR-5.

(Example 16) (1) Manufacturing of color material dispersion G-1 6.5 parts by mass of graft copolymer C of Production Example 3 as dispersant C, 3.9 parts by mass of CI Pigment Green 59 (PG59) as a color material, 9.1 parts by mass of CI Pigment Yellow 150 (PY150), 80.5 parts by mass of PGMEA, 100 parts by mass of zirconia beads with a particle size of 2.0 mm are put into a mayonnaise bottle, shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-compression, and then the zirconia with a particle size of 2.0 mm is taken out To the beads, 200 parts by mass of zirconia beads with a particle diameter of 0.1 mm were added, and the beads were dispersed in a paint shaker for 4 hours as a formal crushing to obtain a color material dispersion G-1.

(2) Production of photosensitive colored resin composition G-1 Add 8.71 parts by mass of the color material dispersion G-1 obtained in (1) above, 0.33 parts by mass of the alkali-soluble resin α solution obtained in Preparation Example 1, and a multifunctional monomer (trade name ARONIX M-403; East Asia Synthetic Co., Ltd. manufacture) 1.19 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (photoinitiator: trade name IRGACURE 907; BASF Co., Ltd. of Japan) Co., Ltd.) 0.06 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE 369; Japanese BASF Company manufacture) 0.06 parts by mass, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzyl oxime)] (photoinitiator: trade name IRGACURE OXE01; Japan BASF Co., Ltd.) 0.03 parts by mass, fluorine-based surfactant (trade name MEGAFAC R-08MH; manufactured by DIC Co., Ltd.) 0.07 parts by mass, and PGMEA 9.95 parts by mass, to obtain photosensitive colored resin composition G-1.

(Examples 17-22) (1) Manufacture of color material dispersion G-2～G-7 In (1) of Example 16, as shown in Table 5 and Table 6, the dispersant D, E, N, O, P, and Q were used instead of the dispersant C, respectively, and it was produced in the same manner as in Example 16, except that Color material dispersion G-2～G-7. (2) Manufacture of photosensitive colored resin composition G-2～G-7 In Example (2), except that the above-mentioned color material dispersion G-2 to G-7 were used instead of the color material dispersion G-1, the photosensitive coloring was obtained in the same manner as in Example 16 (2). Resin composition G-2 to G-7.

(Comparative Examples 6-10) (1) Manufacture of comparative color material dispersion CG-1～CG-5 In (1) of Example 16, as shown in Table 5 and Table 6, comparative graft copolymers L and M, comparative block copolymers R and S, and comparative random copolymer T were used instead of dispersant C, respectively. Except for this, the comparative color material dispersion liquids CG-1 to CG-5 were obtained in the same manner as in the examples. (2) Comparison of the production of photosensitive colored resin compositions CG-1～CG-5 In (2) of Example 16, except that the above-mentioned comparative color material dispersions CG-1 to CG-5 were used instead of the color material dispersion G-1, a comparison was obtained in the same manner as in (2) of Example 16 Photosensitive colored resin composition CG-1 to CG-5.

(Example 23) (1) Manufacturing of color material dispersion B-1 6.5 parts by mass of graft copolymer C of Production Example 3 as dispersant C, 10.4 parts by mass of CI Pigment Blue (PB15:6) as color material, 2.6 parts by mass of CI Pigment Violet 23 (PV23), and 80.5 parts by mass of PGMEA , 100 parts by mass of zirconia beads with a diameter of 2.0 mm are put into a mayonnaise bottle, shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as a pre-compression, and then take out the oxide with a diameter of 2.0 mm For the zirconium beads, 200 parts by mass of zirconium oxide beads with a particle diameter of 0.1 mm were added, and the dispersion was carried out in the same manner by a paint shaker for 4 hours as a formal crushing to obtain a color material dispersion liquid B-1.

(2) Production of photosensitive colored resin composition B-1 Add 6.03 parts by mass of the color material dispersion B-1 obtained in (1) above, 1.39 parts by mass of the alkali-soluble resin α solution obtained in Preparation Example 1, and a multifunctional monomer (trade name ARONIX M-403; East Asia Synthetic Co., Ltd. production) 1.30 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (photoinitiator: trade name IRGACURE 907; BASF Co., Ltd. of Japan) Co., Ltd.) 0.08 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE 369; Japanese BASF Company manufacture) 0.08 parts by mass, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzyl oxime)] (photoinitiator: trade name IRGACURE OXE01; Japan BASF Co., Ltd.) 0.04 parts by mass, fluorine-based surfactant (trade name MEGAFAC R-08MH; manufactured by DIC Co., Ltd.) 0.07 parts by mass, and PGMEA 11.00 parts by mass, to obtain photosensitive colored resin composition B-1.

