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

Abstract

The present application provides a color material dispersion liquid containing a color material, a dispersant, and a solvent, and the dispersant contains at least one of a block copolymer and a graft copolymer, the block copolymer has an A block containing a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the graft copolymer has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and each symbol in the general formula (I) and (II) is as described in the specification.

Description

Technical Field

[0001] This invention relates to a color material dispersion, a dispersant, a photosensitive coloring resin composition, a cured product, a color filter, and a display device. Existing technology

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for LCD monitors has been increasing. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is also constantly rising, leading to a continuously expanding market for LCD monitors. Furthermore, recently, organic light-emitting diode (OLED) displays, which offer high visibility due to their self-emissive nature, have also attracted attention as next-generation image display devices. Regarding the performance of these image display devices, there is a strong expectation for further improvements in image quality, such as enhanced contrast or color reproduction, or reduced power consumption.

[0003] Color filters are used in these liquid crystal display devices or organic light-emitting display devices. For example, in the formation of a color image in a liquid crystal display device, light passing through a color filter is directly colored into the colors of the individual pixels constituting the color filter, and these colored lights are combined to form a color image. As the light source, in addition to the previously used cold cathode tube, sometimes white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements are also used. Furthermore, in organic light-emitting display devices, color filters are used for color adjustment, etc.

[0004] Given this situation, the requirements for color filters are constantly increasing, such as higher brightness or higher contrast, and improved color reproduction.

[0005] Here, the color filter generally has: a transparent substrate; a color layer formed on the transparent substrate and containing color patterns of the three primary colors of red, green and blue; and a light-shielding part formed on the transparent substrate in a manner that divides each color pattern.

[0006] Among the methods for forming pixels in color filters, the pigment dispersion method, which has excellent properties on average, is the most widely used in terms of spectral characteristics, durability, pattern shape, and accuracy.

[0007] Regarding color filters with pixels formed using a pigment dispersion method, pigment miniaturization has been studied to achieve high brightness or high contrast. It is believed that by miniaturizing the pigment, the scattering of light passing through the color filter caused by pigment particles is reduced, thereby achieving high brightness or high contrast.

[0008] However, the micronized pigment particles are prone to agglomeration, which leads to a decrease in dispersibility or dispersion stability.

[0009] As a method to improve the dispersibility of micronized pigments, the use of dispersants is known to be quite effective. For example, in Patent Document 1, in order to prevent pigment aggregation and obtain a finely dispersed pigment dispersion, a pigment dispersion is disclosed, which is formed by dispersing the pigment through an AB block copolymer. The AB block copolymer is characterized in that: the monomer units constituting the polymer substantially contain (meth)acrylate monomers, and the polymer blocks constituting the A chain of the copolymer contain (meth)acrylate monomer units having carboxyl groups, with an acid value of 50 to 250 mg KOH / g, and the polymer blocks constituting the B chain of the copolymer contain acetyl acetoxyethyl methacrylate as monomer units.

[0010] On the other hand, Patent Document 2 describes the following situation: In order to provide a photosensitive resin composition with excellent balance of solubility, photosensitivity and other properties, in a photopolymerizable composition comprising an adhesive resin having carboxyl and / or hydroxyl groups, a photopolymerizable monomer and a photopolymerization initiator, the adhesive resin having carboxyl and / or hydroxyl groups is a copolymer comprising repeating units represented by a specific formula (I), and at least a portion of the carboxyl or hydroxyl groups are formed in a structure having an olefinic unsaturated group at the end, wherein the repeating unit represented by the specific formula (I) is derived from a monomer formed by adding an acid (anhydride) to a hydroxyalkyl methacrylate.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Patent Application Publication No. 2011-241259

[0014] Patent Document 2: Japanese Patent Application Publication No. 2000-227655 Summary of the Invention

[0015] The problem the invention aims to solve

[0016] As mentioned above, in recent years, due to the demand for high brightness and high contrast in color filters, the particle size of the pigments used has gradually become smaller. The increased specific surface area of ​​these smaller pigments makes them more prone to aggregation, thus requiring dispersants with higher dispersion performance. Furthermore, the demand for higher concentrations of pigments in photosensitive resin compositions has increased due to requirements such as high color gamut and thin film formation. If the proportion of pigments in the photosensitive resin composition increases, the binder component decreases relatively. A decrease in binder components related to the curability of the coating film, such as multifunctional monomers or photoinitiators, leads to insufficient curing, resulting in a lower crosslinking density and reduced substrate adhesion. Similarly, an increase in the proportion of pigments that are difficult to dissolve in solvents in the photosensitive resin composition, coupled with a relative decrease in binder components that are easily soluble in solvents, leads to poorer solvent resolvability. Therefore, to achieve the requirement of high pigment concentration in photosensitive resin compositions, techniques are needed to simultaneously address the problems caused by these insufficient binder components. Furthermore, substrate adhesion refers to the adhesion between the formed resist pattern (the patterned cured product of the photosensitive resin composition) and the substrate. Poor substrate adhesion can lead to problems such as pattern peeling due to physical impacts during subsequent processes, resulting in poor display. Additionally, solvent resolvability refers to the property of the solid components of the coloring resin composition, after one drying step, to dissolve again in the solvent. For example, if the photosensitive coloring resin composition adheres to the die lip during coating using a die-applied coating machine, curing will occur during drying. If this cured product is not easily dissolved in the photosensitive coloring resin composition when coating resumes, a portion of the cured product on the die lip can easily peel off and adhere to the coloring layer of, for example, a color filter, causing foreign matter defects. Especially when the colorant concentration of the coloring resin composition is increased, solvent resolvability can become insufficient, leading to a decrease in yield due to the aforementioned foreign matter generated during the color filter manufacturing process.

[0017] The present invention was made in view of the above-mentioned actual situation, and its first objective is to provide a colorant dispersion and a dispersant capable of producing a photosensitive coloring resin composition that simultaneously satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion. Furthermore, the first objective of the present invention is to provide a photosensitive coloring resin composition that simultaneously satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion. Additionally, the first objective of the present invention is to provide a color filter and a display device formed using the photosensitive coloring resin composition.

[0018] Furthermore, a second objective of the present invention is to provide a colorant dispersion capable of producing a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability (reduced developing speed), as a technique to simultaneously solve the problem caused by insufficient binder components. Furthermore, a second objective of the present invention is to provide a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability, and a color filter and display device formed using the photosensitive coloring resin composition.

[0019] Furthermore, as a technology to address the problem caused by insufficient binder components, there is also a need to suppress phenomena such as excessive corrosion of the cured photosensitive resin composition by the developing solution due to alkaline development, or peeling off from the substrate due to physical impacts caused by developing water pressure. However, there has always been a problem that addressing the notch resistance issue would worsen the preservation stability of the composition. Therefore, a third object of the present invention is to provide a photosensitive coloring resin composition with good notch resistance and good preservation stability, a color filter and a display device formed using the photosensitive coloring resin composition.

[0020] Technical means to solve the problem

[0021] The colorant dispersion of the first invention for achieving the first objective described above contains a colorant, a dispersant, and a solvent, and

[0022] The dispersant contains at least one of a graft copolymer and a block copolymer, wherein the graft copolymer has a structural unit represented by general formula (I) and a structural unit represented by general formula (II), and the block copolymer has an A block comprising a structural unit represented by general formula (I) and a structural unit represented by general formula (II).

[0023] [Chemical Formula 1]

[0024]

[0025] (In general formula (I), R) 1 Indicates a hydrogen atom or a methyl group.

[0026] In general formula (II), R 1 ' represents a hydrogen atom or a methyl group, R 2 R represents any aliphatic hydrocarbon group containing an oxygen atom. 3 (This indicates an aliphatic hydrocarbon group.)

[0027] The dispersant of the first invention for achieving the first objective described above is at least one of a graft copolymer and a block copolymer, wherein the graft copolymer has structural units represented by the general formula (I) and the general formula (II), and the block copolymer has an A block comprising the structural units represented by the general formula (I) and the general formula (II).

[0028] The photosensitive coloring resin composition of the first invention for achieving the first objective described above contains a colorant, the dispersant of the first invention described above, a multifunctional monomer, a photoinitiator, and a solvent.

[0029] The second color material dispersion of the present invention, used to achieve the second objective described above, contains a color material, a dispersant, and a solvent.

[0030] The dispersant described above contains at least one of a graft copolymer and a block copolymer. The graft copolymer has structural units derived from a carboxyl-containing olefinic unsaturated monomer and structural units represented by the following general formula (III). The polymer chain in the structural unit represented by the general formula (III) contains at least one structural unit selected from the structural units represented by the following general formula (V) and the following general formula (V'). The block copolymer has: an A block comprising a structural unit derived from a carboxyl-containing olefinic unsaturated monomer; and a B block comprising at least one structural unit selected from the structural units represented by the following general formula (V) and the following general formula (V').

[0031] [Chemical Formula 2]

[0032]

[0033] (In general formula (III), R) 1” A represents a hydrogen atom or a methyl group. 1 (This indicates a direct bond or a divalent linker; Polymer represents a polymer chain.)

[0034] [Chemical Formula 3]

[0035]

[0036] (In general formula (V), R) 11' A is a hydrogen atom or a methyl group. 2' For a divalent linkage base, R 5 It is ethylene or propylene, R 6 It represents a hydrogen atom or a hydrocarbon group, where m represents a number greater than 2 and less than 80;

[0037] In the general formula (V'), R 11” A is a hydrogen atom or a methyl group. 2” For a divalent linkage base, R 7R is an alkylene group having 1 to 10 carbon atoms. 8 R is an alkylene group having 3 to 7 carbon atoms. 9 (This represents a hydrogen atom or a hydrocarbon group, where n is a number greater than 1 and less than 40.)

[0038] The second photosensitive coloring resin composition of the present invention for achieving the second objective described above contains a colorant, a dispersant, a multifunctional monomer, a photoinitiator, and a solvent.

[0039] The dispersant contains at least one of a graft copolymer and a block copolymer. The graft copolymer has structural units derived from a carboxyl-containing olefinic unsaturated monomer and structural units represented by the general formula (III). The polymer chain in the structural unit represented by the general formula (III) contains at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V'). The block copolymer has: an A block containing a structural unit derived from a carboxyl-containing olefinic unsaturated monomer; and a B block containing at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V').

[0040] The third photosensitive coloring resin composition of the present invention for achieving the third objective described above contains a colorant, a dispersant, a multifunctional monomer, a photoinitiator, a solvent, and a multifunctional thiol compound. The dispersant includes at least one type of graft copolymer and block copolymer having structural units derived from carboxyl-containing olefinic unsaturated monomers.

[0041] The color filter of the present invention comprises at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured product of the photosensitive coloring resin composition of the present invention.

[0042] The display device of the present invention includes the color filter of the present invention described above.

[0043] Invention Effects

[0044] According to the first invention, a colorant dispersion and a dispersant are provided that can produce a photosensitive coloring resin composition that simultaneously satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion. Furthermore, according to the invention, a photosensitive coloring resin composition that simultaneously satisfies excellent dispersion stability, solvent resolubility, and substrate adhesion is provided. Furthermore, according to the invention, a color filter and a display device formed using the photosensitive coloring resin composition are provided.

[0045] According to the second invention, a colorant dispersion and a dispersant capable of producing a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability can be provided. Furthermore, according to the second invention, a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability, a color filter formed using the photosensitive coloring resin composition, and a display device can be provided.

[0046] According to the third invention, a photosensitive coloring resin composition with good notch resistance and good storage stability, a color filter formed using the photosensitive coloring resin composition, and a display device can be provided. Attached Figure Description

[0047] Figure 1 A schematic diagram illustrating an example of the color filter of the present invention.

[0048] Figure 2 This is a schematic diagram illustrating an example of the liquid crystal display device of the present invention.

[0049] Figure 3 This is a schematic diagram illustrating an example of the organic light-emitting display device of the present invention. Detailed Implementation

[0050] The following sections will describe in detail the color material dispersion, dispersant, photosensitive coloring resin composition, color filter, and display device of the present invention.

[0051] It should be noted that, in this invention, light includes electromagnetic waves with wavelengths in both the visible and non-visible light regions, as well as radiation, such as microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with wavelengths below 5 μm.

[0052] In this invention, the term (meth)acryloyl group refers to either acryloyl group or methacryloyl group; the term (meth)acrylic acid group refers to either acrylic acid group or methacrylic acid group; and the term (meth)acrylate group refers to either acrylate group or methacrylate group.

[0053] Unless otherwise specified, the chromaticity coordinates x and y in this specification are the coordinates in the XYZ colorimetric system of JIS Z8701:1999, which uses a C-light source for color measurement.

[0054] Furthermore, in this specification, the "~" sign indicating a numerical range is used to mean that the numerical values ​​before and after it are both the lower and upper limits.

[0055] I. The First Invention

[0056] I-1. The first colorant dispersion of the present invention

[0057] The first color material dispersion of the present invention contains a color material, a dispersant, and a solvent.

[0058] The dispersant contains at least one of a graft copolymer and a block copolymer, wherein the graft copolymer has a structural unit represented by general formula (I) and a structural unit represented by general formula (II), and the block copolymer has an A block comprising a structural unit represented by general formula (I) and a structural unit represented by general formula (II).

[0059] [Chemical Formula 4]

[0060]

[0061] (In general formula (I), R) 1 Indicates a hydrogen atom or a methyl group.

[0062] In general formula (II), R 1' R represents a hydrogen atom or a methyl group. 2 R represents any aliphatic hydrocarbon group containing an oxygen atom. 3 (This indicates an aliphatic hydrocarbon group.)

[0063] The first color material dispersion of the present invention uses an acidic dispersant as at least one of a graft copolymer and a block copolymer, wherein the graft copolymer contains the two specific structural units containing acidic groups (the structural unit represented by general formula (I) and the structural unit represented by general formula (II)), and the block copolymer has an A block containing the two specific structural units containing acidic groups.

[0064] Regarding the graft copolymers and block copolymers used in the first invention, it is presumed that: by using structural units represented by the general formula (I) with a rigid structure (hereinafter, sometimes referred to as "structural unit (I)") and structural units represented by the general formula (II) with a flexible structure (hereinafter, sometimes referred to as "structural unit (II)") as adsorption sites on the color material, compared with the case of using structural unit (I) or (II) alone, adsorption can be performed with higher efficiency on both the surface of the color material that is more suitable for adsorption by structural unit (I) and the surface that is more suitable for adsorption by structural unit (II), relative to the surface of the color material in various states such as stereoobstruction or polarity, thus improving the dispersion stability.

[0065] As shown in the comparative examples below, dispersants with acidic groups tend to have the following tendency: the acidic groups of dispersants that cannot be adsorbed onto the colorant cause the solvent resolubility to deteriorate through contact with the solvent. Furthermore, regarding dispersants with acidic groups, it is presumed that if the adsorption force on the colorant is low, the dispersant is free in the solvent and cannot be adsorbed onto the surface of the colorant. As a result, the surface area of ​​the solvent-affinity portion of the dispersant relative to the surface of the colorant decreases, and the contact amount between the acidic groups of the dispersant and the solvent increases. These effects complement each other, leading to a significant deterioration in solvent resolubility. In contrast, regarding the graft copolymers and block copolymers used in the first invention, it is presumed that, as described above, the structural units (I) and (II), which are the adsorption sites of the dispersant, are efficiently adsorbed onto the surface of the colorant and coated with the colorant. As a result, the surface area of ​​the solvent-affinity portion of the dispersant relative to the surface of the colorant increases, and the acidic groups of the dispersant do not easily contact the solvent, thereby improving the solvent resolubility.

[0066] Furthermore, it can be inferred that the substrate adhesion of the coating is improved by the interaction between the structural units (I) and (II) as adsorption sites of the dispersant and the polar groups such as the glass surface of the substrate. It can also be inferred that by using both the rigid structural unit (I) and the flexible structural unit (II) together, compared with the case of using structural unit (I) or (II) alone, the coating can interact with both the surface more suitable for adsorption by structural unit (I) and the surface more suitable for adsorption by structural unit (II) with higher efficiency relative to the substrate surface, thereby improving the substrate adhesion of the coating.

[0067] The color material dispersion of the first invention contains at least a color material, a dispersant, and a solvent, and may also contain other components within the scope that does not impair the effects of the invention.

[0068] Hereinafter, starting with the dispersant of the first invention, each component of the colorant dispersion of the first invention will be described in detail.

[0069] <The dispersant of the first invention>

[0070] In the first invention, at least one of a graft copolymer and a block copolymer is used as a dispersant, wherein the graft copolymer has structural units represented by general formula (I) and general formula (II), and the block copolymer has an A block comprising structural units represented by general formula (I) and general formula (II).

[0071] [Graft copolymer]

[0072] The first graft copolymer used in this invention is a copolymer having structural units represented by the above general formula (I) and the above general formula (II) in the main chain, which function as adsorption sites relative to the colorant, and graft polymer chains that function as solvent affinity sites in the side chains.

[0073] (Structural unit represented by general formula (I), structural unit represented by general formula (II))

[0074] The structural unit represented by general formula (I) is a structural unit derived from (meth)acrylic acid.

[0075] In the structural unit represented by general formula (II), R 2 This indicates that any aliphatic hydrocarbon group containing an oxygen atom can be selected.

[0076] Examples of aliphatic hydrocarbon groups include straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon groups. Examples of such aliphatic hydrocarbon groups include: straight-chain alkylene groups such as methylene, dimethylene (ethylene), trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and decamethylene; branched alkylene groups such as methylmethylene, methylethylene, 1-methylpentylene, and 1,4-dimethylbutylene; and cyclic alkylene groups such as cyclopentylene and cyclohexylene.

[0077] As R 2 The number of carbon atoms in the aliphatic hydrocarbon group can be 1 to 20, and in terms of dispersion stability, 1 to 16 is preferred, 1 to 12 is more preferred, and 2 to 8 is even more preferred.