(Examples 24-29) (1) Manufacture of color material dispersion B-2～B-7 In (1) of Example 23, as shown in Table 7 and Table 8, the dispersant D, E, N, O, P, and Q were used instead of the dispersant C, respectively, and it was produced in the same manner as in Example 23. Color material dispersion B-2～B-7. (2) Manufacture of photosensitive colored resin composition B-2～B-7 In (2) of Example 23, except that the color material dispersions B-2 to B-7 were used instead of the color material dispersion B-1, the photosensitivity was obtained in the same manner as in (2) of Example 23. Colored resin composition B-2 to B-7.

(Comparative Examples 11-15) (1) Manufacture of comparative color material dispersion CB-1～CB-5 In (1) of Example 23, as shown in Table 7 and Table 8, comparative graft copolymers L and M, comparative block copolymers R and S, and comparative random copolymer T were used instead of dispersant C, respectively. Except for this, the comparative color material dispersion liquids CB-1 to CB-5 were obtained in the same manner as in the examples. (2) Comparison of the production of photosensitive colored resin compositions CB-1～CB-5 In (2) of Example 23, the above-mentioned comparative color material dispersions CB-1 to CB-5 were used instead of the color material dispersion B-1. The comparison was obtained in the same manner as in (2) of Example 23, except that Photosensitive colored resin composition CB-1 to CB-5.

[Evaluation method] <Evaluation of dispersion stability of color material dispersion> For the color material dispersions obtained in the Examples and Comparative Examples, the viscosity immediately after preparation and the viscosity after storage at 25°C for 30 days were measured, and the viscosity change rate was calculated based on the viscosity before and after storage, and the viscosity stability was evaluated. . A vibrating viscometer was used in the viscosity measurement to measure the viscosity at 25.0±0.5°C. (Evaluation criteria for dispersion stability) A: The change rate of viscosity before and after storage is less than 10% B: The change rate of viscosity before and after storage is more than 10% and less than 20% C: The change rate of viscosity before and after storage is more than 20% and less than 40% D: The change rate of viscosity before and after storage is more than 40% E: Gelation during dispersion or storage Here, this value is a value when the color material is 13% by mass relative to the total mass of the solvent containing the color material dispersion. If the evaluation result is C, the dispersion stability is relatively good, if the evaluation result is B, the dispersion stability is good, and if the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

＜Solvent resolubility＞ The front end of a glass substrate with a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for color filters obtained in the Examples and Comparative Examples, and coated on the 1 cm portion of the glass substrate. Put the pulled-out glass substrate into a constant temperature and humidity machine with the glass surface as the level, and dry it under the conditions of a temperature of 23°C and a humidity of 80%RH for 30 minutes. Then, the glass substrate with the dried coating film attached was immersed in PGMEA for 15 seconds. At this time, the re-dissolution state of the dried coating film was visually judged and evaluated. (Evaluation criteria for solvent resolubility) A: The dried coating film is completely dissolved B: A flake with a dry coating film is produced in a solvent, and the flake will dissolve soon C: Produce dry film flakes in the solvent, the solution is colored D: Produce dry film flakes in the solvent, the solution is not colored E: No dry film is produced in the solvent, and the solution is not colored If the evaluation result is C, the solvent resolubility is relatively good, if the evaluation result is B, the solvent resolubility is good, and if the evaluation result is A, the solvent resolubility is excellent.

<Substrate Adhesion> Using a spin coater, the photosensitive colored resin composition obtained in the examples and comparative examples was applied to the glass in a thickness that would form a coloring layer with a thickness of 2.0 μm after post-baking. On the substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.), it was then dried using a hot plate at 80°C for 3 minutes to form a colored layer on the glass substrate. Using an ultra-high pressure mercury lamp, the colored layer was irradiated with 60 mJ/cm ² of ultraviolet rays. Then, the colored substrate was post-baked in a clean oven at 230° C. for 30 minutes to form a colored substrate. By the same method as JIS K5400, after making 100 cuts on the obtained colored substrate, the cellophane tape was attached and then peeled off instantly. Using an optical microscope, observe the state change of 100 cuts before and after the test with cellophane tape. (Criteria for evaluation of base material adhesion) A: 100 pieces were confirmed after the test, and there was no change in the state of the cut portion before and after the test B: 100 pieces were confirmed after the test, and the width of the cut portion changed significantly before and after the test C: After the test, it was confirmed that 70 blocks or more and less than 100 blocks. D: After the test, it was confirmed that 30 blocks or more and less than 70 blocks. E: After the test, it was confirmed that it did not reach 30 blocks. Alternatively, if all the colored layers are peeled off, if the evaluation result is C, the substrate adhesion is relatively good, if the evaluation result is B, the substrate adhesion is good, and if the evaluation result is A, the substrate adhesion is excellent.

<Evaluation of development time> Using a spin coater, the photosensitive colored resin composition obtained in the examples and comparative examples was applied to the glass substrate in a thickness that would form a coloring layer with a thickness of 2.0 μm after post-baking. ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.), and then dried using a hot plate at 80°C for 3 minutes to form a colored layer on the glass substrate. An ultra-high pressure mercury lamp was used to irradiate the colored layer with 60 mJ/cm ² of ultraviolet rays through a light shield. Thereafter, the glass substrate on which the colored layer was formed was spray-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and measured until the colored layer was completely dissolved and the glass surface where the colored layer was formed The time until exposure is regarded as the development time. (Evaluation criteria) A: The time until the glass surface is exposed is 15 seconds or less B: The time until the glass surface is exposed exceeds 15 seconds and is 30 seconds or less C: The time until the glass surface is exposed exceeds 30 seconds and is 45 seconds Below D: The time until the glass surface is exposed exceeds 45 seconds and is less than 60 seconds E: The glass surface is not exposed

The above-mentioned evaluation was performed for the color material dispersion liquid and the photosensitive color resin composition obtained in the Example and the comparative example obtained above. The evaluation results are shown in Tables 3 to 8.

[table 3] table 3 Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 1 2 Dispersant A B C D E F G H I J K L M Copolymerization graft graft graft graft graft graft graft graft graft graft graft Comparative grafting Comparative grafting Giant cell Giant monomer (mass ratio) MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/PME-200=70/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/PCL-FM5=60/5/35 MMA/BMA/BzMA=60/10/30 MMA=100 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 Calculated value of polymer chain Tg(℃) 78 78 34 78 31 78 105 78 78 78 78 78 78 Grafted main chain (mass ratio) Giant cell 92.9 89.8 83.7 82.3 77.5 65.2 83.7 77.5 74.4 71.2 68.1 87.8 67.1 Formula (I): MAA 4.2 6.1 9.9 9.8 13.5 20.8 9.9 6.2 4.4 2.4 0.7 12.2 Formula (II): 2-MOES 2.9 4.2 6.4 9.1 14.0 6.4 16.3 21.3 26.4 31.3 32.9 Formula (II): 2-AOEHHP 7.8 Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 80/20 80/20 80/20 80/20 50/50 35/65 20/80 5/95 100/0 0/100 Copolymer Mw/Mn 2.6 2.6 2.5 2.6 2.8 2.6 2.5 2.4 2.8 2.6 2.6 2.7 2.6 Mw 12500 10900 14,300 18400 12500 16600 12600 17,400 16100 11700 13,500 14000 12200 Acid value 35 50 80 80 110 170 80 80 80 80 80 80 80 Color material dispersion/photosensitive coloring resin composition R-1 R-2 R-3 R-4 R-5 R-6 R-7 R-8 R-9 R-10 R-11 CR-1 CR-2 Evaluation Pigment type R177/R291 Dispersion stability C A A A A B A A B C C C D Solvent resolubility B A A A A C B A B B C D D Substrate adhesion C B A B A B B B B C C C D Development time C C A B A A E A A A A D A

[Table 4] Table 4 Example Comparative example 12 13 14 15 3 4 5 Dispersant N O P Q R S T Copolymerization Block Block Block Block Comparison block Comparison block Relatively random (Quality ratio) B block B block (mass ratio) MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA/PME-200=45/20/15/20 MMA/BMA/BzMA/PCL-FM5=40/25/15/20 MMA=100 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 Calculated value of B block Tg(℃) 78 32 34 105 78 78 - B block (total mass) 83.7 83.7 83.7 83.7 87.8 67.1 - (Quality ratio) A block Formula (I): MAA 9.9 9.9 9.9 9.9 12.2 9.9 Formula (II): 2-MOES 6.4 6.4 6.4 6.4 32.9 6.4 Formula (II): 2-AOEHHP Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 80/20 100/0 0/100 80/20 Copolymer Mw/Mn 1.2 1.2 1.2 1.2 1.2 1.2 1.6 Mw 8300 9500 10100 8900 8500 9600 9500 Acid value 80 80 80 80 80 80 80 Color material dispersion/photosensitive coloring resin composition R-12 R-13 R-14 R-15 CR-3 CR-4 CR-5 Evaluation Pigment type R177/R291 Dispersion stability A A A A C D E Solvent resolubility A A A B D D Can't evaluate Substrate adhesion B A A B C D Can't evaluate Development time B A A E D A Can't evaluate