[0078] The so-called R 2 The aliphatic hydrocarbon group containing an oxygen atom has a structure in which the carbon atom in the aforementioned aliphatic hydrocarbon group is replaced by an oxygen atom, or has a structure in which the hydrogen atom in the aforementioned aliphatic hydrocarbon group is replaced by a substituent containing an oxygen atom. As an optional aliphatic hydrocarbon group containing an oxygen atom, examples include structures in which the carbon chain of the hydrocarbon group contains a linker such as -O-, -COO-, or -OCO-. Specifically, as an aliphatic hydrocarbon group containing an oxygen atom, an example is -R... 20 -(OR 21 )j-(here, R 20 and R 21 Each group independently represents an aliphatic hydrocarbon group, where j represents a number from 1 to 80), -R 22 -(OCO-R 23 )k-(here, R 22 and R 23 Each group independently represents an aliphatic hydrocarbon group, and k represents a number from 1 to 40. R 20 R 21 R 22 and R 23The aliphatic hydrocarbon group can be the same as the aforementioned aliphatic hydrocarbon group. Regarding dispersion stability, the aforementioned R... 20 Preferably, it is an alkylene group having 1 to 20 carbon atoms, and the above R 21 Preferably, the alkylene group has 1 to 20 carbon atoms, more preferably 1 to 40, and even more preferably 2 to 25, and even more preferably 2 to 10. Furthermore, regarding dispersion stability, the aforementioned R... 22 Preferably, it is an alkylene group having 1 to 20 carbon atoms, and the above R 23 The preferred carbon number is 1 to 20 alkylene groups, and k is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.

[0079] The above R 20 and the above R 22 Alkylenes having 1 to 12 carbon atoms are preferred, and alkylenes having 2 to 8 carbon atoms are more preferred.

[0080] The above R 21 Preferably, it is an alkylene group having 2 to 8 carbon atoms, more preferably ethylene or propylene.

[0081] The above R 23 Preferably, the alkylene group has 2 to 8 carbon atoms, and more preferably, it has 3 to 7 carbon atoms.

[0082] In addition, examples of substituents containing oxygen atoms include hydroxyl or alkoxy groups.

[0083] In the structural unit represented by general formula (II), as R 2 In terms of solvent resolubility, it can be an aliphatic hydrocarbon group, and can be an aliphatic hydrocarbon group with 1 to 20 carbon atoms.

[0084] In the structural unit represented by general formula (II), R 3 It represents an aliphatic hydrocarbon group.

[0085] Examples of aliphatic hydrocarbon groups include straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon groups. Examples of such aliphatic hydrocarbon groups include: straight-chain alkylene groups such as methylene, dimethylene (ethylene), trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and decamethylene; branched alkylene groups such as methylmethylene, methylethylene, 1-methylpentylene, and 1,4-dimethylbutylene; cyclic alkylene groups such as cyclopentylene and cyclohexylene; and unsaturated alkylene groups such as -CH=CH- group.

[0086] As R 3 The number of carbon atoms in the aliphatic hydrocarbon group can be 1 to 20, and in terms of dispersion stability, 1 to 16 is preferred, 2 to 12 is more preferred, and 2 to 6 is even more preferred.

[0087] The structural unit represented by general formula (II) can be derived, for example, from monomers that are products of addition reactions of (meth)acrylates with hydroxyl groups with aliphatic dicarboxylic acids or aliphatic dicarboxylic anhydrides.

[0088] Examples of (meth)acrylates having hydroxyl groups include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and ε-caprolactone modified with unsaturated fatty acid hydroxyalkyl esters.

[0089] In addition, examples of aliphatic dicarboxylic acids or aliphatic dicarboxylic anhydrides include: malonic acid, succinic acid, glutaric acid, adipic acid, 1,6-hexanedicarboxylic acid, hexahydrophthalic acid, succinic anhydride, adipic anhydride, hexahydrophthalic anhydride, maleic anhydride, etc.

[0090] In graft copolymers, the structural unit represented by general formula (I) may contain one type or more structural units. In addition, the structural unit represented by general formula (II) may contain one type or more structural units.

[0091] Regarding the stability of dispersion, when the total number of structural units represented by general formula (I) and general formula (II) is set to 100 parts by mass, the content ratio of the structural unit represented by general formula (I) is preferably 35 parts by mass or more, more preferably 50 parts by mass or more, and preferably 95 parts by mass or less, more preferably 85 parts by mass or less.

[0092] (Structural units with grafted polymer chains)

[0093] The above-mentioned graft copolymer has graft polymer chains in the side chains that function as solvent affinity parts.

[0094] The polymer chain is preferably 20 (g / 100g solvent) or more at 23°C relative to the organic solvent used in combination.

[0095] The solubility of the polymer chain can be measured by the solubility of the raw material introduced into the polymer chain during the preparation of the graft copolymer. For example, when introducing the polymer chain into the graft copolymer, if a polymeric oligomer (macromonomer) containing a polymer chain and a group having an olefinic unsaturated double bond at its end is used, it is sufficient that the polymeric oligomer has the aforementioned solubility. Furthermore, when introducing the polymer chain by using a polymer chain containing a reactive group that can react with the reactive groups contained in the copolymer after forming the copolymer with a monomer containing a group having an olefinic unsaturated double bond, it is sufficient that the polymer chain containing the reactive group has the aforementioned solubility.

[0096] The graft copolymer used in the first invention preferably has a structural unit represented by the following general formula (III), wherein the structural unit has a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II) in the main chain that functions as an adsorption site for colorant, and further has a polymer chain in the side chain that functions as a solvent affinity part.

[0097] [Chemical Formula 5]

[0098]

[0099] (In general formula (III), R) 1” A represents a hydrogen atom or a methyl group. 1 (Indicates direct bonding or divalent linkage; Polymer indicates polymer chain)

[0100] In the above general formula (III), A 1 For direct bonding or divalent linkage. As A 1 The divalent linker in the polymer chain is not particularly limited, as long as it can link a carbon atom derived from an olefinic unsaturated double bond to the polymer chain. Examples of divalent linkers include: straight-chain, branched, or cyclic alkylene groups; straight-chain, branched, or cyclic alkylene groups with hydroxyl groups; aryl groups; -CONH- groups; -COO- groups; -NHCOO- groups; ether groups (-O- groups); thioether groups (-S- groups); and combinations thereof. It should be noted that in this invention, the orientation of the bond in the divalent linker is arbitrary. That is, when the divalent linker contains -CONH-, -CO can be on the carbon atom side of the main chain and -NH can be on the nitrogen atom side of the side chain, or conversely, -NH can be on the carbon atom side of the main chain and -CO can be on the nitrogen atom side of the side chain.

[0101] In terms of dispersion, A in general formula (III) 1 Preferably, the divalent linkage contains a -CONH- group or a -COO- group, and more preferably, the divalent linkage contains a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0102] In terms of the dispersibility and dispersion stability of the colorant, the polymer chain preferably contains at least one structural unit represented by the following general formula (IV).

[0103] [Chemical Formula 6]

[0104]

[0105] (In general formula (IV), R) 11 A is a hydrogen atom or a methyl group. 2 For a divalent linkage base, R 4 (Optionally, a hydrocarbon group having substituents and optionally containing heteroatoms)

[0106] In general formula (IV), A 2 It is a divalent linked base. As A 2 The divalent linker in the above can be exemplified by A. 1 The same group as the divalent linker in the group.

[0107] Regarding the dispersibility and dispersion stability of the colorant, A in general formula (IV) 2 Preferably, it contains a divalent linker containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group.

[0108] R 4 Examples of hydrocarbon groups containing heteroatoms include alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 2 to 18 carbon atoms, aryl groups, and combinations of aralkyl or alkyl-substituted aryl groups.

[0109] The alkyl group having 1 to 18 carbon atoms can be any of the following: linear, branched, or cyclic. Examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, borneol, isoborneol, dicyclopentyl, adamantyl, and lower alkyl-substituted adamantyl. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 6.

[0110] The alkenyl group with 2 to 18 carbon atoms can be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond in the alkenyl group is not limited, but a double bond at the end of the alkenyl group is preferred in terms of the reactivity of the obtained polymer. The alkenyl group preferably has 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.

[0111] Examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl. The number of carbon atoms in the aryl group is preferably 6 to 24, and more preferably 6 to 12.

[0112] Furthermore, examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl, and they may also have substituents. The number of carbon atoms in the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.

[0113] In addition, straight-chain or branched alkyl groups with 1 to 30 carbon atoms can be bonded to the aromatic rings of the above-mentioned aryl, aralkyl, etc. as substituents.

[0114] As R 4 The hydrocarbon group in the hydrocarbon group, in terms of dispersion stability, is preferably selected from one or more of alkyl groups having 1 to 18 carbons, aryl groups having 6 to 12 carbons that can be substituted by alkyl groups, and aralkyl groups having 7 to 14 carbons that can be substituted by alkyl groups, and is preferably selected from one or more of phenyl groups that can be substituted by methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, alkyl-substituted phenyl groups, and benzyl groups.

[0115] R 4 The hydrocarbon group containing heteroatoms has a structure in which the carbon atom in the aforementioned hydrocarbon group is replaced by a heteroatom, or a structure in which the hydrogen atom in the aforementioned hydrocarbon group is replaced by a substituent containing a heteroatom. Examples of heteroatoms that may be optionally contained in the hydrocarbon group include oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms. Examples of hydrocarbon groups that may optionally contain heteroatoms include structures in which the carbon chain of the hydrocarbon group contains linking groups such as -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-, and -O-NH-.

[0116] Furthermore, the hydrocarbon group may also have substituents within a range that does not impair the dispersion properties of the graft copolymer. Examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups, nitro groups, cyano groups, epoxy groups, isocyanate groups, thiol groups, etc.

[0117] In addition, as R 4 The optional hydrocarbon group containing heteroatoms can also be a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linker group containing heteroatoms. For example, the structural unit represented by general formula (IV) can also be a structure obtained by reacting glycidyl (meth)acrylate with a structural unit derived from (meth)acrylic acid. That is, in general formula (IV) -A 2 -R 4The structure can also be represented by -COO-CH2CH(OH)CH2-OCO-CR=CH2 (where R is a hydrogen atom or a methyl group). Furthermore, the structural unit represented by general formula (IV) can also be a structure obtained by reacting a 2-isocyanate alkyl ester of (meth)acrylate with a structural unit derived from a hydroxyalkyl ester of (meth)acrylate. That is, R in general formula (IV) 4 It can also be represented by the structure -R'-OCONH-R”-OCO-CR=CH2 (where R' and R” are independently alkylene groups, and R is a hydrogen atom or a methyl group).

[0118] The monomers that are structural units represented by the derived general formula (IV) preferably have structural units derived from, for example, the following: methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 2-ethoxyethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate, Adamantane methacrylate, methacrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, phenoxyethyl methacrylate, methoxy polyethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, unsaturated fatty acid hydroxyalkyl esters modified with ε-caprolactone, etc. However, it is not limited to these.

[0119] In this invention, as the above-mentioned R 4 Among these, those with excellent solubility in the following organic solvents are preferred, and can be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when the above-mentioned organic solvent is an ether-alcohol-acetic acid ester, ether-based, ester-based, or alcohol-based organic solvent commonly used as an organic solvent for colorant dispersions, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxy polyethylene glycol, methoxy polyethylene glycol, polyethylene glycol, etc., are preferred.

[0120] In the polymer chain described above, the structural unit represented by the general formula (IV) may be a single type or a mixture of two or more types.

[0121] Regarding the dispersibility and dispersion stability of the colorant, when the total structural units of the polymer chain are set to 100% by mass, the total ratio of the structural units represented by the general formula (IV) can also be 100% by mass. Regarding the dispersibility and dispersion stability of the colorant, when the total structural units of the polymer chain are set to 100% by mass, the total ratio of the structural units represented by the general formula (IV) is preferably 40% by mass or more, and more preferably 70% by mass or more.

[0122] Furthermore, regarding the polymer chain of the macromonomer, the structural unit represented by the above general formula (IV) includes at least one structural unit selected from the structural units represented by the following general formula (V) and the following general formula (V'). In this case, the substrate adhesion is improved, the development time is shortened, and the cross-sectional shape of the resist pattern is more likely to become a positive cone shape, which is therefore preferred. If the cross-sectional shape of the resist pattern becomes an inverted cone shape, there is a concern that the ITO film formed on the resist pattern may experience broken lines, resulting in poor display.

[0123] [Chemical Formula 7]

[0124]

[0125] (In general formula (V), R) 11' A is a hydrogen atom or a methyl group. 2' For a divalent linkage base, R 5 It is ethylene or propylene, R 6 It represents a hydrogen atom or a hydrocarbon group, where m represents a number greater than 2 and less than 80;

[0126] In the general formula (V'), R 11” A is a hydrogen atom or a methyl group. 2” For a divalent linkage base, R 7 R is an alkylene group having 1 to 10 carbon atoms. 8 R is an alkylene group having 3 to 7 carbon atoms. 9 (This represents a hydrogen atom or a hydrocarbon group, where n is a number greater than 1 and less than 40.)

[0127] In the structural units represented by the above general formula (V) and general formula (V'), A 2' and A 2” Each is independently a divalent linker. As A 2' and A 2” The divalent linker in the above can be exemplified by A. 2 The same group as the divalent linker in the group.

[0128] Regarding the solubility of organic solvents used in color filters, A 2' and A2” Each is preferably a divalent linker containing a -CONH- group or a -COO- group, and more preferably a -CONH- group or a -COO- group.

[0129] In the above general formula (V), m represents the number of repeating units of the ethylene oxide chain or propylene oxide chain, and represents a number of 2 or more, wherein, in terms of substrate adhesion, 3 or more is preferred, and more preferably 4 or more.

[0130] On the other hand, the upper limit of m is 80 or less, and in terms of solubility in organic solvents used for color filters, it is preferably 50 or less.

[0131] R 6 It is a hydrogen atom or a hydrocarbon group, as the above R 6 The hydrocarbon group in the group can be, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, and combinations of aralkyl or alkyl-substituted aryl groups.

[0132] As mentioned above, R 6 The hydrocarbon group in it can be exemplified by the R group mentioned above. 4 The same group as the hydrocarbon group in it.

[0133] As R 6 The hydrocarbon group in the hydrocarbon group, in terms of dispersion stability, is preferably selected from one or more of alkyl groups having 1 to 18 carbons, aryl groups having 6 to 12 carbons that can be substituted by alkyl groups, and aralkyl groups having 7 to 14 carbons that can be substituted by alkyl groups, and is preferably selected from one or more of phenyl groups that can be substituted by methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, alkyl-substituted phenyl groups, and benzyl groups.

[0134] In the above general formula (V'), R 7 It is an alkylene group having 1 to 10 carbon atoms, wherein, in terms of solvent resolubility, an alkylene group having 2 to 8 carbon atoms is preferred.

[0135] R 8 It is an alkylene group having 3 to 7 carbon atoms, wherein, in terms of substrate adhesion, an alkylene group having 3 to 5 carbon atoms is preferred, and an alkylene group having 5 carbon atoms is even more preferred.

[0136] R 9 It is a hydrogen atom or a hydrocarbon group, as the above R 9 The hydrocarbon group in it can react with the above R 6 The hydrocarbon groups are the same.

[0137] In the above general formula (V'), n represents the number of repeating units of the lactone chain, and represents a number of 1 or more, preferably 2 or more, and more preferably 3 or more.

[0138] On the other hand, the upper limit of n is 40 or less, and in terms of solubility in organic solvents used for color filters, 20 or less is preferred.

[0139] In the polymer chain described above, at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V') may be a single unit or a mixture of two or more units.

[0140] To improve substrate adhesion, shorten development time, and facilitate the transformation of the resist pattern's cross-sectional shape into a conical shape, when the total structural units of the polymer chain in the macromonomer of the graft copolymer are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V') is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Regarding solvent resolvability, when the total structural units of the polymer chain are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V') is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0141] The structural units of the polymer chain in the structural unit represented by the above general formula (III) of the above graft copolymer may optionally contain other structural units, in addition to the structural unit represented by the above general formula (IV) which includes at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V').

[0142] Other structural units can be exemplified by structural units derived from olefinic unsaturated monomers that can copolymerize with olefinic unsaturated monomers that derive the structural units represented by the above general formula (IV).

[0143] Monomers that derive other structural units include, for example, styrene-based monomers such as styrene and α-methylstyrene; and vinyl ethers such as phenyl vinyl ethers.

[0144] In terms of the effects of the present invention, when the total number of structural units in the polymer chain of the above-mentioned graft copolymer represented by the above-mentioned general formula (III) 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.

[0145] Furthermore, in terms of the dispersibility and dispersion stability of the colorant, the mass-average molecular weight Mw of the polymer chain is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 15,000 or less, and even more preferably 12,000 or less.

[0146] By ensuring that the mass-average molecular weight Mw of the polymer chain is within the aforementioned range, sufficient stereorepulsion effect as a dispersant can be maintained, and the increased specific surface area of ​​the solvent-affinity portion of the dispersant can effectively exert the effects described above.

[0147] The mass-average molecular weight Mw of the polymer chains described above can be determined in the same manner as that of the dispersants described below, for the polymeric oligomers or polymer chains containing reactive groups described above.

[0148] Furthermore, the polymer chain contains structural units represented by the general formula (IV) and has a glass transition temperature of 85°C or below. This improves the development time delay and coating suitability, and is therefore preferred. To increase production efficiency, it is required to increase the coating speed of the photosensitive coloring resin composition. If the coating suitability is excellent, uneven stripes are less likely to occur during high-speed coating.

[0149] Here, the glass transition temperature (Tg) of the polymer chain of the graft copolymer in this invention can be calculated by the following formula.

[0150] 1 / Tg=Σ(Xi / Tgi)

[0151] Here, the polymer is assumed to be a copolymer of n monomer components 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. Σ is the sum of i = 1 to n. It should be noted, however, that the values ​​of the glass transition temperature (Tgi) of the homopolymer of each monomer can be adopted from the Polymer Handbook (3rd Edition) (J. Brandrup, E. Himmergut, Wiley-Interscience, 1989).

[0152] Furthermore, regarding dispersion stability, the acid value of the aforementioned polymer chain is preferably 10 mg KOH / g or less, and more preferably 0 mg KOH / g or less. Here, the acid value can be measured in the same manner as the acid value of the dispersant described below for the aforementioned polymeric oligomer or the aforementioned polymer chain containing reactive groups.

[0153] The polymer chain may optionally contain structural units containing acidic groups, such as structural units selected from the structural units represented by the above general formula (I) and structural units represented by the above general formula (II), as long as the effect of the present invention is not impaired. In terms of dispersion stability, when the total structural units of the polymer chain are set to 100% by mass, the total ratio of structural units containing acidic groups is preferably 5% by mass or less, and more preferably 0% by mass.