[table 5] table 5 Example Comparative example 16 17 18 6 7 Dispersant C D E L M Copolymerization graft graft graft Comparative grafting Comparative grafting Giant cell Giant cell m2 m1 m3 m1 m1 Giant monomer (mass ratio) MMA/PME-200=70/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/PCL-FM5=60/5/35 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 Calculated value of polymer chain Tg(℃) 34 78 31 78 78 Grafted main chain (mass ratio) Giant cell 83.7 82.3 77.5 87.8 67.1 Formula (I): MAA 9.9 9.8 13.5 12.2 Formula (II): 2-MOES 6.4 9.1 32.9 Formula (II): 2-AOEHHP 7.8 Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 100/0 0/100 Copolymer Mw/Mn 2.5 2.6 2.8 2.7 2.6 Mw 14,300 18400 12500 14000 12200 Acid value 80 80 110 80 80 Color material dispersion/photosensitive coloring resin composition G-1 G-2 G-3 CG-1 CG-2 Evaluation Pigment type G59/Y150 Dispersion stability A A A C D Solvent resolubility A A A D D Substrate adhesion A B A C D Development time A B A D A

[Table 6] Table 6 Example Comparative example 19 20 twenty one twenty two 8 9 10 Dispersant N O P Q R S T Copolymerization Block Block Block Block Comparison block Comparison block Relatively random (Quality ratio) B block B block (mass ratio) MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA/PME-200=45/20/15/20 MMA/BMA/BzMA/PCL-FM5=40/25/15/20 MMA=100 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 Calculated value of B block Tg(℃) 78 32 34 105 78 78 - B block (total mass) 83.7 83.7 83.7 83.7 87.8 67.1 - (Quality ratio) A block Formula (I): MAA 9.9 9.9 9.9 9.9 12.2 9.9 Formula (II): 2-MOES 6.4 6.4 6.4 6.4 32.9 6.4 Formula (II): 2-AOEHHP Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 80/20 100/0 0/100 80/20 Copolymer Mw/Mn 1.2 1.2 1.2 1.2 1.2 1.2 1.6 Mw 8300 9500 10100 8900 8500 9600 9500 Acid value 80 80 80 80 80 80 80 Color material dispersion/photosensitive coloring resin composition G-4 G-5 G-6 G-7 CG-3 CG-4 CG-5 Evaluation Pigment type G59/Y150 Dispersion stability A A A A C D E Solvent resolubility A A A B D D Can't evaluate Substrate adhesion B A A B C D Can't evaluate Development time B A A E D A Can't evaluate

[Table 7] Table 7 Example Comparative example twenty three twenty four 25 11 12 Dispersant C D E L M Copolymerization graft graft graft Comparative grafting Comparative grafting Giant cell Giant cell m2 m1 m3 m1 m1 Giant monomer (mass ratio) MMA/PME-200=70/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/PCL-FM5=60/5/35 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 Calculated value of polymer chain Tg(℃) 31 78 31 78 78 Grafted main chain (mass ratio) Giant cell 83.7 82.3 77.5 87.8 67.1 Formula (I): MAA 9.9 9.8 13.5 12.2 Formula (II): 2-MOES 6.4 9.1 32.9 Formula (II): 2-AOEHHP 7.8 Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 100/0 0/100 Copolymer Mw/Mn 2.5 2.6 2.8 2.7 2.6 Mw 14,300 18400 12500 14000 12200 Acid value 80 80 110 80 80 Color material dispersion/photosensitive coloring resin composition B-1 B-2 B-3 CB-1 CB-2 Evaluation Pigment type B15: 6/V23 Dispersion stability A A A C D Solvent resolubility A A A D D Substrate adhesion A B A C D Development time A B A D A

[Table 8] Table 8 Example Comparative example 26 27 28 29 13 14 15 Dispersant N O P Q R S T Copolymerization Block Block Block Block Comparison block Comparison block Relatively random (Quality ratio) B block B block (mass ratio) MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA/PME-200=45/20/15/20 MMA/BMA/BzMA/PCL-FM5=40/25/15/20 MMA=100 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 MMA/BMA/BzMA=60/10/30 Calculated value of B block Tg(℃) 78 32 34 105 78 78 - B block (total mass) 83.7 83.7 83.7 83.7 87.8 67.1 - (Quality ratio) A block Formula (I): MAA 9.9 9.9 9.9 9.9 12.2 9.9 Formula (II): 2-MOES 6.4 6.4 6.4 6.4 32.9 6.4 Formula (II): 2-AOEHHP Formula (I)/Formula (II) (mass ratio) 80/20 80/20 80/20 80/20 100/0 0/100 80/20 Copolymer Mw/Mn 1.2 1.2 1.2 1.2 1.2 1.2 1.6 Mw 8300 9500 10100 8900 8500 9600 9500 Acid value 80 80 80 80 80 80 80 Color material dispersion/photosensitive coloring resin composition B-4 B-5 B-6 B-7 CB-3 CB-4 CB-5 Evaluation Pigment type B15: 6/V23 Dispersion stability A A A A C D E Solvent resolubility A A A B D D Can't evaluate Substrate adhesion B A A B C D Can't evaluate Development time B A A E D A Can't evaluate