[0154] Furthermore, regarding dispersion stability and long-term stability when mixed with polyfunctional thiol compounds, the amine value of the polymer chain is preferably 10 mg KOH / g or less, and more preferably 0 mg KOH / g or less. Here, the amine value of the polymer chain represents the mass (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid component of the polymeric oligomer or the polymer chain containing reactive groups, and is a value determined by the method described in JIS K 7237:1995.

[0155] The polymer chain may also optionally contain nitrogen-containing structural units, as long as it does not impair the effect of the present invention. In terms of dispersion stability and stability over time when mixed with polyfunctional thiol compounds, when the total structural units of the polymer chain are set to 100% by mass, the total ratio of nitrogen-containing structural units is preferably 3% by mass or less, and more preferably 0% by mass.

[0156] In the above-mentioned graft copolymer, the total content ratio of the structural units represented by general formula (I) and general formula (II) is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass. If the total content ratio of the structural units represented by general formula (I) and general formula (II) in the graft copolymer is within the above range, the ratio of the affinity site for the colorant in the graft copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed. Therefore, the adsorption of the colorant becomes good, and excellent dispersibility, dispersion stability, and solvent resolubility can be obtained.

[0157] On the other hand, in the above-mentioned graft copolymer, the total content ratio of the structural units containing the graft polymer chain and the structural units represented by the above general formula (III) is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 65% ​​to 91% by mass. If the total content ratio of the structural units containing the graft polymer chain and 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 portion in the graft copolymer becomes appropriate, sufficient stereorepulsion effect as a dispersant can be maintained, and the effect of the increased specific surface area of ​​the solvent affinity portion of the dispersant on the above-mentioned effect can be improved.

[0158] It should be noted that the content ratio of the above structural units is calculated based on the amount of monomers added during the synthesis of the graft copolymer, which derive the structural units represented by the above general formula (I), the above general formula (II), and the above general formula (III).

[0159] The graft copolymer used in the first invention may also have other structural units besides those represented by general formula (I), general formula (II), and general formula (III), without impairing the effects of the invention. Regarding these other structural units, olefinically unsaturated monomers capable of copolymerizing with olefinically unsaturated monomers that derive structural units from general formula (I) may be appropriately selected to introduce other structural units.

[0160] Other structural units that copolymerize with the structural units represented by general formula (I) and general formula (II) above in the main chain include, for example, the structural units represented by general formula (IV). Furthermore, structural units containing acidic groups that differ from the structural units represented by general formula (I) and general formula (II) above may also be included as other structural units.

[0161] Examples of structural units containing acidic groups include those derived from olefinic unsaturated monomers containing acidic groups, such as carboxyl groups, sulfonic acid groups, and phosphate groups. Examples of carboxyl-containing olefinic unsaturated monomers include the addition reaction products of monomers with hydroxyl groups, such as vinylbenzoic acid, maleic acid, monoalkyl maleic acid esters, fumaric acid, methylene succinic acid, butenoic acid, cinnamic acid, acrylic acid dimers, and 2-hydroxyethyl (meth)acrylate, with anhydrides containing aromatic rings, such as phthalic acid. Examples of phosphate-containing olefinic unsaturated monomers include 2-acryloyloxyethyl phosphate esters. Examples of sulfonic acid-containing olefinic unsaturated monomers include acryloyloxyethyl sulfonic acid.

[0162] In the above-mentioned graft copolymer, the total content 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.

[0163] (Method for manufacturing graft copolymers)

[0164] In the first invention, the method for manufacturing the graft copolymer is not particularly limited, as long as it is a method capable of manufacturing a graft copolymer having structural units represented by general formula (I) and general formula (II). When manufacturing a graft copolymer having structural units represented by general formula (I) and general formula (II), for example, the following method can be used: copolymerizing a polymeric oligomer (macromonomer) containing (meth)acrylic acid, a monomer represented by general formula (IIa) below, and a polymeric oligomer containing the polymer chain and a group having an olefinic unsaturated double bond at its end as a copolymer component, thereby manufacturing the graft copolymer.

[0165] Other monomers may also be used as needed, and graft copolymers may be manufactured using known polymerization methods.

[0166] [Chemical Formula 8]

[0167]

[0168] (In general formula (IIa), R) 1' R 2 and R 3 The same situation applies as in general formula (II).

[0169] Furthermore, when manufacturing graft copolymers having structural units represented by general formula (I) and general formula (II) above, after adding polymerizing (meth)acrylic acid, the monomer represented by general formula (IIa) above, and other olefinic unsaturated monomers to form a copolymer, a polymer chain containing reactive groups that can react with the reactive groups contained in the copolymer can be introduced into the polymer chain. Specifically, for example, after synthesizing a copolymer having substituents such as alkoxy, hydroxyl, carboxyl, amino, epoxy, isocyanate, or hydrogen-bonding groups, the copolymer can be reacted with a polymer chain containing functional groups that react with the substituents to introduce the polymer chain.

[0170] For example, a polymer chain with a carboxyl group at the end can be reacted with a copolymer with a glycidyl group on the side chain, or a polymer chain with a hydroxyl group at the end can be reacted with a copolymer with an isocyanate group on the side chain to introduce the polymer chain.

[0171] Furthermore, additives commonly used in polymerization, such as polymerization initiators, dispersion stabilizers, and chain transfer agents, can also be used in the above polymerization process.

[0172] [Block copolymer]

[0173] The block copolymer used in the first invention has an A block that functions as an adsorption site for colorants, the A block comprising the structural unit represented by general formula (I) and the structural unit represented by general formula (II) above. Preferably, the block copolymer used in the first invention further has a B block that functions as a solvent affinity portion.

[0174] (A segment)

[0175] The structural units represented by general formula (I) and general formula (II) in block A are the same as those described in the graft copolymer, and therefore are omitted here.

[0176] In block A, the structural unit represented by general formula (I) and the structural unit represented by general formula (II) can also be block copolymerized. However, in order to achieve high adsorption efficiency on both the surface where structural unit (I) is more suitable for adsorption and the surface where structural unit (II) is more suitable, relative to the surface of the color material in various states such as stereoblock or polarity, random copolymerization is preferred.

[0177] In segment A, the structural unit represented by general formula (I) may contain one type or more structural units. In addition, the structural unit represented by general formula (II) may contain one type or more structural units.

[0178] Regarding the stability of dispersion, when the total number of structural units represented by general formula (I) and general formula (II) is set to 100 parts by mass, the content ratio of the structural unit represented by general formula (I) is preferably 35 parts by mass or more, more preferably 50 parts by mass or more, and preferably 95 parts by mass or less, more preferably 85 parts by mass or less.

[0179] Within block A, other structural units may be included in addition to the structural units represented by general formula (I) and general formula (II) without impairing the effects of the present invention. Regarding these other structural units, olefinically unsaturated monomers capable of copolymerizing with olefinically unsaturated monomers that derive structural units from general formula (I) may be appropriately selected to introduce other structural units.

[0180] Other structural units included in block A without impairing the effects of the present invention may include, for example, the structural units represented by the above general formula (IV). Furthermore, structural units containing acidic groups, different from the structural units represented by the above general formula (I) and the structural units represented by the above general formula (II), may also be included as other structural units.

[0181] The structural units represented by the above general formula (IV), and the structural units containing acidic groups that are different from the structural units represented by the above general formula (I) and the structural units represented by the above general formula (II), are the same as those described in the graft copolymer, and therefore are omitted here.

[0182] The total percentage of other structural units contained in block A is not particularly limited, as long as it is within the range that does not impair the effect of the present invention. However, in terms of dispersibility and dispersion stability, it is preferred to be 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass.

[0183] That is, in terms of dispersion and dispersion stability, the total content ratio of the structural units represented by general formula (I) and general formula (II) contained in block A is preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.

[0184] (B-segment)

[0185] In the block copolymer used in the first invention, the B-block is a block that functions as a solvent-affinity component. The B-block is preferably selected appropriately from olefinic unsaturated monomers capable of copolymerizing with those derived from the structural units represented by general formula (I) and general formula (II), in a manner that exhibits solvent affinity, depending on the solvent. Preferably, the B-block is introduced such that, as a standard, the solubility of the block copolymer relative to the solvent used in combination at 23°C is 20 (g / 100g solvent) or more.

[0186] In the block copolymer used in the first invention, in order to achieve good solvent affinity, good dispersibility and dispersion stability of the colorant, the B block, which functions as the solvent affinity part, preferably contains at least one structural unit represented by the above general formula (IV).

[0187] The structural unit represented by the above general formula (IV) included in the B block can be the same as that described in the graft copolymer, so the description is omitted here.

[0188] In the above B block, the structural unit represented by the above general formula (IV) can be a single type or a combination of two or more types.

[0189] Regarding the dispersibility and dispersion stability of the colorant, when the total structural units of the B-block are set to 100% by mass, the total ratio of structural units represented by the general formula (IV) can also be 100% by mass. Regarding the dispersibility and dispersion stability of the colorant, when the total structural units of the B-block are set to 100% by mass, the total ratio of structural units represented by the general formula (IV) is preferably 40% by mass or more, and more preferably 70% by mass or more.

[0190] Furthermore, the above-mentioned B segment includes at least one structural unit selected from the structural units represented by the above-mentioned general formula (IV) and the structural units represented by the above-mentioned general formula (V) and the above-mentioned general formula (V'), which improves the substrate adhesion, shortens the development time, and makes the cross-sectional shape of the resist pattern easier to become a positive cone shape, and is therefore preferred.

[0191] As included in the above-mentioned B block, at least one structural unit selected from the structural units represented by the above-mentioned general formula (V) and the structural units represented by the above-mentioned general formula (V') may be the same as that described in the graft copolymer, and therefore the description is omitted here.

[0192] In the above B block, at least one 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') can be a single type or a combination of two or more types.

[0193] To improve substrate adhesion, shorten development time, and facilitate the transformation of the resist pattern's cross-sectional shape into a conical shape, when the total structural units of the aforementioned B-block are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the aforementioned general formula (V) and the structural units represented by the aforementioned general formula (V') is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Regarding solvent resolvability, when the total structural units of the aforementioned B-block are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the aforementioned general formula (V) and the structural units represented by the aforementioned general formula (V') is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0194] In the above-mentioned B block, in addition to the structural unit represented by the above-mentioned general formula (IV) which includes at least one structural unit selected from the structural unit represented by the above-mentioned general formula (V) and the structural unit represented by the above-mentioned general formula (V'), other structural units may also be optionally included.

[0195] Other structural units can be exemplified by structural units derived from olefinic unsaturated monomers that can copolymerize with olefinic unsaturated monomers that derive the structural units represented by the above general formula (IV).

[0196] Monomers that derive other structural units include, for example, styrene-based monomers such as styrene and α-methylstyrene; and vinyl ethers such as phenyl vinyl ethers.

[0197] In terms of the effects of the present invention, when the total structural unit of the polymer chain in the B block 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.

[0198] Regarding the dispersibility and dispersion stability of the colorant, the mass-average molecular weight Mw of the B block is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 15,000 or less, and even more preferably 12,000 or less.

[0199] By ensuring that the mass-average molecular weight Mw of the B-block is within the aforementioned range, sufficient stereorepulsion effect as a dispersant can be maintained, and the aforementioned effects exerted by the increased specific surface area of ​​the solvent-affinity portion of the dispersant can be improved.

[0200] The mass-average molecular weight Mw of the B-block alone can be determined in the same manner as the dispersant described below for polymers containing only the B-block.

[0201] Furthermore, the B block contains the structural unit represented by the general formula (IV) above, and the glass transition temperature of the B block is below 85°C, which improves the development time delay and coating suitability, and is therefore preferred.

[0202] Here, the glass transition temperature (Tg) of the B-block polymer chain in this invention can be calculated by the following formula.

[0203] 1 / Tg=Σ(Xi / Tgi)

[0204] Here, the polymer is assumed to be a copolymer of n monomer components 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. Σ is the sum of i = 1 to n. Furthermore, the glass transition temperature (Tgi) of the homopolymer of each monomer can be obtained from the Polymer Handbook (3rd Edition) (J. Brandrup, E. Himmergut, Wiley-Interscience, 1989).

[0205] Furthermore, regarding dispersion stability, the acid value of the aforementioned B-block is preferably below 10 mg KOH / g, and more preferably 0 mg KOH / g. Here, the acid value can be measured for polymers containing only the B-block in the same manner as for the acid value of the dispersants described below.

[0206] The B block may optionally contain at least one structural unit containing an acidic group, selected from the structural units represented by the above general formula (I) and the structural units represented by the above general formula (II), 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 B block are set to 100% by mass, the total ratio of structural units containing acidic groups is preferably 5% by mass or less, and more preferably 0% by mass.

[0207] Furthermore, regarding dispersion stability, the amine value of the aforementioned B-block is preferably below 10 mg KOH / g, and more preferably 0 mg KOH / g. Here, the amine value of the B-block can be measured in the same manner as the amine value of the polymer chain for polymers containing only the B-block.

[0208] The B-block may also optionally contain nitrogen-containing structural units, as long as the effect of the present invention is not compromised. In terms of dispersion stability and stability over time when mixed with polyfunctional thiols, when the total structural units of the B-block are set to 100% by mass, the total ratio of nitrogen-containing structural units is preferably 3% by mass or less, more preferably 0% by mass.

[0209] Furthermore, the aforementioned B-block can be selected in a manner that functions as a solvent affinity component, and the structural unit can include one type or a mixture of two or more types. When the aforementioned B-block contains two or more structural units, the two or more structural units can also be randomly copolymerized within the B-block.

[0210] There is no particular limitation on the bonding sequence of the block copolymers, as long as the colorant can be stably dispersed. However, the bonding sequence of the A block bonded to one end of the block copolymer is preferred in terms of its excellent interaction with the colorant and its ability to effectively suppress the aggregation of dispersants. AB-type block copolymers or ABA-type block copolymers are preferred, with AB-type block copolymers being more preferred.

[0211] In the block copolymer described above, the total content ratio of the structural units represented by general formula (I) and general formula (II) is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass. If the total content ratio of the structural units represented by general formula (I) and general formula (II) in the block copolymer is within the above range, the ratio of the affinity site for the colorant in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed. Therefore, the adsorption of the colorant becomes good, and excellent dispersibility, dispersion stability, and solvent resolubility can be obtained.

[0212] On the other hand, in the above-mentioned block copolymer, the total content of B blocks is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 65% ​​to 91% by mass. If the total content of B blocks in the block copolymer is within the above range, the ratio of solvent-affinity portions in the block copolymer becomes appropriate, sufficient steric repulsion effect as a dispersant can be maintained, and the effect of the increased specific surface area of ​​the solvent-affinity portions of the dispersant on the above-mentioned effect can be improved.

[0213] It should be noted that the content ratio of the above structural units is calculated based on the amount of monomers added during the synthesis of the block copolymer, which derive the structural units represented by the above general formula (I), the above general formula (II), and the above general formula (IV).

[0214] (Method for manufacturing block copolymers)

[0215] There are no particular limitations on the manufacturing method of the aforementioned block copolymers. Block copolymers can be manufactured by known methods, with living polymerization being preferred. This is because it produces copolymers with uniform molecular weight that are less prone to chain transfer or deactivation, thus improving dispersibility. Examples of living polymerization methods include living radical polymerization, living anionic polymerization such as group transfer polymerization, and living cationic polymerization. Copolymers can be manufactured by sequentially polymerizing monomers using these methods. For example, a block copolymer can be manufactured by first manufacturing block A and then polymerizing the structural units constituting block B with block A. Alternatively, the polymerization order of block A and block B in the above manufacturing method can be reversed. Furthermore, block A and block B can be manufactured separately, and then block A and block B can be coupled together.

[0216] [Properties of dispersants]

[0217] Furthermore, regarding dispersibility and dispersion stability, the mass-average molecular weight (Mw) of at least one of the graft copolymers and block copolymers is preferably 4,000 or more, more preferably 5,000 or more, and even more preferably 6,000 or more. On the other hand, regarding solvent resolubility, it is preferably 50,000 or less, more preferably 30,000 or less.

[0218] Furthermore, in terms of dispersion stability, the ratio (Mw / Mn) of the mass-average molecular weight Mw to the number-average molecular weight Mn of the dispersant used in the above-mentioned graft copolymer is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

[0219] Furthermore, in terms of dispersion stability, the ratio (Mw / Mn) of the mass-average molecular weight Mw to the number-average molecular weight Mn of the dispersant used in the block copolymer is preferably 1.8 or less, more preferably 1.6 or less, and even more preferably 1.4 or less.

[0220] It should be noted that, in this invention, the mass-average molecular weight Mw and number-average molecular weight Mn are values ​​obtained by GPC (gel permeation chromatography). The determination was performed using an HLC-8120 GPC manufactured by Tosoh Corporation, with the eluent being N-methylpyrrolidone containing 0.01 mol / L lithium bromide. The calibration curves were performed using polystyrene standards Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, and 580 (all from the Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and the assay column was set to two TSK-GEL ALPHA-M columns (manufactured by Tosoh Corporation).

[0221] In this invention, in terms of dispersion stability, the acid value of at least one of the above-mentioned graft copolymer and block copolymer is preferably 30 mg KOH / g or more, more preferably 35 mg KOH / g or more, and even more preferably 40 mg KOH / g or more.

[0222] On the other hand, in terms of solvent resolubility, the acid value of at least one of the above-mentioned graft copolymers and block copolymers is preferably 180 mg KOH / g or less, more preferably 160 mg KOH / g or less, and even more preferably 140 mg KOH / g or less.

[0223] The acid value of the dispersant represents the mass (mg) of potassium hydroxide required to neutralize the acidic components contained in 1g of the solid component of the copolymer, and is a value determined by the method described in JIS K 0070:1992.

[0224] In this invention, the content ratio or structure of each structural unit of the dispersant can be determined using various mass analysis methods, such as NMR. Furthermore, the dispersant can be decomposed by pyrolysis or the like as needed, and the obtained decomposition products can be analyzed using high-performance liquid chromatography, gas chromatography-mass analyzer, NMR, elemental analysis, XPS / ESCA, and TOF-SIMS.

[0225] The first dispersant of the present invention is at least one of a graft copolymer and a block copolymer, wherein the graft copolymer has structural units represented by the above general formula (I) and structural units represented by the above general formula (II), and the block copolymer has an A block comprising structural units represented by the above general formula (I) and structural units represented by the above general formula (II).

[0226] In the color material dispersion of the first invention, as a dispersant, it contains at least one of a graft copolymer and a block copolymer. The graft copolymer has structural units represented by the general formula (I) and the general formula (II) above. The block copolymer has an A block containing structural units represented by the general formula (I) and the general formula (II) above. However, it may also optionally contain other known dispersants, as long as the effect of the invention is not impaired.

[0227] In the dispersant used in the color material dispersion of the first invention, the total content ratio of at least one of the above-mentioned graft copolymer and block copolymer is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0228] 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 its content is appropriately selected according to the type of color material used and, consequently, the concentration of solid components in the following photosensitive coloring resin composition.

[0229] The content of the dispersant, relative to 100 parts by mass of the total solids in the colorant dispersion, is preferably in the range of 3 to 60 parts by mass, and more preferably in the range of 5 to 45 parts by mass. If the content is above the lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the photosensitive coloring resin composition is even better. Furthermore, if the content is below the upper limit, the development residue becomes good.

[0230] It should be noted that, in this invention, the solid component includes all components other than the solvent mentioned above, including monomers dissolved in the solvent.

[0231] <Color material>

[0232] In this invention, the colorant 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 dye salt compounds can be used alone or in mixtures of two or more. Among them, organic pigments are preferred because they have high color rendering and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Dye Index (CI; published by The Society of Dyers and Colourists), specifically compounds labeled with the Dye Index (CI) number as described below.

[0233] 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 derivative pigments of CI Pigment Yellow 150;

[0234] CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;

[0235] CI pigments: purple 1, 19, 23, 29, 32, 36, 38;

[0236] 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, 5 7:2, 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, 2 33, 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;

[0237] CI Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 61, 79, 80;

[0238] 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;

[0239] CI Pigment Brown 23, 25;

[0240] CI Pigment Black 1, 7.

[0241] In addition, specific examples of the aforementioned inorganic pigments include: titanium dioxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, litharge, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, brown clay, titanium black, synthetic iron black, carbon black, etc.

[0242] For example, when the colorant dispersion of the present invention is used to form a pattern of a light-shielding layer on a substrate of a color filter as described in the photosensitive coloring resin composition, a black pigment with high light-shielding properties is formulated into the ink. Examples of black pigments with high light-shielding properties include inorganic pigments such as carbon black and iron oxide; or organic pigments such as phthalocyanine black.

[0243] Examples of dispersible dyes include those that can be dispersed by giving the dye various substituents or by combining it with solvents with low solubility.

[0244] Salt-forming compounds of dyes refer to compounds formed by the formation of salts between dyes and counterions. Examples include salt-forming compounds of basic dyes and acids, salt-forming compounds of acidic dyes and bases, and lake pigments formed by using known lake formation (salting) methods to make solvent-soluble dyes insoluble in solvents.

[0245] In this invention, by combining a colorant containing at least one selected from dyes and salt-forming compounds of dyes with the dispersant of the present invention, the dispersibility and dispersion stability of the colorant can be improved.

[0246] The dyes mentioned above can be appropriately selected from previously known dyes. Examples of such dyes include: azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthones dyes, coumarin dyes, anthocyanin dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, phthalocyanine dyes, etc.

[0247] It should be noted that, according to the standard, as long as the amount of dye dissolved relative to 10g of solvent (or mixed solvent) is less than 10mg, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

[0248] When the colorant contains at least one selected from pyrrolopyrroledione pigments, anthraquinone pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, dioxazine pigments, triarylmethane dyes, quinophthalone dyes, coumarin dyes, phthalocyanine dyes, and salt compounds of these dyes, a high-brightness coloring layer can be formed by using the dispersant described above, which is therefore preferred. Furthermore, the colorant preferably contains at least one selected from pyrrolopyrroledione pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, dioxazine pigments, triarylmethane dyes, quinophthalone dyes, and salt compounds of these dyes.

[0249] Examples of pyrrolopyrrole dione pigments include CI Pigment Red 254, 255, 264, 272, 291 and pyrrolopyrrole dione pigments represented by the following general formula (i), wherein R is preferably selected from CI Pigment Red 254, 272, 291 and the following general formula (i). 21 and R22 At least one of 4-bromophenyl pyrrolopyrrole dione pigments.

[0250] [Chemical Formula 9]

[0251] General formula (i)

[0252]

[0253] (In general formula (i), R) 21 and R 22 (Each is independently 4-chlorophenyl or 4-bromophenyl)

[0254] Anthraquinone pigments include, for example, CI Pigment Red 177.

[0255] Examples of quinoline pigments include CI pigment yellow 138.

[0256] 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 which, CI Pigment Blue 15:6 is preferred.

[0257] Examples of zinc phthalocyanine pigments include CI pigments 58 and 59.

[0258] Examples of aluminum phthalocyanine pigments include CI pigments Green 62 and 63.

[0259] Examples of dioxazine pigments include CI pigment Violet 23.

[0260] Examples of quinoline dyes include: CI Disperse Yellow 54, 64, 67, 134, 149, 160; CI Solvent Yellow 114, 157, etc.; among which, CI Disperse Yellow 54 is preferred.

[0261] Examples of triarylmethane dyes include: Basic Red 9 (CI); Basic Blue 1 and 7 (CI).

[0262] Examples of phthalocyanine dyes include Basic Blue 140 (CI).

[0263] The average primary particle size of the colorant used in this invention is not particularly limited, as long as it can emit the desired color when the color layer of the color filter is formed. It varies depending on the type of colorant used, but is preferably in the range of 10 nm to 100 nm, and more preferably 15 nm to 60 nm. By ensuring that the average primary particle size of the colorant is within the above range, a display device equipped with a color filter manufactured using the colorant dispersion of this invention can become a high-contrast and high-quality display device.

[0264] Furthermore, the average dispersed particle size of the colorant in the colorant dispersion varies depending on the type of colorant used, preferably in the range of 10 nm to 100 nm, and more preferably in the range of 15 nm to 60 nm.

[0265] The average dispersed particle size of the colorant in the colorant dispersion is the dispersed particle size of the colorant particles dispersed in a dispersion medium containing at least a solvent, and is measured using a laser scattering particle size analyzer. As for the particle size measurement using the laser scattering particle size analyzer, the colorant dispersion can be appropriately diluted (e.g., 1000 times) to a concentration measurable by the laser scattering particle size analyzer using the solvent, and then measured at 23°C using a laser scattering particle size analyzer (e.g., the Nanotrac particle size analyzer UPA-EX150 manufactured by Nikkiso Corporation) via dynamic light scattering. The average dispersed particle size here is the volume average particle size.

[0266] The colorant used in this invention can be manufactured by known methods such as recrystallization and solvent salt milling. Alternatively, commercially available colorants can be micronized before use.

[0267] In the colorant dispersion of the present invention, the content of the colorant is not particularly limited. In terms of dispersibility and dispersion stability, the content of the colorant is preferably in the range of 5 to 80 parts by mass relative to 100 parts by mass of the total solids in the colorant dispersion, and more preferably in the range of 8 to 70 parts by mass.

[0268] In particular, when forming a coating film or coloring layer with a high concentration of colorant, the content of colorant is preferably in the range of 30 to 80 parts by mass relative to 100 parts by mass of the total solids in the colorant dispersion, and more preferably in the range of 40 to 75 parts by mass.

[0269] Solvent

[0270] The solvent used in this invention is not particularly limited, as long as it is an organic solvent that can dissolve or disperse the components in the colorant dispersion without reacting with them. Solvents can be used alone or in combination of two or more.

[0271] Specific examples of solvents include: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; and glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate. Carbitol acetate solvents such as carbitol acetate (BCA), methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are suitable for solubility of other components. Specifically, the solvent used in this invention, in terms of solubility of other components or coating suitability, is preferably selected from one or more of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

[0272] In the colorant dispersion of the present invention, the solvent as described above, relative to the total amount of the colorant dispersion containing the solvent, is typically within the range of preferably 55% to 95% by mass, more preferably 65% ​​to 90% by mass, and even more preferably 70% to 88% by mass. If the solvent is too little, the viscosity tends to increase, thereby reducing dispersibility. Furthermore, if the solvent is too much, the colorant concentration decreases, making it difficult to achieve the target chromaticity coordinates.

[0273] <Other Ingredients>

[0274] The colorant dispersion of the present invention may also be further formulated with dispersion aid resin and other components as needed, as long as the effect of the present invention is not compromised.

[0275] Examples of alkali-soluble resins used as dispersing aids include those exemplified in the following photosensitive coloring resin compositions. Due to the steric hindrance provided by the alkali-soluble resin, the colorant particles are less likely to come into contact with each other, thereby stabilizing the dispersion or reducing the amount of dispersant through this stabilizing effect.

[0276] In addition, other components include, for example, surfactants to improve wettability, silane coupling agents to improve adhesion, defoamers, anti-shrinkage agents, antioxidants, anti-coagulation agents, and ultraviolet absorbers.

[0277] The colorant dispersion of the present invention is used as a pre-preparation for the preparation of the following photosensitive coloring resin composition. That is, the colorant dispersion is a colorant dispersion prepared in a preliminary stage before preparing the following photosensitive coloring resin composition, having a high ratio of (mass of colorant component in the composition) / (mass of solids component other than colorant component in the composition). Specifically, the ratio of (mass of colorant component in the composition) / (mass of solids component other than colorant component in the composition) is generally 1.0 or higher. By mixing the colorant dispersion with the following components, a photosensitive coloring resin composition with excellent dispersibility can be prepared.

[0278] <Preparation Method of Pigment Dispersion>

[0279] In this invention, the method for manufacturing the color material dispersion is not particularly limited, as long as it is a method that can obtain a color material dispersion by dispersing the color material in a solvent using the above-mentioned dispersant.

[0280] From the viewpoint of excellent dispersibility and dispersion stability of the colorant, the method for manufacturing the colorant dispersion of the present invention can be exemplified by the following steps: a step of preparing the above-mentioned dispersant; and a step of dispersing the colorant in a solvent in the presence of the above-mentioned dispersant.

[0281] In the above manufacturing method, the colorant can be dispersed using a previously known disperser.

[0282] Specific examples of dispersers include: roller mills such as two-roll mills and three-roll mills, ball mills such as vibrating ball mills, paint conditioners, continuous disc bead mills, and continuous ring bead mills. For preferred dispersion conditions in bead mills, the bead particle size used is preferably 0.03 mm to 3.0 mm, more preferably 0.05 mm to 2.0 mm.

[0283] Specifically, the method can be exemplified as follows: pre-dispersion is performed using 2.0 mm zirconia beads with a relatively large particle size, followed by formal dispersion using 0.1 mm zirconia beads with a relatively small particle size. Furthermore, after dispersion, filtration is preferably performed using a 0.5 μm to 2 μm filter.

[0284] <Applications>

[0285] The colorant dispersion and dispersant of the first invention can produce a photosensitive coloring resin composition that simultaneously satisfies excellent dispersion stability, solvent resolubility and substrate adhesion, and are therefore suitable for use as a color filter.

[0286] Furthermore, the color material dispersion and dispersant of the first invention can also be used in coloring resin compositions or thermosetting coloring resin compositions that do not require photosensitive components.

[0287] The color material dispersion and dispersant of the present invention are used in various applications requiring excellent dispersion stability of fine color materials, and are also used in inkjet inks or printing inks, recording instruments, cosmetics, etc.

[0288] I-2. The first photosensitive coloring resin composition of the present invention

[0289] The photosensitive coloring resin composition of the first invention is characterized by containing a colorant, the dispersant of the first invention described above, a multifunctional monomer, a photoinitiator, and a solvent.

[0290] Since the photosensitive coloring resin composition of the first invention contains the dispersant, colorant and solvent of the first invention described above, it can simultaneously satisfy excellent dispersion stability, solvent resolubility and substrate adhesion, just as described in the colorant dispersion of the first invention.

[0291] The photosensitive coloring resin composition of the first invention contains at least a colorant, a dispersant, a multifunctional monomer, a photoinitiator, and a solvent, and may further contain other components without impairing the effects of the invention. Hereinafter, the components contained in the photosensitive coloring resin composition of the first invention will be described, but since the dispersant, colorant, and solvent are the same as those described in the colorant dispersion of the first invention, their descriptions are omitted here.

[0292] <Multifunctional Monomer>

[0293] There are no particular limitations on the multifunctional monomers used in the photosensitive coloring resin composition, as long as they can be polymerized by the following photoinitiator. Compounds having two or more olefinic unsaturated double bonds are generally used, and multifunctional (meth)acrylates having two or more acryloyl or methacryloyl groups are particularly preferred.

[0294] As for such multifunctional (meth)acrylates, any appropriate selection from previously known sources may be used. Specific examples include those described in Japanese Patent Application Publication No. 2013-029832.

[0295] These multifunctional (meth)acrylates can be used alone or in combination of two or more. Furthermore, when the photosensitive coloring resin composition of the present invention requires excellent photocurability (high sensitivity), the multifunctional monomer preferably has three or more polymerizable double bonds (trifunctional), preferably poly(meth)acrylates of polyols with three or more nucleotides or their dicarboxylic acid modifications, specifically preferably: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0296] There are no particular limitations on the content of the aforementioned multifunctional monomers used in the photosensitive coloring resin composition. For example, it is preferably in the range of 5% to 60% by mass, and more preferably in the range of 10% to 40% by mass, relative to the total solid content of the photosensitive coloring resin composition. If the content of the multifunctional monomers is less than the aforementioned lower limit, there is a possibility of insufficient photocuring, resulting in the exposed portion dissolving during development. Furthermore, if the content of the multifunctional monomers is greater than the aforementioned upper limit, there is a concern about a decrease in alkaline developability.

[0297] <Photoinitiator>

[0298] There are no particular limitations on the photoinitiator used in the photosensitive coloring resin composition of the present invention, and one or more of the previously known initiators may be used.

[0299] Examples of photoinitiators include: aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-amino ketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone. Specific examples of photoinitiators include: aromatic ketones such as benzophenone, 4,4'-bis(diethylaminobenzophenone), and 4-methoxy-4'-dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazolium dimer; and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole. Halomethyl-S-triazine compounds such as 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzoyl, benzoyl Benzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyl diphenyl sulfide, benzoin dimethyl ether, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanone, 2,4-diethylthioxanone, 2,4-dimethylthioxanone, isopropylthioxanone, 4-benzoyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2 -(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, etc.

[0300] Among these, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, and diethylthioxanone are preferred. Combining an α-aminoacetophenone-based initiator such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one with a thioxanone-based initiator such as diethylthioxanone improves development tolerance by adjusting sensitivity and suppressing water spots.

[0301] When using α-aminoacetophenone-based initiators and thioxanthone-based initiators, the total content of these initiators relative to the total solid content of the photosensitive coloring resin composition is preferably 5% to 15% by mass. If the initiator dosage is 15% by mass or less, sublimation during the process is reduced, which is therefore preferable. If the initiator dosage is 5% by mass or more, development resistance, such as water spots, is improved.

[0302] In this invention, from the viewpoint of improving sensitivity, the photoinitiator preferably includes an oxime ester-based photoinitiator. Furthermore, by using an oxime ester-based photoinitiator, it is easier to suppress uneven linewidth within the surface when forming fine line patterns. Moreover, by using an oxime ester-based photoinitiator, there is a tendency to increase the residual film yield and improve the effect of suppressing water spots. Furthermore, water spots refer to the phenomenon where, if an ingredient that enhances alkaline developability is used, traces resembling water penetration appear after rinsing with pure water following alkaline development. These water spots disappear after post-baking, so they are not a problem for the finished product; however, during the visual inspection of the patterned surface after development, they are detected as unevenness, resulting in the inability to distinguish between normal and abnormal products. Therefore, if the inspection sensitivity of the inspection device decreases during visual inspection, the final yield of the color filter product will decrease, thus causing problems.

[0303] From the viewpoint of reducing contamination of the photosensitive coloring resin composition or device caused by decomposition products, this oxime ester photoinitiator is preferably one that has an aromatic ring, more preferably one that has a condensation ring containing an aromatic ring, and even more preferably one that has a condensation ring containing a benzene ring and a heterocyclic ring.

[0304] As an oxime ester photoinitiator, an appropriate selection can be made from the oxime ester photoinitiators described in 1,2-octanedione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone-1-(o-acetyl oxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2010-527338, and Japanese Patent Application Publication No. 2013-041153. Commercially available products include IRGACURE OXE-01, Adeka Arkles NCI-930 (with a diphenyl sulfide backbone), TR-PBG-345, TR-PBG-304 (with a carbazole backbone), TR-PBG-365 (with a fluorene backbone), and TR-PBG-3057 (all manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.). Especially in terms of brightness, oxime ester-based photoinitiators with a diphenyl sulfide or fluorene backbone are preferred. Furthermore, oxime ester-based photoinitiators with a carbazole backbone are preferred due to their higher sensitivity.

[0305] Furthermore, the use of two or more oxime ester-based photoinitiators is preferred because it readily improves brightness and residual film yield, and effectively suppresses water spot formation. In particular, the use of two oxime ester-based photoinitiators with a diphenyl sulfide skeleton, or a combination of an oxime ester-based photoinitiator with a diphenyl sulfide skeleton and an oxime ester-based photoinitiator with a fluorene skeleton, is preferred due to its high brightness and high heat resistance. Moreover, the use of an oxime ester-based photoinitiator with a carbazole skeleton and an oxime ester-based photoinitiator with a fluorene skeleton, or a diphenyl sulfide oxime ester-based photoinitiator, is preferred due to its excellent sensitivity and brightness.

[0306] Furthermore, combining a photoinitiator with a tertiary amine structure with an oxime ester-based photoinitiator suppresses water spots and improves sensitivity, making it preferable. This is because photoinitiators with a tertiary amine structure have an intramolecular tertiary amine structure that acts as an oxygen quencher, thus the free radicals generated by the self-initiator are less likely to lose activity due to oxygen, thereby improving sensitivity. Commercially available examples of such photoinitiators with a tertiary amine structure include: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (e.g., IRGACURE 907; manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone (e.g., IRGACURE 369; manufactured by BASF), and 4,4'-bis(diethylamino)benzophenone (e.g., Hicure ABP; manufactured by Kawaguchi Pharmaceutical Co., Ltd.).