(Example 30) To the photosensitive colored resin composition R-3 obtained in Example 3 was added 0.07 parts by mass of a multifunctional thiol compound (trade name: KARENZ MTPE1; pentaerythritol tetrakis (3-mercaptobutyrate); manufactured by Showa Denko Corporation; Effective solid content 40%) to obtain photosensitive colored resin composition R-3a.

(Comparative Example 16) (1) Manufacturing of comparative dispersant U (amine graft copolymer) Add 150.0 parts by mass of PGMEA, 3.0 parts of iodine, 2,2'-azobis(4-methoxy-2, 4-Dimethylvaleronitrile) (trade name: V-70; manufactured by Wako Pure Chemical Industries, Ltd.), 46.6 parts by mass MMA, 7.8 parts by mass BMA, 23.3 parts by mass BzMA, 0.04 parts by mass succinimide, one side in nitrogen Stir under flow, while stirring at 40°C for 5 hours, to produce a copolymer of B block. The calculated value of Tg of the obtained copolymer was 78°C. Then, 22.4 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added, and the mixture was stirred at 40°C for 5 hours. The solid content was measured and converted based on the non-volatile content. As a result, the polymerization conversion rate was 99%. The reaction solution was reprecipitated with 3000 parts by mass of hexane, thereby obtaining 99.0 parts by mass of AB block comparative copolymer U. The weight average molecular weight (Mw) of the comparative copolymer U obtained in this way was 9600, the Mw/Mn was 1.2, and the amine value was 80 mgKOH/g.

(2)Comparative color material dispersion liquid CR-6 manufacturing In Example 1 (1), except that Comparative Dispersant U was used instead of Dispersant A, the same procedure as in Example 1 was carried out to obtain a comparative color material dispersion CR-6. (3) Comparison of the production of the photosensitive colored resin composition CR-6 In Example 30, the above-mentioned comparative color material dispersion CR-6 was used instead of the color material dispersion R-3, except that the same procedure as in Example 30 was carried out to obtain a comparative photosensitive colored resin composition containing a polyfunctional thiol compound.物CR-6.

[Evaluation method] <Notch resistance of photosensitive colored resin composition> The photosensitive colored resin composition obtained in Examples 3, 30 and Comparative Example 16 was stored at room temperature for 3 days, and then spin-coated was used. The cloth machine, after post-baking, will form a coloring layer with a thickness of 2.0 μm on the glass substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.), and then use a hot plate at 60°C Dry for 3 minutes, thereby forming a colored layer. An ultra-high pressure mercury lamp was used to irradiate the colored layer with 30 mJ/cm ² of ultraviolet rays through a mask with a mask opening width of 80 μm and a mask light shielding width of 160 μm. The glass plate on which the colored layer was formed was shower-developed for 100 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer. Observe the developed substrate with an optical microscope at 10 times, and measure the number of notches on the edge of the colored layer in the range of 50 mm×50 mm. Furthermore, in the required 80 μm-wide linear coloring pattern, the part that is cut out by 5 μm or more is regarded as a gap at the edge. (Evaluation criteria for notch resistance) A: No notch B: Less than 20 C: 20 or more and less than 50 D: 50 or more If the notch resistance evaluation criteria is A, B, or C, it can be used practically If the evaluation result is B, and then A, the effect is more excellent.

<Storage stability of photosensitive colored resin composition> For the photosensitive colored resin compositions obtained in Examples 3, 30 and Comparative Example 16, the viscosity immediately after preparation and the viscosity after storage at 40°C for 30 days were measured, and the viscosity change rate was calculated based on the viscosity before and after storage. , And evaluate the viscosity stability. A vibrating viscometer was used in the viscosity measurement to measure the viscosity at 25.0±0.5°C. (Evaluation criteria for dispersion stability) A: The change rate of viscosity before and after storage is less than 10% B: The change rate of viscosity before and after storage is more than 10% and less than 20% C: The change rate of viscosity before and after storage is more than 20% and less than 40% D: The change rate of viscosity before and after storage is more than 40% If the evaluation result is C, the storage stability is relatively good, if the evaluation result is B, the storage stability is good, and if the evaluation result is A, the storage stability of the color material dispersion liquid is excellent. The evaluation results are shown in Table 9.

[Table 9] Table 9 Example 3 Example 30 Comparative example 16 Photosensitive colored resin composition R-3 R-3a CR-6 Dispersant C C U Multifunctional thiol compound - 〇 〇 Notch resistance C A B Storage stability A A D

[Summary of Results of the First Invention] According to the comparison between the examples of the first invention and the comparative examples, it can be seen that in the first invention of the first invention using the graft copolymers or block copolymers specified in the invention, examples 1-29 can simultaneously satisfy A photosensitive colored resin composition with excellent dispersion stability, solvent resolubility, and substrate adhesion. In contrast, when used as a dispersant for graft copolymers or block copolymers containing only one of the structural unit represented by the above general formula (I) and the structural unit represented by the above general formula (II) In Comparative Examples 1 to 4, 6 to 9, and 11 to 14, the solvent re-solubility deteriorated. In Comparative Examples 2, 4, 7, 9, 12, In 14, dispersion stability and substrate adhesion were further deteriorated. In Comparative Examples 5, 10, and 15 in which random copolymers existing in the same monomer ratio as the block copolymer N of Example 12 and the like were used as dispersants, coagulation occurred during the dispersion process when the color material dispersion was prepared. Since it gelled, the color material dispersion liquid could not be recovered, and evaluation as a photosensitive colored resin composition could not be performed. It is also clear in the examples that if it is used in a polymer chain that contains the structural unit represented by the above general formula (IV) and the glass transition temperature of the polymer chain is below 85°C, or if it contains the structure represented by the above general formula (IV) A dispersant whose glass transition temperature of the B block of the structural unit is below 85°C can shorten the development time. In addition, it is also clear in the examples that if it is used in a polymer chain or B block, it contains a structural unit selected from the structural unit represented by the above general formula (V) and the structural unit represented by the above general formula (V'). The dispersant of at least one structural unit in the group improves the adhesion of the substrate and shortens the development time. In addition, according to Table 9, it is also clear in the examples that if a dispersant having an acidic group-containing structural unit and a polyfunctional thiol compound are used in combination in the photosensitive colored resin composition, the notch resistance is improved and the photosensitivity is improved. The storage stability of the colored resin composition becomes good.

Example II series: the second invention (Production Examples II-1 to II-3: Production of graft copolymers II-A to II-C) The macromonomers m2 and m3 were prepared in the same manner as the synthesis examples 2 and 3 of the Example I series. In the production example 1 of the embodiment I series, as shown in Table 10, the type of the macromonomer and the mass ratio of the macromonomer to the carboxyl-containing ethylenically unsaturated monomer were changed instead of using 92.9 parts by mass of the macromonomer Except m1, 4.2 parts by mass of MAA, and 2.9 parts by mass of 2-MOES, graft copolymers II-A to II-C were produced in the same manner as in Production Example 1 of the Example I series. Table 10 shows the weight average molecular weight (Mw), Mw/Mn, and acid value of the graft copolymers II-A to II-C obtained.

(Examples II-1～II-3) (1) Manufacturing of color material dispersion II-R-1～II-R-3 In (1) of Example 1 of the Example I series, as shown in Table 10, graft copolymers II-A to II-C as dispersants were used instead of dispersant A. In addition, the same as the examples Example 1 of the I series similarly produced color material dispersion liquids II-R-1 to II-R-3.

(2) Manufacture of photosensitive colored resin composition II-R-1～II-R-3 In Example 1 (2) of Example I series, the above-mentioned color material dispersion liquids II-R-1 to II-R-3 were used instead of color material dispersion liquid R-1. Otherwise, the same as in Example I In the same manner as in Example 1 (2) of the series, photosensitive colored resin compositions II-R-1 to II-R-3 were obtained. The evaluation was performed in the same manner as the evaluation of the adhesion to the substrate and the evaluation of the development time of the Example I series. The results are shown together with Comparative Examples 6 and 7 of the Example I series.