[0307] Furthermore, combining thioxanone-based initiators with oxime ester-based photoinitiators can adjust sensitivity, suppress water spots, and improve development tolerance. Therefore, it is preferred to combine two or more oxime ester-based photoinitiators with thioxanone-based initiators to improve brightness, residual film rate, make sensitivity easier to adjust, have a higher suppression effect on water spots, and improve development tolerance.

[0308] The content of the photoinitiator used in the photosensitive coloring resin composition of the present invention is typically about 0.01 to 100 parts by weight relative to 100 parts by weight of the aforementioned multifunctional monomer, preferably 5 to 60 parts by weight. If this content is above or below the aforementioned lower limit, photocuring is sufficiently carried out, and the dissolution of the exposed portion during development is suppressed. On the other hand, if it is below the aforementioned upper limit, the yellowing of the obtained coloring layer is weakened, and the decrease in brightness can be suppressed.

[0309] Furthermore, the total content of photoinitiators used in the photosensitive coloring 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 coloring resin composition, and more preferably in the range of 1.0% by mass to 8.0% by mass.

[0310] <Other Ingredients>

[0311] The photosensitive coloring resin composition of the present invention may also include, as needed, polyfunctional thiol compounds, alkali-soluble resins, antioxidants, and various additives.

[0312] (Polyfunctional thiols)

[0313] From the viewpoint of improving notch resistance and good storage stability, the photosensitive resin composition of the present invention preferably contains a polyfunctional thiol compound. Here, notch resistance refers to the property of easily suppressing the peeling of the cured photosensitive resin composition from the substrate due to excessive corrosion by the developing solution used in alkaline development or physical impact caused by the developing water pressure. During exposure, the polyfunctional thiol compound generates sulfur-containing free radicals through free radicals generated by the photoinitiator. It is presumed that the unsaturated bonds of the polyfunctional monomers, etc., of these sulfur-containing free radicals undergo a thiol-ene reaction, thereby crosslinking and improving the curability of the coating, resulting in improved notch resistance. It should be noted that when a Michael addition catalyst such as a tertiary amine is present, such as when an amine-based dispersant is used, a Michael addition reaction occurs between the polyfunctional thiol compound and the unsaturated bonds of the polyfunctional monomers, etc. Therefore, if a polyfunctional thiol compound is used in a photosensitive resin composition containing an amine-based dispersant, a Michael addition reaction will occur during storage, thereby easily leading to decreased stability over time. In contrast, as described above, the photosensitive resin composition of the present invention exhibits good storage stability even when containing polyfunctional thiol compounds, due to the use of an acid-based dispersant.

[0314] The polyfunctional thiol compounds used in this invention are compounds having two or more thiol groups within one molecule.

[0315] The polyfunctional thiol compound may be appropriately selected from known compounds having two or more thiol groups within one molecule. In the photosensitive resin composition of the present invention, a single polyfunctional thiol compound may be used alone, or two or more may be used in combination.

[0316] Specific examples of polyfunctional thiols include: 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2-cyclohexanedithiol, decanedithiol, ethylene glycol dimercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, 1,4-butanediol dimercaptoacetate, 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trimethylolpropane tri(3- Examples of esters include: thiopropionate, pentaerythritol tetramercaptoacetate, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), and dipentaerythritol hexa(3-mercaptopropionate); esters of various polyols with thioacetic acid, mercaptopropionic acid, and other thiol-containing carboxylic acids, trimercaptopropionate tri(2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0317] Polyfunctional thiols can also be polyfunctional thiols with substituents at the α- and / or β-positions of the carbon atom relative to the thiol group. Specific examples of this include: 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis(1-mercaptoethyl)benzene, di(1-mercaptoethyl) phthalate, di(2-mercaptopropyl) phthalate, di(3-mercaptobutyl) phthalate, di(3-mercaptoisobutyl) phthalate, etc.

[0318] Examples of other esters include: ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane tri(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... 2-Mercaptopropionate, Trimethylolpropanetri(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), Butanediol bis(3-Mercaptoisobutyrate), Octylene glycol bis(3-Mercaptoisobutyrate), Trimethylolpropanetri(3-Mercaptoisobutyrate), Pentaerythritol Tetra(3-Mercaptoisobutyrate), 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 tri(2-mercaptoisobutyrate), pentaerythritol tetra(2-mercaptoisobutyrate), dipentaerythritol hexa(2-mercaptoisobutyrate), ethylene glycol bis(4-mercaptovalerate), propylene glycol bis(4-mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate) Esters), 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-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), trimethylolpropane tri(3-mercaptovalerate), pentaerythritol tetra(3-mercaptovalerate), dipentaerythritol hexa(3-mercaptovalerate), etc.

[0319] In this invention, the polyfunctional thiol compound is preferably a polyfunctional secondary thiol compound having a secondary thiol group to which the carbon atom bonded by the thiol group is a secondary carbon atom. This is because secondary thiols are less reactive than primary thiols, and therefore less likely to react with the components in the photosensitive resin composition, resulting in excellent storage stability of the photosensitive resin composition.

[0320] Furthermore, the case where the aforementioned polyfunctional thiol compound is represented by the following general formula (A) will improve notch resistance and storage stability, and is therefore preferred.

[0321] [Chemical Formula 10]

[0322]

[0323] (In general formula (A), R) a R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. b (This indicates an alkylene group with 1 to 6 carbon atoms, Q indicates a polyol residue with 2 to 6 hydroxyl groups, and s is an integer from 2 to 6.)

[0324] In general formula (A), R a It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Regarding the storage stability of the photosensitive resin composition, R... a Alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are more preferred.

[0325] Alkyl groups having 1 to 6 carbon atoms can be straight-chain, branched, or cyclic, and examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, cyclopentyl, cyclohexyl, etc. Furthermore, alkylene groups having 1 to 6 carbon atoms can be straight-chain or branched, and examples include: methylene, ethylene, trimethylene, propylene, various butylene groups, various pentylene groups, various hexylene groups, etc.

[0326] Furthermore, Q represents a residue of the polyol that forms an ester with a specific thiol-containing carboxylic acid. Examples of polyols used herein include ethylene glycol, propylene glycol, butanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc., but are not limited to these. p represents the number of esters formed by the specific thiol-containing carboxylic acid and the polyol, and is an integer from 2 to 6 corresponding to the number of hydroxyl groups of the residues in the polyol with 2 to 6 hydroxyl groups.

[0327] In the polyfunctional thiol compounds used in this invention, the number of thiol groups in one molecule is preferably three or more, and from the viewpoint of improving the storage stability and notch resistance of the photosensitive resin composition, three to six groups are preferred.

[0328] The polyfunctional thiols used in this invention include butanediol bis(3-mercaptopropionate) (BDTP), trimethylolpropane tris(3-mercaptopropionate) (TMTP), pentaerythritol tetra(3-mercaptopropionate) (PETP), tris(2-hydroxyethyl) isocyanurate tris(3-mercaptopropionate) (THEIC-BMPA), pentaerythritol tetra(3-mercaptobutyrate) (PTMP), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolethane tris(3-mercaptobutyrate) (TEMB), and pentaerythritol tetra(3-mercaptopropionate). β-thiol alkyl derivatives such as PEMP; thiol alkyl esters such as ethylene glycol dimercaptoacetate (EGTG), butylene glycol dimercaptoacetate (BDTG), hexanediol dimercaptoacetate (HDTG), trimethylolpropane trimercaptoacetate (TMTG), pentaerythritol tetramercaptoacetate (PETG); 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred because they improve notch resistance and have good storage stability, but are not limited thereto.

[0329] The content of the polyfunctional thiol compound, relative to the total solid content of the photosensitive coloring resin composition, is preferably in the range of 0.01% to 15.0% by mass, more preferably in the range of 0.1% to 10.0% by mass, and even more preferably in the range of 0.5% to 5.0% by mass. If it is above the lower limit, notch resistance is easily improved. On the other hand, if it is below the upper limit, the formation of developing residue is easily suppressed.

[0330] (Alkali-soluble resin)

[0331] In the photosensitive coloring resin composition of the present invention, since the dispersant has a carboxyl group, it can also function as an alkali-soluble resin. Therefore, the alkali-soluble resin, which is different from the above-mentioned dispersant, is not an essential component.

[0332] From the viewpoint of easily adjusting alkali solubility, the photosensitive coloring resin composition of the present invention preferably contains an alkali-soluble resin that is different from the dispersant described above.

[0333] The alkali-soluble resin of the present invention has acidic groups, functions as an adhesive resin, and can be appropriately selected from those that are soluble relative to the alkaline developing solution used in pattern formation.

[0334] In this invention, the term "alkali-soluble resin" can be defined as having an acid value of 40 mg KOH / g or higher.

[0335] The preferred alkali-soluble resin in this invention is a resin having acidic groups, typically a resin having carboxyl groups. Specific examples include acrylic copolymers and styrene-acrylic copolymers having carboxyl groups, as well as epoxy (meth)acrylate resins having carboxyl groups. Among these, resins with carboxyl groups on the side chains and further with photopolymerizable functional groups such as olefinic unsaturated groups on the side chains are particularly preferred. This is because the presence of photopolymerizable functional groups improves the strength of the cured film. Furthermore, two or more of these acrylic copolymers, styrene-acrylic copolymers, and epoxy acrylate resins can be mixed and used.

[0336] Acrylic resins, such as acrylic copolymers containing carboxyl-containing structural units and styrene-acrylic copolymers containing carboxyl groups, are polymers (copolymers) obtained by copolymerizing carboxyl-containing olefinic unsaturated monomers and other copolymerizable monomers as needed, using known methods.

[0337] Examples of carboxyl-containing olefinic unsaturated monomers include: (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleic acid esters, fumaric acid, methylene succinic acid, butenoic acid, cinnamic acid, and acrylic acid dimers. Furthermore, monomers with hydroxyl groups, such as 2-hydroxyethyl (meth)acrylic acid, can be used as addition reaction products of cyclic anhydrides such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, as well as ω-carboxyl-polycaprolactone mono(meth)acrylic acid esters. Additionally, monomers containing anhydrides, such as maleic anhydride, methylene succinic anhydride, and methyl maleic anhydride, can also be used as precursors for the carboxyl group. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, and glass transition temperature.

[0338] From the viewpoint of excellent adhesion of the coloring layer, alkali-soluble resins preferably contain hydrocarbon rings. It has been observed that coloring layers obtained by having hydrocarbon rings, which are large functional groups, exhibit good solvent resistance, and in particular, suppress swelling of the coloring layer. The exact mechanism is not yet fully understood, but it is presumed that the inclusion of large hydrocarbon rings within the coloring layer inhibits molecular movement within the layer, resulting in increased coating strength and thus suppressing solvent-induced swelling.

[0339] Examples of such hydrocarbon rings include cyclic aliphatic hydrocarbon rings with optional substituents, aromatic rings with optional substituents, and combinations thereof. The hydrocarbon ring may have substituents such as carbonyl, carboxyl, oxycarbonyl, and amide groups. In the case of including an aliphatic ring, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is enhanced.

[0340] Specific examples of hydrocarbon rings include: aliphatic hydrocarbon rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornene, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, biphenylene, diphenylmethane, triphenylmethane, and styrene; or the CARDO structure represented by the following chemical formula (ii).

[0341] [Chemical Formula 11]

[0342] Chemical formula (ii)

[0343]

[0344] When an aliphatic ring is included as a hydrocarbon ring, it is preferred because the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved.

[0345] Furthermore, when the CARDO structure represented by the above chemical formula (ii) is included, the curability of the coloring layer is improved, and the solvent resistance (inhibition of NMP swelling) is also improved, which is particularly preferred.

[0346] From the viewpoint that the amount of each structural unit can be easily adjusted and that the amount of structural units with the above-mentioned hydrocarbon ring can be easily increased to improve the function of the structural unit, it is preferable to use an acrylic copolymer that contains structural units with the above-mentioned hydrocarbon ring in addition to structural units with carboxyl groups.

[0347] Acrylic copolymers containing structural units with carboxyl groups and the aforementioned hydrocarbon rings can be prepared by using olefinic unsaturated monomers with hydrocarbon rings as the aforementioned "other copolymerizable monomers".

[0348] Examples of olefinic unsaturated monomers having the aforementioned hydrocarbon rings include cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantane methacrylate, isobornyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styrene. From the viewpoint that the cross-sectional shape of the developed colored layer is better maintained during heat treatment, cyclohexyl methacrylate, dicyclopentyl methacrylate, adamantane methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and styrene are preferred.

[0349] Furthermore, the alkali-soluble resin used in this invention preferably has olefinic double bonds in its side chains. When olefinic double bonds are present, during the curing process of the resin composition in the color filter manufacturing process, the alkali-soluble resin can form cross-linking bonds with the dispersant of this invention. Additionally, the alkali-soluble resin can form cross-linking bonds with each other or with photopolymerizable compounds. Therefore, when an alkali-soluble resin with olefinic double bonds in its side chains is used in combination with the dispersant of this invention, the film strength of the cured film is further improved by utilizing a synergistic effect. This further enhances the brightness of the coloring layer and the crack resistance of the ITO film, thereby improving development resistance. Furthermore, the thermal shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.

[0350] The method for introducing olefinic double bonds into alkali-soluble resins can be appropriately selected from previously known methods. For example, the following methods can be used: adding a compound having both epoxy groups and olefinic double bonds in the molecule, such as glycidyl (meth)acrylate, to the carboxyl group of the alkali-soluble resin, thereby introducing the olefinic double bond into the side chain; or when introducing a hydroxyl structural unit into the copolymer, adding a compound having both isocyanate groups and olefinic double bonds in the molecule, thereby introducing the olefinic double bond into the side chain.

[0351] The alkali-soluble resin used in this invention may further contain other structural units such as methyl (meth)acrylate and ethyl (meth)acrylate, which have ester groups. These ester-group structural units not only function as components that suppress the alkali solubility of the photosensitive coloring resin composition, but also as components that enhance solubility relative to the solvent, and consequently, solvent resolubility.

[0352] The alkali-soluble resin used in this invention preferably comprises acrylic copolymers and styrene-acrylic copolymers, which are acrylic resins containing structural units having carboxyl groups and structural units having hydrocarbon rings. More preferably, acrylic copolymers and styrene-acrylic copolymers, which are acrylic resins containing structural units having carboxyl groups, structural units having hydrocarbon rings and structural units having olefin double bonds, are acrylic resins.

[0353] Regarding alkali-soluble resins, by appropriately adjusting the amount of each structural unit added, alkali-soluble resins with the desired properties can be prepared.

[0354] From the viewpoint of obtaining a good pattern, the amount of carboxyl-containing olefinic unsaturated monomer added is preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of monomer. On the other hand, from the viewpoint of suppressing film roughness on the surface of the pattern after development, the amount of carboxyl-containing olefinic unsaturated monomer added is preferably 50% by mass or less, more preferably 40% by mass or less, relative to the total amount of monomer.

[0355] If the ratio of carboxyl-containing olefinic unsaturated monomers is above the lower limit mentioned above, the obtained coating film has sufficient solubility relative to the alkaline developer. Furthermore, if the ratio of carboxyl-containing olefinic unsaturated monomers is below the upper limit mentioned above, there is a tendency for the formed pattern to detach from the substrate or for the film on the pattern surface to become rough when developed with the alkaline developer.

[0356] Furthermore, in acrylic resins such as acrylic copolymers containing olefinic double bonds and styrene-acrylic copolymers, which are more preferably used as alkali-soluble resins, the amount of the compound containing both epoxy groups and olefinic double bonds relative to the carboxyl-containing olefinic unsaturated monomer is preferably 10% to 95% by mass, more preferably 15% to 90% by mass.

[0357] The weight-average molecular weight (Mw) of the preferred carboxyl-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. If it is below 1,000, the adhesive function after curing will be significantly reduced; if it is above 50,000, it will be difficult to form a pattern when developed with an alkaline developer.

[0358] It should be noted that polystyrene can be used as a standard substance, THF as a solvent, and the weight-average molecular weight (Mw) of the carboxyl-containing copolymer can be determined using the Shodex GPC System-21H.

[0359] There are no particular limitations on the type of epoxy (meth)acrylate resin containing carboxyl groups, but epoxy (meth)acrylate compounds obtained by reacting an epoxy compound with the reaction product of a monocarboxylic acid containing an unsaturated group and an acid anhydride are more suitable.

[0360] Epoxy compounds, monocarboxylic acids containing unsaturated groups, and acid anhydrides may be appropriately selected from those known to the public. Epoxy (meth)acrylate resins containing carboxyl groups may be used alone or in combination with two or more.

[0361] Regarding alkali-soluble resins, in terms of their developability (solubility) relative to the alkaline aqueous solution used in the developer, it is preferable to select those with an acid value of 50 mg KOH / g or higher. In terms of both 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 mg KOH / g or higher and 300 mg KOH / g or lower, and more preferably 70 mg KOH / g or higher and 200 mg KOH / g or lower.

[0362] It should be noted that the acid value of alkali-soluble resins can be determined according to JIS K 0070:1992.

[0363] From the viewpoint of achieving improved film strength, enhanced developability, and superior adhesion to the substrate in cured films, the olefin unsaturated bond equivalent in the case where the side chains of the alkali-soluble resin have olefin unsaturated groups is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. If the olefin unsaturated bond equivalent is 100 or more, the developability and adhesion are excellent. Furthermore, if the olefin unsaturated bond equivalent is 2000 or less, the ratio of other structural units such as those with carboxyl groups and hydrocarbon rings can be relatively increased, thus resulting in excellent developability and heat resistance.

[0364] Here, the so-called olefin unsaturated bond equivalent is the weight-average molecular weight of olefin unsaturated bonds per mole in the above-mentioned alkali-soluble resin, expressed by the following formula (1).

[0365] Equation (1) Equivalent weight of unsaturated olefinic bonds (g / mol) = W(g) / M(mol)

[0366] (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of alkali double bonds contained in the alkali-soluble resin W (g))

[0367] The equivalent of the aforementioned olefinic unsaturated bonds can also be calculated, for example, by determining the number of olefinic double bonds contained in 1g of alkali-soluble resin according to the iodine value test method described in JIS K 0070:1992.