[Table 10] Table 10 Example Comparative example II-1 II-2 II-3 6 7 Dispersant II-A II-B II-C L M Copolymerization graft graft graft Comparative grafting Comparative grafting Giant monomer (mass ratio) Giant cell m3 m2 m2 m1 m1 MMA 60.0 70.0 70.0 60.0 60.0 BMA 10.0 10.0 BzMA 5.0 30.0 30.0 PME-200 30.0 30.0 PCL-FM5 35.0 Calculated value of polymer chain Tg(℃) 31 34 34 78 78 Grafted main chain (mass ratio) Giant cell 79.5 87.8 80.0 87.8 67.1 Formula (I): MAA 12.2 20.0 12.2 Formula (II): 2-MOES 20.5 32.9 Copolymer Mw/Mn 2.6 2.7 2.7 2.7 2.6 Mw 12300 13,400 17,800 14000 12200 Acid value 50 80 130 80 80 Color material dispersion/photosensitive coloring resin composition II-R-1 II-R-2 II-R-3 CR-1 CR-2 Evaluation Pigment type R177/R291 Substrate adhesion A A A C D Development time A A A D A

[Summary of results of the second invention] According to the comparison of Examples II-1 to II-3 and Comparative Examples, it is clear that in Examples II-1 to II-3 using the graft copolymer or block copolymer specified in the second invention, It is possible to obtain a photosensitive colored resin composition that satisfies both excellent substrate adhesion and developability (shortening of developing time). In the series of Examples 3, 5, 13, 14, 16, 18, 20, 21, 23, 25, 27 and 28, which are equivalent to the series of Examples of the second invention, the excellent substrate adhesion and development time are also clarified The shortening effect.

Embodiment III series: the third invention (Examples III-1 to III-2) (1) Manufacturing of color material dispersion III-R-1～III-R-2 The graft copolymers L and M were prepared in the same manner as the comparative graft copolymers L to M of Comparative Production Examples 1 to 2 of the Example I series. In (1) of Example 1 of the Example I series, as shown in Table 11, the graft copolymers L and M as dispersants were used instead of the dispersant A. Otherwise, the same as the implementation of the Example I series In Example 1, the color material dispersion liquids III-R-1 to III-R-2 were produced in the same manner.

(2) Production of photosensitive colored resin composition III-R-1～III-R-2 In the example 30 of the example I series, the above-mentioned color material dispersion liquids III-R-1 to III-R-2 were used instead of the color material dispersion liquid R-3. Otherwise, the same as the examples of the example I series 30 In the same manner, photosensitive colored resin compositions III-R-1 to III-R-2 to which a polyfunctional thiol compound was added were obtained. The evaluation was performed in the same manner as the evaluation of notch resistance and the evaluation of storage stability of the Example I series. The results are shown together with Comparative Example 16 of the Example I series.

[Table 11] Table 11 Example III-1 Example III-2 Comparative example 16 Photosensitive colored resin composition III-R-1 III-R-2 CR-6 Dispersant L M U Multifunctional thiol compound 〇 〇 〇 Notch resistance A A B Storage stability A A D

[Summary of the results of the third invention] According to the comparison of Examples III-1 to III-2 and the comparative example, it is clear that the dispersant and the polyfunctional thiol compound specified in the third invention are combined with a dispersant having an acidic group-containing structural unit In Examples III-1 to III-2, notch resistance was improved, and the storage stability of the photosensitive colored resin composition became good. In Example 30 corresponding to the series of Example I of the third invention, the effects of excellent notch resistance and storage stability were also clarified.

1: substrate 2: Shading part 3: Coloring 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: luminescent layer 75: electron injection layer 76: cathode 80: organic light-emitting body 100: organic light emitting display device

Fig. 1 is a schematic diagram showing an example of the color filter of the present invention. Fig. 2 is a schematic diagram showing an example of 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.

Claims (14)

A color material dispersion liquid, which contains a color material, a dispersant, and a solvent, and the dispersant contains at least one of a graft copolymer and a block copolymer, and the graft copolymer has the following general formula (I) The structural unit represented and the structural unit represented by the following general formula (II), and the block copolymer has a structure including the structural unit represented by the following general formula (I) and the structure represented by the following general formula (II) A block of unit; [化1]

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, in the general formula (II), R ^1'represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group that may contain an oxygen atom, and R ³ represents a fat Group hydrocarbon group). The color material dispersion liquid of claim 1, wherein in the dispersant, the graft copolymer has a structural unit represented by the following general formula (III), and the polymerization of the structural unit represented by the general formula (III) The material chain contains the structural unit represented by the following general formula (IV), the glass transition temperature of the polymer chain in the structural unit represented by the general formula (III) is 85°C or less, and the block copolymer has the following In the B block of the structural unit represented by the general formula (IV), the glass transition temperature of the B block is below 85°C; [化2]

(In the general formula (III), R ^1'' represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain) [化3]