[0368] The alkali-soluble resin used in the photosensitive coloring resin composition can be used alone or in combination of two or more types. There is no particular limitation on the content of the alkali-soluble resin, but relative to the total solid content of the photosensitive coloring resin composition, it is preferably in the range of 1% to 60% by mass, and more preferably in the range of 5% to 40% by mass. If the content of the alkali-soluble resin is above or below the aforementioned lower limit, sufficient alkaline developability is obtained; furthermore, if the content of the alkali-soluble resin is below the aforementioned upper limit, film roughness or pattern gaps can be suppressed during development.

[0369] (Antioxidants)

[0370] From the viewpoint of improving heat resistance, inhibiting fading of pigments, and enhancing brightness, the photosensitive coloring resin composition of the present invention preferably further contains an antioxidant. The antioxidant can be appropriately selected from those previously known. Specific examples of antioxidants include hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc., and hindered phenolic antioxidants are preferred in terms of heat resistance. Latent antioxidants, such as those described in International Publication No. 2014 / 021023, may also be used.

[0371] Examples of hindered phenolic antioxidants include: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010; manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114; manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)-1,3,5-trimethylbenzene (trade name: IRGANOX 1330; manufactured by BASF), and 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: SUMILIZER). MDP-S (manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081; manufactured by BASF), and diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: IRGANOX 195; manufactured by BASF), etc. Among these, pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010; manufactured by BASF) is preferred in terms of heat resistance and lightfastness.

[0372] If the photosensitive coloring resin composition of the present invention contains the above-mentioned oxime ester photoinitiator and antioxidant, the brightness is improved by utilizing the synergistic effect, the residual film rate is improved, and the linearity is further improved when forming fine line patterns or the ability to form fine line patterns according to the mask linewidth design is improved, which is therefore preferred.

[0373] The content of the antioxidant, relative to the total solid content of the photosensitive coloring resin composition, is preferably 0.1% to 10.0% by mass, more preferably 0.5% to 5.0% by mass. If the content is above the lower limit, the heat resistance and lightfastness are excellent. On the other hand, if the content is below the upper limit, the coloring resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

[0374] When an antioxidant is used in combination with the aforementioned oxime ester-based photoinitiator, the amount of antioxidant used is preferably 1 to 250 parts by mass, more preferably 3 to 80 parts by mass, and even more preferably 5 to 45 parts by mass, relative to 100 parts by mass of the total amount of the aforementioned oxime ester-based photoinitiator. If the amount falls within the above range, the combination will produce excellent results.

[0375] (Various additives)

[0376] The photosensitive coloring resin composition of the present invention may also contain various additives.

[0377] Examples of additives include: polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, and adhesion promoters.

[0378] Specific examples of surfactants and plasticizers include those described in Japanese Patent Application Publication No. 2013-029832.

[0379] In addition, examples of silane coupling agents include: 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, and X-12-967C (manufactured by Shin-Etsu Silicones). Among these, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103, which have methacrylyl or acryloyl groups, are preferred in terms of adhesion to the SiN substrate.

[0380] Regarding the content of the silane coupling agent, relative to 100 parts by weight of the total solids in the photosensitive coloring resin composition, the silane coupling agent is preferably 0.05 parts by weight or more and 10.0 parts by weight or less, more preferably 0.1 parts by weight or more and 5.0 parts by weight or less. If it is above the lower limit and below the upper limit, the substrate adhesion is excellent.

[0381] <Formulation ratio of each component in the photosensitive coloring resin composition>

[0382] The total content of the colorant, relative to the total solid content of the photosensitive coloring resin composition, is preferably in the range of 3% to 65% by mass, and more preferably in the range of 4% to 60% by mass. If it is above the lower limit, the coloring layer has sufficient color concentration when the photosensitive coloring resin composition is coated to a specified film thickness (typically 1.0 μm to 5.0 μm). Furthermore, if it is below the upper limit, a coloring layer with excellent storage stability and sufficient hardness or adhesion to the substrate can be obtained. Especially when forming a coloring layer with a high colorant concentration, the content of the colorant, relative to the total solid content of the photosensitive coloring resin composition, is preferably in the range of 15% to 75% by mass, and more preferably in the range of 25% to 70% by mass.

[0383] Furthermore, the content of the dispersant is not particularly limited, as long as it can uniformly disperse the colorant. However, for example, relative to the total solid content of the photosensitive coloring resin composition, it is preferably in the range of 1% to 40% by mass, more preferably in the range of 2% to 30% by mass, and even more preferably in the range of 3% to 25% by mass. If it is above the lower limit, the dispersibility and dispersion stability of the colorant are excellent, and the storage stability of the photosensitive coloring resin composition is even better. In addition, if it is below the upper limit, the developability becomes good. Especially when forming a coloring layer with a high concentration of colorant, the content of the dispersant relative to the total solid content of the photosensitive coloring resin composition is preferably in the range of 2% to 25% by mass, more preferably in the range of 3% to 20% by mass.

[0384] Furthermore, the solvent content only needs to be appropriately set within a range that allows for the precise formation of the coloring layer. Relative to the total amount of the photosensitive coloring resin composition containing the solvent, the solvent content is preferably in the range of 55% to 95% by mass, and more preferably in the range of 65% to 88% by mass. By keeping the solvent content within the aforementioned range, excellent coatability can be achieved.

[0385] <Method for manufacturing photosensitive coloring resin composition>

[0386] The method for manufacturing the photosensitive coloring resin composition of the present invention is not particularly limited. For example, it can be obtained by adding a multifunctional monomer, a photoinitiator, an alkali-soluble resin (optional), and other components to the color material dispersion of the present invention, and then mixing it using a known mixing method. Alternatively, it can be obtained by adding a color material, the dispersant of the present invention, the multifunctional monomer, the photoinitiator, a solvent, an alkali-soluble resin (optional), and other components, and then mixing it using a known mixing method.

[0387] <Applications>

[0388] The photosensitive coloring resin composition of the first invention is suitable for use in color filters because it simultaneously satisfies excellent dispersion stability, solvent resolubility and substrate adhesion.

[0389] The photosensitive coloring resin composition of the present invention is used in various applications requiring excellent dispersion stability of fine colorants, and is also used in inkjet inks or printing inks.

[0390] I-3. The first color filter of the present invention

[0391] The color filter of the first invention comprises at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured product of the photosensitive coloring resin composition of the first invention.

[0392] One side reference Figure 1 The color filter of this invention will now be described. Figure 1 A schematic cross-sectional view illustrating an example of the color filter of the present invention. According to... Figure 1 The color filter 10 of the present invention includes a substrate 1, a light-shielding part 2, and a coloring layer 3.

[0393] <shading layer>

[0394] The coloring layer used in the color filter of the present invention is at least one coloring layer that is a cured product of the photosensitive coloring resin composition of the present invention described above.

[0395] The coloring layer is usually formed in the opening of the light-shielding part on the substrate below, and usually contains a coloring pattern of three or more colors.

[0396] Furthermore, there are no particular limitations on the arrangement of the color layers; for example, they can be arranged in a striped, mosaic, triangular, or 4-pixel configuration, among other common arrangements. Additionally, the width and area of ​​the color layers can be set arbitrarily.

[0397] The thickness of the coloring layer can be appropriately controlled by adjusting the coating method, the concentration or viscosity of the solid components in the photosensitive coloring resin composition, etc., and is usually preferably in the range of 1μm to 5μm.

[0398] This colored layer can be formed, for example, by the following method.

[0399] First, the photosensitive coloring resin composition of the present invention is coated onto the substrate using coating methods such as spraying, dip coating, rod coating, roller coating, spin coating, and die coating to form a wet coating film. Spin coating and die coating are preferred methods.

[0400] Subsequently, after the wet coating is dried using a heating plate or oven, it is exposed to light through a mask with a specified pattern, causing the alkali-soluble resin and multifunctional monomers to undergo a photopolymerization reaction to form a cured coating. Examples of light sources used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet light, and electron beams. The exposure amount is adjusted appropriately according to the light source used or the thickness of the coating.

[0401] In addition, heat treatment can be performed after exposure to promote the polymerization reaction. The heating conditions are appropriately selected based on the mixing ratio of the components in the photosensitive coloring resin composition or the thickness of the coating film.

[0402] Next, a developing solution is used to develop the coating, dissolving and removing the unexposed areas, thereby forming a film with the desired pattern. The developing solution is typically a solution made by dissolving an alkali in water or a water-soluble solvent. Appropriate amounts of surfactants may also be added to this alkaline solution. Alternatively, conventional methods can be used for development.

[0403] After development, the coating is typically cleaned with the developer, cured with the photosensitive coloring resin composition, and then dried to form a colored layer. It should be noted that after development, heat treatment can also be performed to ensure complete curing of the coating. There are no particular limitations on the heating conditions; they should be selected appropriately based on the intended use of the coating.

[0404] <Light shielding part>

[0405] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate described below, and can be configured to be the same as the light-shielding portion generally used as a light-shielding portion in a color filter.

[0406] The shape of the pattern for the light-shielding part is not particularly limited; for example, stripes or a matrix pattern can be used. The light-shielding part can also be a thin film of metal such as chromium obtained by sputtering or vacuum evaporation. Alternatively, the light-shielding part can be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, or organic pigments in a resin binder. When the resin layer contains light-shielding particles, methods include using a photosensitive resist and patterning by development, using inkjet ink containing light-shielding particles for patterning, and heat transfer of the photosensitive resist.

[0407] The film thickness of the light-shielding part is set to about 0.2 μm to 0.4 μm when it is a metal film, and to about 0.5 μm to 2 μm when it is formed by dispersing or dissolving black pigment in adhesive resin.

[0408] <Substrate>

[0409] As a substrate, transparent substrates, silicon substrates, and substrates on which aluminum, silver, or silver / copper / palladium alloy thin films are formed can be used. Other color filter layers, resin layers, TFTs, and other transistors and circuits can also be formed on these substrates.

[0410] The transparent substrate used in the color filter of this invention is not particularly limited, as long as it is a substrate that is transparent to visible light, and the 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 flexible materials that are flexible, such as transparent resin films, optical resin plates, and flexible glass.

[0411] The thickness of the transparent substrate is not particularly limited and can be used for applications of the color filter according to the present invention, for example, a thickness of about 100 μm to 1 mm.

[0412] Furthermore, in addition to the aforementioned substrate, light-shielding portion and coloring layer, the color filter of the present invention may also have, for example, an outer coating layer or a transparent electrode layer, and further form an alignment film or columnar spacer, etc.

[0413] I-4. The first display device of the present invention

[0414] The first feature of the display device of the present invention is that it has the color filter described above. The configuration of the display device in the first invention is not particularly limited, and can be appropriately selected from previously known display devices, such as liquid crystal displays or organic light-emitting displays.

[0415] Liquid crystal display device

[0416] As a liquid crystal display device of the present invention, an example of such a liquid crystal display device may be provided, which includes the color filter, the opposing substrate, and the liquid crystal layer formed between the color filter and the opposing substrate described above.

[0417] The liquid crystal display device of the present invention will be described with reference to the accompanying drawings. Figure 2 This is a schematic diagram illustrating an example of the liquid crystal display device of the present invention. Figure 2 As illustrated, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

[0418] It should be noted that the liquid crystal display device of the present invention is not limited to this. Figure 2 The configuration shown can be configured as is commonly known in liquid crystal display devices that use color filters.

[0419] There is no particular limitation on the driving method of the liquid crystal display device of the present invention, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include TN method, IPS method, OCB method, and MVA method. In the present invention, it is suitable to use any of the above methods.

[0420] Furthermore, the opposing substrate can be appropriately selected from the driving method of the liquid crystal display device according to the present invention.

[0421] Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals with different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

[0422] As a method for forming the liquid crystal layer, methods commonly used for manufacturing liquid crystal cells can be used, such as vacuum injection or liquid crystal droplet method. After forming the liquid crystal layer by the above method, the liquid crystal cell is slowly cooled to room temperature, thereby aligning the encapsulated liquid crystal.

[0423] Organic light-emitting display device

[0424] As an organic light-emitting display device of the present invention, an organic light-emitting display device including the color filter and organic light-emitting body of the present invention can be cited as an example.

[0425] The organic light-emitting display device of the present invention will be described with reference to the accompanying drawings. Figure 3 This is a schematic diagram illustrating an example of the organic light-emitting display device of the present invention. (See diagram below.) Figure 3 As illustrated, the organic light-emitting display device 100 of the present invention includes a color filter 10 and an organic light-emitting element 80. An organic protective layer 50 and an inorganic oxide film 60 may also be provided between the color filter 10 and the organic light-emitting element 80.

[0426] Examples of methods for stacking the organic light-emitting element 80 include: sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, an emissive layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter; or attaching the organic light-emitting element 80 formed on another substrate to an inorganic oxide film 60. The transparent anode 71, hole injection layer 72, hole transport layer 73, emissive layer 74, electron injection layer 75, cathode 76, and other components of the organic light-emitting element 80 are suitable for use with known methods. An organic light-emitting display device 100 manufactured in this manner can be applied, for example, to a passively driven organic EL display or an actively driven organic EL display.

[0427] It should be noted that the organic light-emitting display device of the present invention is not limited to this. Figure 3 The configuration shown can be configured as is commonly known in liquid crystal display devices that use color filters.

[0428] II. The Second Invention

[0429] The following describes in detail the color material dispersion, photosensitive coloring resin composition, color filter, liquid crystal display device, and organic light-emitting display device of the second invention in sequence.

[0430] II-1. The second color material dispersion of the present invention

[0431] The second color material dispersion of the present invention contains color material, dispersant and solvent.

[0432] The dispersant contains at least one of a graft copolymer and a block copolymer. The graft copolymer has a structural unit derived from a carboxyl-containing olefinic unsaturated monomer and a structural unit represented by the following general formula (III). The polymer chain in the structural unit represented by the general formula (III) contains at least one structural unit selected from the structural units represented by the following general formula (V) and the following general formula (V'). The block copolymer has: an A block containing a structural unit derived from a carboxyl-containing olefinic unsaturated monomer; and a B block containing at least one structural unit selected from the structural units represented by the following general formula (V) and the following general formula (V').

[0433] [Chemical Formula 12]

[0434]

[0435] (In general formula (III), R) 1” A represents a hydrogen atom or a methyl group. 1 (Indicates direct bonding or divalent linkage; Polymer indicates polymer chain)

[0436] [Chemical Formula 13]

[0437]

[0438] (In general formula (V), R) 11' A is a hydrogen atom or a methyl group. 2' For a divalent linkage base, R 5 It is ethylene or propylene, R 6 It represents a hydrogen atom or a hydrocarbon group, where m represents a number greater than 2 and less than 80;

[0439] In the general formula (V'), R 11” A is a hydrogen atom or a methyl group. 2” For a divalent linkage base, R 7 R is an alkylene group having 1 to 10 carbon atoms. 8 R is an alkylene group having 3 to 7 carbon atoms. 9 (This represents a hydrogen atom or a hydrocarbon group, where n is a number greater than 1 and less than 40.)

[0440] The second color material dispersion of the present invention uses the above-mentioned specific graft copolymer or block copolymer as a dispersant. The above-mentioned specific graft copolymer or block copolymer contains structural units derived from carboxyl-containing olefinic unsaturated monomers, and at least one structural unit selected from the structural units represented by the above-mentioned general formula (V) and the structural units represented by the above-mentioned general formula (V'). Therefore, a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability (shortening of development time) can be produced.

[0441] Regarding the specific graft copolymer or block copolymer used in the second invention, it is believed that: since it contains structural units derived from carboxyl-containing olefinic unsaturated monomers, the substrate adhesion of the coating film is improved by interacting with polar groups such as glass surfaces that serve as substrates; and since it contains structural units having polyethylene oxide chains, polypropylene oxide chains, or ester chains, the oxygen atoms contained in the polyethylene oxide chains, polypropylene oxide chains, or ester chains undergo hydrogen bonding with the alkaline developer, making it easily soluble in the alkaline developer during development, thereby shortening the development time.

[0442] The second color material dispersion of the present invention contains at least a color material, a dispersant and a solvent, and may also contain other components within the scope of not impairing the effect of the present invention.

[0443] Hereinafter, the components of the colorant dispersion of this second invention will be described in detail, starting with the dispersant, which is a feature of the second invention.

[0444] <The dispersant used in the second invention>

[0445] The dispersant used in the second invention is a dispersant of the second invention, having structural units derived from carboxyl-containing olefinic unsaturated monomers and structural units represented by the above general formula (III). The polymer chain in the structural unit represented by the general formula (III) is at least one of graft copolymers and block copolymers. The graft copolymer contains at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V'). The block copolymer has: A block, which contains structural units derived from carboxyl-containing olefinic unsaturated monomers; and B block, which contains at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V').

[0446] [Graft copolymer]

[0447] The second graft copolymer used in this invention has structural units derived from carboxyl-containing olefinic unsaturated monomers that function as adsorption sites for colorants in the main chain, and further has structural units represented by the above general formula (III) in the side chain, which includes graft polymer chains that function as solvent affinity parts. The graft polymer chains include at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V').

[0448] The structural unit derived from the carboxyl-containing olefinic unsaturated monomer in the second invention may be the same as the structural unit derived from the carboxyl-containing olefinic unsaturated monomer in the first invention, and may be selected from at least one of the structural units represented by the general formula (I) and the general formula (II) in the first invention.

[0449] The structural unit represented by the above general formula (I) can be the same as the structural unit represented by the above general formula (I) in the first invention. The structural unit represented by the above general formula (II) can be the same as the structural unit represented by the above general formula (II) in the first invention.

[0450] The second graft copolymer used in this invention has a structural unit represented by the above-described general formula (III), wherein the polymer chain contained in the structural unit represented by general formula (III) functions as a solvent-affinity component. In the graft copolymer used in this invention, the polymer chain in the structural unit represented by general formula (III) contains at least one structural unit selected from the structural units represented by general formula (V) and the structural units represented by general formula (V').

[0451] The structural unit represented by the above general formula (III) can be the same as the structural unit represented by the above general formula (III) in the first invention. The structural unit represented by the above general formula (V) can be the same as the structural unit represented by the above general formula (V) in the first invention. The structural unit represented by the above general formula (V') can be the same as the structural unit represented by the above general formula (V') in the first invention.

[0452] In the polymer chain described above, at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V') may be a single unit or a mixture of two or more units.

[0453] Regarding improved substrate adhesion and shortened development time, when the total structural units of the polymer chain in the macromonomer of the graft copolymer are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V') is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Regarding solvent resolvability, when the total structural units of the polymer chain are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V') is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0454] The second invention uses a graft copolymer whose structural unit in the polymer chain represented by the above general formula (III) preferably includes, in addition to including at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V'), a structural unit represented by the above general formula (IV) that is different from the structural units selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V').

[0455] 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 described above.

[0456] In the polymer chain described above, the structural unit represented by the general formula (IV), which is different from at least one structural unit selected from the group consisting of the structural units represented by the general formula (V) and the structural units represented by the general formula (V'), may be a single type or a mixture of two or more types.

[0457] When the total structural units of the polymer chains in the macromonomer of the graft copolymer are set to 100% by mass, the total ratio of the structural units represented by the general formula (IV) that are different from at least one of the structural units represented by the general formula (V) and the structural units represented by the general formula (V') is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, in terms of solvent resolubility. In terms of improving substrate adhesion and shortening development time, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0458] Furthermore, in addition to the structural units of the polymer chain in the structural unit represented by the above general formula (III) of the graft copolymer used in the second invention, other structural units may also be included in the structural unit represented by the above general formula (IV), which includes at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V').

[0459] As another structural unit, examples can be given of structural units derived from olefinic unsaturated monomers capable of copolymerizing with olefinic unsaturated monomers that derive the structural unit represented by the above general formula (IV). The monomers from which this other structural unit is derived, and their total ratio, can be the same as those used in the first invention described above for deriving other structural units.

[0460] Furthermore, the mass-average molecular weight Mw, glass transition temperature, acid value, and amine value of the polymer chain described above can be the same as those of the polymer chain in the graft copolymer used in the first invention described above.

[0461] In the second invention, the total content ratio of the structural units derived from carboxyl-containing olefinic unsaturated monomers in the above-mentioned graft copolymer is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass. If the total content ratio of the structural units derived from carboxyl-containing olefinic unsaturated monomers in the graft copolymer is within the above range, the ratio of the affinity site for the colorant in the graft copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed. Therefore, the adsorption of the colorant becomes good, and excellent dispersibility, dispersion stability, and solvent resolubility can be obtained.

[0462] On the other hand, in the above-mentioned graft copolymer, the total content ratio of the structural units represented by the above-mentioned general formula (III) is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 65% ​​to 91% by mass. If the total content ratio of the structural units represented by the above-mentioned general formula (III) in the graft copolymer is within the above range, the ratio of the solvent affinity portion in the graft copolymer becomes appropriate, sufficient stereorepulsion effect as a dispersant can be maintained, and the effect of the increased specific surface area of ​​the solvent affinity portion of the dispersant on the above-mentioned effect can be improved.

[0463] It should be noted that the content ratio of the above structural units is calculated based on the amount of monomers added during the synthesis of the graft copolymer, including the structural units derived from the carboxyl-containing olefinic unsaturated monomers and the structural units represented by the above general formula (III).

[0464] Secondly, the graft copolymers used in this invention may also have other structural units besides the structural units derived from carboxyl-containing olefinic unsaturated monomers and the structural units represented by the general formula (III) described above, without impairing the effects of this invention. Regarding these other structural units, olefinic unsaturated monomers capable of copolymerizing with olefinic unsaturated monomers that derive structural units such as those represented by the general formula (III) described above may be appropriately selected to introduce other structural units.

[0465] Other structural units copolymerized with the structural unit represented by general formula (III) above can be exemplified by structural units represented by general formula (IV) above. In the above graft copolymer, the total content of other structural units copolymerized with the main chain is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass.

[0466] [Block copolymer]

[0467] The second block copolymer used in this invention has: an A block comprising a structural unit derived from a carboxyl-containing olefinic unsaturated monomer and functioning as an adsorption site for colorants; and a B block comprising at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V') and functioning as a solvent affinity part.

[0468] In the A block of the block copolymer used in the second invention, the structural units derived from the carboxyl-containing olefinic unsaturated monomer described above may be the same as those described in the graft copolymer used in the second invention.

[0469] In the case where block A contains two or more structural units derived from carboxyl-containing olefinic unsaturated monomers, the two or more structural units may also be block copolymerized. However, in terms of adsorption efficiency on the surface of the color material that is more suitable for adsorption than the surface of the color material in various states such as stereohindrance or polarity, random copolymerization is preferred.

[0470] In the A block of the block copolymer used in the second invention, other structural units may be included, in addition to the structural units derived from the carboxyl-containing olefinic unsaturated monomers described above, without impairing the effects of the invention. Regarding these other structural units, olefinic unsaturated monomers may be appropriately selected for copolymerization to introduce other structural units.

[0471] Other structural units included in segment A without impairing the effects of the present invention may include, for example, the structural unit represented by the above general formula (IV). 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 present invention described above.

[0472] The total percentage of the structural units derived from the carboxyl-containing olefinic unsaturated monomers contained in block A is not particularly limited, as long as it is within the range that does not impair the effect of the present invention. However, in terms of dispersibility and dispersion stability, it is preferred to be 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.

[0473] The total percentage of other structural units contained in block A is not particularly limited, as long as it is within the range that does not impair the effect of the present invention. However, in terms of dispersibility and dispersion stability, it is preferred to be 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass.

[0474] (B-segment)

[0475] In the second block copolymer used in this invention, the B block is a block that functions as a solvent affinity part and includes at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V').

[0476] In the B block of the block copolymer used in the second invention, at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V') may be the same as those described in the graft copolymer used in the second invention.

[0477] In the block copolymer used in the second invention, from the perspective of improving solvent affinity and improving the dispersibility and dispersion stability of the colorant, the B block, which functions as the solvent affinity part, may further include the structural unit represented by the above general formula (IV) that is different from at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V').

[0478] The structural unit represented by the above general formula (IV) included in the B block can be the same as that described in the above graft copolymer.

[0479] In the above B block, the structural unit represented by the above general formula (IV) may be a single type or a combination of two or more structural units, including at least one 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').

[0480] Regarding the dispersibility and dispersion stability of the colorant, in the aforementioned B block, when the total structural units of the B block are set to 100% by mass, the total ratio of the structural units represented by the aforementioned general formula (IV), which includes at least one structural unit selected from the structural units represented by the aforementioned general formula (V) and the structural units represented by the aforementioned general formula (V'), may also be 100% by mass. Regarding the dispersibility and dispersion stability of the colorant, in the aforementioned B block, when the total structural units of the B block are set to 100% by mass, the total ratio of the structural units represented by the aforementioned general formula (IV) is preferably 40% by mass or more, and more preferably 70% by mass or more.

[0481] Furthermore, in the above-mentioned B block, at least one structural unit selected from 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 a single type or a combination of two or more types.

[0482] Regarding improving substrate adhesion and shortening development time, when the total structural units of the aforementioned B-block are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the aforementioned general formula (V) and the structural units represented by the aforementioned general formula (V') is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Regarding solvent resolvability, when the total structural units of the aforementioned B-block are set to 100% by mass, the total ratio of at least one structural unit selected from the structural units represented by the aforementioned general formula (V) and the structural units represented by the aforementioned general formula (V') is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0483] Furthermore, in the above-mentioned B block, the structural unit represented by the above-mentioned general formula (IV), which is different from at least one structural unit selected from the structural units represented by the above-mentioned general formula (V) and the structural units represented by the above-mentioned general formula (V'), may be a single type or a mixture of two or more types.

[0484] When the total structural units of the above-mentioned B block are set to 100% by mass, the total ratio of the structural units represented by the above-mentioned general formula (IV) that are different from at least one structural unit selected from the structural units represented by the above-mentioned general formula (V) and the structural units represented by the above-mentioned general formula (V') is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, in terms of improving substrate adhesion and shortening development time, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0485] In the above B block, in addition to the structural unit represented by the above general formula (IV) which includes at least one 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'), other structural units may also be optionally included.

[0486] As another structural unit, examples can be given of structural units derived from olefinic unsaturated monomers capable of copolymerizing with olefinic unsaturated monomers that derive the structural unit represented by the above general formula (IV). The monomers from which this other structural unit is derived, and their total ratio, can be the same as those used in the first invention described above for deriving other structural units.

[0487] Furthermore, the mass-average molecular weight Mw, glass transition temperature, acid value, amine value, copolymerization method, and bonding sequence of the B-block can be the same as those of the B-block in the block copolymer used in the first invention described above.

[0488] In the block copolymer described above, the total content ratio of the structural units derived from carboxyl-containing olefinic unsaturated monomers is preferably 3% to 60% by mass, more preferably 6% to 45% by mass, and even more preferably 9% to 35% by mass. If the total content ratio of the structural units derived from carboxyl-containing olefinic unsaturated monomers in the block copolymer is within the above range, the ratio of the affinity site for the colorant in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed. Therefore, the adsorption of the colorant becomes good, and excellent dispersibility, dispersion stability, and solvent resolubility can be obtained.

[0489] On the other hand, in the above-mentioned block copolymer, the total content of B blocks is preferably 40% to 97% by mass, more preferably 55% to 94% by mass, and even more preferably 65% ​​to 91% by mass. If the total content of B blocks in the block copolymer is within the above range, the ratio of solvent-affinity portions in the block copolymer becomes appropriate, sufficient steric repulsion effect as a dispersant can be maintained, and the effect of the increased specific surface area of ​​the solvent-affinity portions of the dispersant on the above-mentioned effect can be improved.

[0490] It should be noted that the content ratio of the above structural units is calculated based on the amount of structural units derived from carboxyl-containing olefinic unsaturated monomers, and monomers selected from at least one of the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V') added during the synthesis of the block copolymer.

[0491] The mass-average molecular weight Mw and acid value of at least one of the graft copolymers and block copolymers used in the second invention may be the same as those of at least one of the graft copolymers and block copolymers used in the first invention.

[0492] In the color material dispersion of the second invention, the dispersant contains the graft copolymer and block copolymer used in the second invention, but may also optionally contain other known dispersants, as long as the effect of the invention is not impaired.

[0493] In the dispersant used in the color material dispersion of the second invention, the total content of at least one of the graft copolymer and the block copolymer used in the second invention is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0494] In the color material dispersion of the second invention, at least one of the above-mentioned graft copolymer and block copolymer is used as a dispersant, and its content is appropriately selected according to the type of color material used and, consequently, the concentration of solid components in the following photosensitive coloring resin composition.

[0495] The content of dispersant in the color material dispersion can be the same as that in the color material dispersion of the first invention described above.

[0496] In the second color material dispersion of the present invention, the color material, solvent, and other components may be the same as those in the first color material dispersion of the present invention.

[0497] <Preferred form of the colorant dispersion of the second invention>

[0498] In the second color material dispersion of the present invention, in the dispersant, the polymer chain in the structural unit represented by the general formula (III) of the graft copolymer further includes a structural unit represented by the general formula (IV) that is different from at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V'). The glass transition temperature of the polymer chain in the structural unit represented by the general formula (III) is 85°C or less. The B block of the block copolymer further includes a structural unit represented by the general formula (IV) that is different from at least one structural unit selected from the structural units represented by the general formula (V) and the structural units represented by the general formula (V'). The glass transition temperature of the B block is 85°C or less. This is preferred because it improves the development time delay and coating suitability. In order to improve production efficiency, it is required to increase the coating speed of the photosensitive coloring resin composition. If the coating suitability is excellent, it is not easy to produce uneven stripes during high-speed coating.

[0499] In the colorant dispersion of the second invention, in terms of dispersion stability and solvent resolubility, the acid value of at least one of the above-mentioned graft copolymer and block copolymer is preferably 30 mg KOH / g to 180 mg KOH / g.

[0500] II-2. The second photosensitive coloring resin composition of the present invention

[0501] The second photosensitive coloring resin composition of the present invention contains a colorant, the dispersant of the second invention described above, a multifunctional monomer, a photoinitiator, and a solvent.

[0502] In the photosensitive coloring resin composition of the second invention, the dispersant of the second invention described above can be the same as the dispersant described in the color material dispersion of the second invention.

[0503] The second photosensitive coloring resin composition of the present invention, by containing the dispersant, colorant and solvent of the second invention described above, can simultaneously satisfy excellent substrate adhesion and developability, just as described in the colorant dispersion of the second invention.

[0504] The second photosensitive coloring resin composition of the present invention contains at least a colorant, the dispersant of the second invention described above, a multifunctional monomer, a photoinitiator, and a solvent, and may further contain other components without impairing the effects of the present invention.

[0505] In the second photosensitive coloring resin composition of the present invention, the colorant, solvent, multifunctional monomer, photoinitiator, and other components may be the same as those in the first photosensitive coloring resin composition of the present invention.

[0506] <Preferred form of the photosensitive coloring resin composition of the second invention>

[0507] From the perspective of improved notch resistance and good storage stability, the photosensitive coloring resin composition of the second invention preferably further contains a polyfunctional thiol compound. This polyfunctional thiol compound may be the same as the polyfunctional thiol compound in the first invention described above.

[0508] In terms of improved notch resistance and good storage stability, the photosensitive coloring resin composition of the second invention preferably contains a polyfunctional thiol compound represented by the above general formula (A).

[0509] In the second photosensitive coloring resin composition of the present invention, from the viewpoint of easily improving notch resistance and easily suppressing the generation of development residue, the content of the above-mentioned polyfunctional thiol compound is preferably, for example, 0.001 parts by mass to 15.0 parts by mass, or 0.01 parts by mass to 15.0 parts by mass, relative to 100 parts by mass of total solids in the coloring resin composition.

[0510] <Application>

[0511] Secondly, the photosensitive coloring resin composition of the present invention can simultaneously satisfy excellent substrate adhesion and developability (shortened development time), and is therefore suitable for use in color filters.

[0512] II-3. The second color filter of the present invention

[0513] The second color filter of the present invention includes at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured product of the photosensitive coloring resin composition of the second invention described above.

[0514] The second color filter of the present invention can be manufactured into a color filter with excellent production performance by having at least one of the coloring layers being a cured product of the photosensitive coloring resin composition of the second invention described above.

[0515] The second color filter of the present invention, as long as it has the cured product of the photosensitive coloring resin composition of the second invention described above, i.e., the coloring layer, may have the same other components as those described in the first color filter of the present invention.

[0516] II-4. The second display device of the present invention

[0517] The liquid crystal display device of the second invention is characterized by having the color filter described above.

[0518] In the second invention, by using the color filter of the second invention described above, a display device with excellent productivity can be provided.

[0519] The display device of the second invention, as long as it has the color filter of the second invention described above, can have the same other configurations as those described in the display device of the first invention, so the description is omitted here.

[0520] According to the second invention, a colorant dispersion and a dispersant capable of producing a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability can be provided. Furthermore, according to the second invention, a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability, a color filter formed using the photosensitive coloring resin composition, and a display device can be provided.

[0521] III. The Third Invention

[0522] III-1. The third photosensitive coloring resin composition of the present invention

[0523] The third photosensitive coloring resin composition of the present invention contains a colorant, a dispersant, a multifunctional monomer, a photoinitiator, a solvent, and a multifunctional thiol compound, wherein the dispersant comprises at least one type of graft copolymer and block copolymer having structural units derived from carboxyl-containing olefinic unsaturated monomers.

[0524] The third photosensitive coloring resin composition of the present invention, by containing a polyfunctional thiol compound and the dispersant comprising at least one of a graft copolymer and a block copolymer having structural units derived from carboxyl-containing olefinic unsaturated monomers, exhibits good notch resistance and good storage stability. It is presumed that, according to this combination, through the effects described in the first photosensitive coloring resin composition of the present invention, the photosensitive coloring resin composition exhibits good notch resistance and good storage stability.

[0525] The third photosensitive coloring resin composition of the present invention contains at least a colorant, the dispersant used in the third invention, a multifunctional monomer, a photoinitiator, a solvent, and a multifunctional thiol compound, and may further contain other components without impairing the effects of the present invention.

[0526] Hereinafter, starting with the dispersant, which is a feature of the third invention, each component of the photosensitive coloring resin composition of the third invention will be described in detail.

[0527] <The dispersant used in the third invention>

[0528] Third, the dispersant used in this invention comprises at least one type of graft copolymer and block copolymer having structural units derived from carboxyl-containing olefinic unsaturated monomers.

[0529] [Graft copolymer]

[0530] The third type of graft copolymer used in this invention is a copolymer in which the main chain has structural units derived from carboxyl-containing olefinic unsaturated monomers that function as adsorption sites for colorants, and the side chains have graft polymer chains that function as solvent affinity sites.

[0531] The structural units derived from carboxyl-containing olefinic unsaturated monomers in the third invention may be the same as the structural units derived from carboxyl-containing olefinic unsaturated monomers in the graft copolymers used in the second invention.

[0532] The structural unit with grafted polymer chains in the third invention may be the same as the structural unit with grafted polymer chains in the first invention described above.

[0533] In the third graft copolymer used in this invention, the total content ratio of the structural units derived from carboxyl-containing olefinic unsaturated monomers can be the same as the total content ratio of the structural units represented by general formula (I) and general formula (II) in the graft copolymer used in the first invention. Furthermore, in the third graft copolymer used in this invention, the content ratio of structural units having grafted polymer chains can be the same as the content ratio of structural units having grafted polymer chains in the graft copolymer used in the first invention.

[0534] [Block copolymer]

[0535] The third block copolymer used in this invention has an A block, which comprises a structural unit derived from a carboxyl-containing olefinic unsaturated monomer and functions as an adsorption site for colorants. Preferably, the block copolymer used in this invention further has a B block that functions as a solvent-affinity component.

[0536] Regarding the block copolymer used in the third invention, the A block containing structural units derived from carboxyl-containing olefinic unsaturated monomers may be the same as the A block in the block copolymer used in the second invention described above, which contains structural units derived from carboxyl-containing olefinic unsaturated monomers.

[0537] The B-block of the block copolymer used in the third invention, which functions as a solvent affinity component, may be the same as the B-block in the block copolymer used in the first invention.