(In the general formula (IV), R ¹¹ is a hydrogen atom or a methyl group, A ² is a divalent linking group, and R ⁴ is a hydrocarbon group that may have a substituent and may contain a hetero atom). The color material dispersion of claim 1 or 2, wherein in the dispersant, at least one of the graft copolymer and the block copolymer has an acid value of 30 mgKOH/g to 180 mgKOH/g. The color material dispersion liquid of claim 1 or 2, wherein in the dispersant, the graft copolymer has a structural unit represented by the following general formula (III), and in the structural unit represented by the general formula (III) The polymer chain includes at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (V) and the structural unit represented by the following general formula (V'), and the block copolymerization The product has a B block, and the B block contains at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (V) and a structural unit represented by the following general formula (V') ; [化4]

(In the general formula (III), R ^1'' represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain) [Chemical 5]

(Formula (V) in, R ^{11 'based} hydrogen atom or a methyl group, A ^2' based divalent linking group, R ⁵ or extension line extending ethyl propyl, R ⁶ a hydrogen atom or a hydrocarbon-based, m represents 2 or more A number below 80; In the general formula (V'), R ^11" is a hydrogen atom or a methyl group, A ^2" is a divalent linking group, R ⁷ is an alkylene group with 1 to 10 carbon atoms, and R ⁸ It is an alkylene group having 3 to 7 carbon atoms, R ⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 to 40). A dispersant, which is at least one of a graft copolymer and a block copolymer. The graft copolymer has a structural unit represented by the following general formula (I) and a structure represented by the following general formula (II) Unit, the block copolymer has an A block comprising a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II); [化6]

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, in the general formula (II), R ^1'represents a hydrogen atom or a methyl group, R ² represents an aliphatic hydrocarbon group that may contain an oxygen atom, and R ³ represents a fat Group hydrocarbon group). The dispersant of claim 5, wherein the graft copolymer has a structural unit represented by the following general formula (III), and the polymer chain in the structural unit represented by the general formula (III) comprises the following general formula ( The structural unit represented by IV), the glass transition temperature of the polymer chain in the structural unit represented by the general formula (III) is 85°C or less, and the block copolymer has the structure represented by the following general formula (IV) For the B block of the structural unit, the glass transition temperature of the B block is below 85°C; [化7]

(In the general formula (III), R ^1'' represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain) [Chemical Formula 8]

(In the general formula (IV), R ¹¹ is a hydrogen atom or a methyl group, A ² is a divalent linking group, and R ⁴ is a hydrocarbon group that may have a substituent and may contain a hetero atom). Such as the dispersant of claim 5 or 6, its acid value is 30 mgKOH/g～180 mgKOH/g. The dispersant according to claim 5 or 6, wherein the graft copolymer has a structural unit represented by the following general formula (III), and the polymer chain in the structural unit represented by the general formula (III) contains selected from At least one structural unit in the group consisting of the structural unit represented by the general formula (IV) and the structural unit represented by the following general formula (IV'), and the block copolymer has a B block, and the B The block includes at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (IV) and a structural unit represented by the following general formula (IV'); [化9]

(In the general formula (III), R ^1'' represents a hydrogen atom or a methyl group, A ¹ represents a direct bond or a divalent linking group, and Polymer represents a polymer chain) [Chemical Formula 10]

(Formula (V) in, R ^{11 'based} hydrogen atom or a methyl group, A ^2' based divalent linking group, R ⁵ or extension line extending ethyl propyl, R ⁶ a hydrogen atom or a hydrocarbon-based, m represents 2 or more A number below 80; In the general formula (V'), R ^11" is a hydrogen atom or a methyl group, A ^2" is a divalent linking group, R ⁷ is an alkylene group with 1 to 10 carbon atoms, and R ⁸ It is an alkylene group having 3 to 7 carbon atoms, R ⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 to 40). A photosensitive colored resin composition containing a color material, a dispersant such as any one of claims 5 to 8, a multifunctional monomer, a photoinitiator, and a solvent. The photosensitive colored resin composition of claim 9, which further contains a polyfunctional thiol compound. The photosensitive colored resin composition according to claim 10, wherein the above-mentioned multifunctional thiol compound is a multifunctional thiol compound represented by the following general formula (A); [化11]

In (Formula ^(A), R ^a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms of, R ^b represents 1 to 6 carbon atoms extension of the group, Q represents a residue of the polyol hydroxyl number of 2 to 6, s is an integer of 2-6). A cured product, which is a cured product of the photosensitive colored resin composition according to any one of claims 9 to 11. A color filter is provided with at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claim 12. A display device having the above-mentioned color filter as claimed in claim 13.

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