[0538] In the block copolymer used in the third invention, the total content ratio of the structural units derived from carboxyl-containing olefinic unsaturated monomers can be the same as the total content ratio of the structural units represented by general formula (I) and general formula (II) in the block copolymer used in the first invention. Furthermore, in the block copolymer used in the third invention, the total content ratio of B blocks can be the same as the total content ratio of B blocks in the block copolymer used in the first invention.

[0539] Furthermore, the dispersants used in the third invention may be the same as those used in the first invention, except for at least one of the graft copolymers and block copolymers used in the third invention.

[0540] In the third photosensitive coloring resin composition of the present invention, the colorant, solvent, multifunctional monomer, photoinitiator, multifunctional thiol compound and other components may be the same as those in the first photosensitive coloring resin composition of the present invention.

[0541] <Preferred form of the photosensitive coloring resin composition of the third invention>

[0542] Regarding the photosensitive coloring resin composition of the third invention, it is preferable that the polyfunctional thiol compound is a polyfunctional thiol compound represented by the above general formula (A), which improves notch resistance and provides good storage stability.

[0543] In the third photosensitive coloring resin composition of the present invention, the content of the above-mentioned polyfunctional thiol compound relative to 100 parts by weight of the total solids content in the coloring resin composition is, for example, 0.001 parts by weight to 15.0 parts by weight. When it is 0.01 parts by weight to 15.0 parts by weight, it is easy to improve notch resistance and easy to suppress the generation of developing residue, and therefore preferred.

[0544] In the third photosensitive coloring resin composition of the present invention, the graft copolymer has a structural unit represented by the general formula (III), the polymer chain in the structural unit represented by the general formula (III) includes a structural unit represented by the 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 a B block including a structural unit represented by the general formula (IV), and the glass transition temperature of the B block is 85°C or less. The above situation is preferred because it improves the development time delay and improves the coating suitability.

[0545] In terms of dispersion stability and solvent resolubility, the photosensitive coloring resin composition of the third invention preferably has an acid value of 30 mg KOH / g to 180 mg KOH / g in the above-mentioned dispersant, at least one of the above-mentioned graft copolymer and block copolymer.

[0546] <Application>

[0547] Thirdly, the photosensitive coloring resin composition of the present invention is suitable for use in color filters because of its good notch resistance and good storage stability.

[0548] III-3. The third color filter of the present invention

[0549] The color filter of the third invention includes at least a substrate and a coloring layer disposed on the substrate, wherein at least one of the coloring layers is a cured product of the photosensitive coloring resin composition of the third invention described above.

[0550] The third color filter of the present invention can be made into a color filter with excellent defects by having at least one of the coloring layers being a cured product of the photosensitive coloring resin composition of the third invention described above.

[0551] The third color filter of the present invention, as long as it has the cured product of the photosensitive coloring resin composition of the third invention described above, i.e., the coloring layer, may have the same other components as those described in the color filter of the first invention.

[0552] III-4. The third display device of the present invention

[0553] The liquid crystal display device of the third invention is characterized in that it has the color filter described above.

[0554] In the third invention, by using the color filter of the third invention described above, a display device with excellent performance can be manufactured with defects suppressed.

[0555] The display device of the third invention, as long as it has the color filter of the third invention described above, can have the same other configurations as those described in the display device of the first invention, so the description is omitted here.

[0556] According to the third invention, a photosensitive coloring resin composition with good notch resistance and good storage stability, a color filter formed using the photosensitive coloring resin composition, and a display device can be provided.

[0557] Example

[0558] The present invention will now be specifically described with reference to embodiments. These descriptions are not intended to limit the scope of the invention.

[0559] The acid values ​​of the graft copolymers and block copolymers were determined according to the determination method described in the specification of the present invention.

[0560] The weight-average molecular weight (Mw) and Mw / Mn of the graft copolymer and block copolymer were determined according to the determination method described in the specification of the present invention above, using GPC (gel permeation chromatography) as a standard polystyrene conversion value.

[0561] 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 using the following formula.

[0562] 1 / Tg=Σ(Xi / Tgi)

[0563] Here, the block copolymer is defined as a copolymer of n monomer components 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. Σ is the sum of i = 1 to n. It should be noted that the glass transition temperature (Tgi) of the homopolymer of each monomer is taken from the Polymer Handbook (3rd Edition) (J. Brandrup, E. Himmergut, Wiley-Interscience, 1989). The specific glass transition temperature (Tgi) of the homopolymer of each monomer used in the examples and comparative examples is as follows.

[0564] Methacrylic acid (MAA): 185℃

[0565] Butyl methacrylate (BMA): 20℃

[0566] Benzyl methacrylate (BzMA): 54℃

[0567] Methyl methacrylate (MMA): 105℃

[0568] Methoxylated polyethylene glycol monomethacrylate (trade name: PME-200; manufactured by Nippon Oil Co., Ltd.; BLEMMER PME-200; ethoxide repeat number = 4): -59℃

[0569] Unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone (PCL-FM5) (trade name: PLACACCEL FM5; manufactured by Daicel Inc.; caprolactone chain repeat number = 5): -47℃

[0570] Example I series: First invention

[0571] (Synthesis Example 1: Manufacturing of macromonomer m1)

[0572] 30.0 parts by weight of propylene glycol methyl ether acetate (PGMEA) were added to a reactor equipped with a cooling tube, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was stirred under a nitrogen stream while being heated to 90°C. A mixed solution of 60.0 parts by weight of methyl methacrylate (MMA), 10.0 parts by weight of butyl methacrylate (BMA), 30.0 parts by weight of benzyl methacrylate (BzMA), 7.0 parts by weight of mercaptopropionic acid, and 1.0 part by weight of α,α'-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the reaction was further carried out for 3 hours. After cooling, the reaction solution was diluted with 200 parts by weight of tetrahydrofuran (THF) and redeprecipitated with 3000 parts by weight of hexane, thereby obtaining 106.0 parts by weight of a white powder. Subsequently, 50.0 parts by weight of PGMEA, 3.7 parts by weight of glycidyl methacrylate (GMA), 0.15 parts by weight of N,N-dimethyldodecylamine, and 0.1 parts by weight of p-methoxyphenol were added to 50.0 parts by weight of the white powder. The mixture was stirred at 110°C for 24 hours while air was introduced. After cooling, the reaction solution was reprecipitated with 3000 parts by weight of hexane to obtain 52.0 parts by weight of the macromonomer m1.

[0573] The obtained macromonomer m1 was confirmed by GPC (gel permeation chromatography) under conditions of N-methylpyrrolidone / polystyrene standard with 0.01 mol / L lithium bromide. The results showed a weight-average molecular weight (Mw) of 4800 and a molecular weight distribution (Mw / Mn) of 1.6. The calculated Tg value was 78℃.

[0574] (Synthesis Examples 2-4: Manufacturing of macromonomers m2-m4)

[0575] In the preparation of macromonomer m1 in Synthesis Example 1, as shown in Table 1, 70.0 parts by mass of MMA and 30.0 parts by mass of methoxy polyethylene glycol monomethacrylate (manufactured by Nippon Oil Co., Ltd.; trade name: BLEMMER PME-200; ethoxide repeat number = 4) 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. Otherwise, macromonomer m2 was prepared in the same manner as in Synthesis Example 1. The obtained macromonomer m2 had a weight-average molecular weight (Mw) of 6500 and a molecular weight distribution (Mw / Mn) of 1.7. The calculated Tg value was 34°C.

[0576] In the preparation of macromonomer m1 in Synthesis Example 1, as shown in Table 1, 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: PLACEL FM5; manufactured by Daicel Inc.; caprolactone chain repeat number = 5) (PCL-FM5) 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. Otherwise, macromonomer m3 was prepared in the same manner as in Synthesis Example 1. The obtained macromonomer m3 had a weight-average molecular weight (Mw) of 5200 and a molecular weight distribution (Mw / Mn) of 1.6. The calculated Tg value was 31°C.

[0577] In the preparation of macromonomer m1 in 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 B2MA. Otherwise, macromonomer m4 was prepared in the same manner as in Synthesis Example 1. The obtained macromonomer m2 had a weight-average molecular weight (Mw) of 4300 and a molecular weight distribution (Mw / Mn) of 1.6. The calculated Tg value was 105℃.

[0578] (Manufacturing Example 1: Manufacturing of Graft Copolymer A)

[0579] 100.0 parts by mass of PGMEA were added to a reactor equipped with a cooling pipe, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was stirred under a nitrogen flow while being heated to 85°C. Over 1.5 hours, 92.9 parts by mass of a mixed solution of macromonomer m1 from Synthesis Example 1, 4.2 parts by mass of methacrylic acid (MAA), 2.9 parts by mass of 2-methacryloyloxyethyl succinate (2-MOES), 1.3 parts by mass of n-dodecyl mercaptan, 50.0 parts by mass of PGMEA, and 1.0 part by mass of AIBN were added dropwise. After heating and stirring for 3 hours, a mixture of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes, and the mixture was then matured at the same temperature for 1 hour. After cooling, the reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 99.0 parts by mass of graft copolymer A. The obtained graft copolymer A has a weight-average molecular weight (Mw) of 12,500, an Mw / Mn ratio of 2.6, and an acid value of 35 mg KOH / g.

[0580] (Manufacturing Examples 2-11: Manufacturing of Graft Copolymers B-K)

[0581] In Manufacturing Example 1, as shown in Table 1, the types of macromonomers and the mass ratio of macromonomers, monomers of structural units represented by derivative formula (I), and monomers of structural units represented by derivative formula (II) were changed. Instead, 92.9 parts by mass of macromonomer m1, 4.2 parts by mass of MAA, and 2.9 parts by mass of 2-MOES were used. Otherwise, graft copolymers B to K were manufactured in the same manner as in Manufacturing Example 1. The weight-average molecular weight (Mw), Mw / Mn, and acid value of the obtained graft copolymers B to K are shown in Table 1.

[0582] Furthermore, 2-AOEHHP represents 2-acryloyloxyethyl hexahydrophthalic acid derived from the structural unit represented by the above general formula (II).

[0583] (Comparative Manufacturing Examples 1-2: Comparative Manufacturing of Graft Copolymers L-M)

[0584] In Manufacturing Example 1, as shown in Table 1, only one of the macromonomer and either MAA or 2-MOES was used, and the mass ratio was changed to replace 92.9 parts by mass of macromonomer m1, 4.2 parts by mass of MAA, and 2.9 parts by mass of 2-MOES. Otherwise, the comparative graft copolymers L to M were manufactured in the same manner as in Manufacturing Example 1. The weight-average molecular weight (Mw), Mw / Mn, and acid value of the obtained comparative graft copolymers L to M are shown in Table 1.

[0585] [Table 1]

[0586]

[0587] (Manufacturing Example 12: Manufacturing of Block Copolymer N)

[0588] A B-block copolymer was prepared by adding 150.0 parts by weight of PGMEA, 3.0 parts by weight of iodine, 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) (trade name: V-70; manufactured by Wako Pure Chemical Industries, Ltd.), 50.2 parts by weight of MMA, 8.4 parts by weight of BMA, 25.1 parts by weight of BzMA, and 0.04 parts by weight of succinimide to a reactor equipped with a cooling pipe, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was stirred under a nitrogen stream at 40°C for 5 hours. The calculated Tg of the obtained copolymer was 78°C.

[0589] Subsequently, 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 composition was determined and converted to non-volatile content, resulting in a polymerization conversion rate of 99%. The reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 99.0 parts by mass of AB block copolymer N. The block copolymer N obtained in this manner has a weight-average molecular weight (Mw) of 8300, an Mw / Mn ratio of 1.2, and an acid value of 80 mg KOH / g.

[0590] (Manufacturing Examples 13-15: Manufacturing of Block Copolymers O-Q)

[0591] In Manufacturing Example 12, as shown in Table 2, the type and mass ratio of the B-block monomers were changed, replacing 50.2 parts by mass of methyl methacrylate (MMA), 8.4 parts by mass of n-butyl methacrylate (BMA), and 25.1 parts by mass of benzyl methacrylate (BzMA) with those of the B-block monomers. Otherwise, the block copolymers O to Q were manufactured in the same manner as in Manufacturing Example 12. The weight-average molecular weight (Mw), Mw / Mn, and acid value of the obtained block copolymers O to Q are shown in Table 2.

[0592] (Comparative Manufacturing Examples 3-4: Manufacturing of Comparative Block Copolymers R-S)

[0593] In Manufacturing Example 12, as shown in Table 2, the mass ratio of the monomers for the B block was changed, and only one of MAA or 2-MOES was used as the monomer for the A block, with the mass ratio also changed. Otherwise, the comparative block copolymers R to S were manufactured in the same manner as in Manufacturing Example 12. The weight-average molecular weight (Mw), Mw / Mn, and acid value of the obtained comparative block copolymers R to S are shown in Table 2.

[0594] (Comparative Manufacturing Example 5: Comparative Manufacturing of Random Copolymer T)

[0595] Comparative random copolymer T was manufactured using monomers of the same type and mass ratio as those used in manufacturing example 12 for the B-block monomer and the A-block monomer.

[0596] Specifically, 300 parts by mass of PGMEA were added to a reactor equipped with a cooling pipe, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. After heating to 100°C under a nitrogen atmosphere, 50.2 parts by mass of MMA, 8.4 parts by mass of BMA, 25.1 parts by mass of BzMA, 9.9 parts by mass of MAA, 6.4 parts by mass of 2-MOES, 6 parts by mass of PERBUTYL O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were added dropwise over 1.5 hours. The reaction was then maintained at 100°C and continued. Two hours after the addition of the above main chain forming mixture, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor was added to stop the polymerization. The reaction solution was then reprecipitated with 3000 parts by mass of hexane, thereby producing a comparative random copolymer T. The weight-average molecular weight (Mw), Mw / Mn, and acid value of the obtained comparative random copolymer T are shown in Table 2.

[0597] [Table 2]

[0598]

[0599] (Preparation Example 1: Preparation of Alkali-Soluble Resin α)

[0600] 300 parts by mass of PGMEA were added to a reactor equipped with a cooling pipe, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. After heating to 100°C under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of PERBUTYL O (manufactured by Nippon Oil Co., Ltd.), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan) were added dropwise over 1.5 hours. The reaction was then maintained at 100°C and continued. Two hours after the addition of the above main chain forming mixture, 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization.

[0601] Subsequently, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA), an epoxy-containing compound, were added. After heating to 110°C, 0.8 parts by mass of triethylamine were added and an addition reaction was carried out at 110°C for 15 hours to obtain an alkali-soluble resin α solution (weight average molecular weight (Mw) 8500, acid value 75 mg KOH / g, solid content 40% by mass).

[0602] (Example 1)

[0603] (1) Manufacturing of colorant dispersion R-1

[0604] 6.5 parts by weight of graft copolymer A (used as dispersant A in Manufacturing Example 1), 6.5 parts by weight of CI Pigment Red 177 (PR177) and CI Pigment Red 291 (PR291) (used as colorants), 80.5 parts by weight of PGMEA, and 100 parts by weight of 2.0 mm zirconia beads were placed into a mayonnaise bottle and shaken for 1 hour using a paint shaker (manufactured by Asada Tetsuko Co., Ltd.) as pre-crushing. Then, 200 parts by weight of 0.1 mm zirconia beads were added and dispersed for 4 hours using the paint shaker as formal crushing to obtain colorant dispersion R-1.

[0605] (2) Manufacturing of photosensitive coloring resin composition R-1

[0606] Add 8.71 parts by weight of the color material dispersion R-1 obtained in (1) above, 0.33 parts by weight of the alkali-soluble resin α solution obtained in Preparation Example 1, 1.19 parts by weight of the multifunctional monomer (trade name ARONIX M-403; manufactured by Toa Synthetic Co., Ltd.), 0.06 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (photoinitiator: trade name IRGACURE907; manufactured by BASF Corporation, Japan), 0.06 parts by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE 369; manufactured by BASF Corporation, Japan), 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (photoinitiator: trade name IRGACURE) 0.03 parts by weight of OXE01 (manufactured by BASF Corporation, Japan), 0.07 parts by weight of fluorinated surfactant (trade name MEGAFAC R-08MH; manufactured by DIC Corporation), and 9.95 parts by weight of PGMEA were used to obtain a photosensitive coloring resin composition R-1.

[0607] (Examples 2-15)

[0608] (1) Manufacturing of color material dispersions R-2 to R-15

[0609] In Example 1(1), as shown in Tables 3 and 4, dispersants B, C, D, E, F, G, H, I, J, K, N, O, P and Q were used instead of dispersant A. Otherwise, color material dispersions R-2 to R-15 were prepared in the same manner as in Example 1.

[0610] (2) Manufacturing of photosensitive coloring resin compositions R-2 to R-15

[0611] In Example 1 (2), the above-mentioned color material dispersions R-2 to R-15 were used instead of color material dispersion R-1, otherwise, the photosensitive coloring resin compositions R-2 to R-15 were obtained in the same manner as in Example 1 (2).

[0612] (Comparative Examples 1-5)

[0613] (1) Comparison of the manufacturing of colorant dispersions CR-1 to CR-5

[0614] In Example 1(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. Otherwise, comparative colorant dispersions CR-1 to CR-5 were obtained in the same manner as in Example 1.

[0615] (2) Comparison of the manufacturing processes of photosensitive coloring resin compositions CR-1 to CR-5

[0616] In Example 1 (2), the comparative colorant dispersions CR-1 to CR-5 were used instead of the colorant dispersion R-1, and otherwise, the comparative photosensitive colorant resin compositions CR-1 to CR-5 were obtained in the same manner as in Example 1 (2).

[0617] (Example 16)

[0618] (1) Manufacturing of colorant dispersion G-1

[0619] 6.5 parts by mass of the graft copolymer C (used as dispersant C in Manufacturing Example 3), 3.9 parts by mass of CI pigment green 59 (PG59) and CI pigment yellow 150 (PY150) (used as colorants), 80.5 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm zirconia beads were placed into a mayonnaise bottle and shaken for 1 hour using a paint shaker (manufactured by Asada Tetsuko Co., Ltd.) as pre-crushing. Then, 200 parts by mass of 0.1 mm zirconia beads were added and dispersed for 4 hours using the paint shaker as formal crushing to obtain colorant dispersion G-1.

[0620] (2) Manufacturing of photosensitive coloring resin composition G-1

[0621] Add 8.71 parts by weight of the color material dispersion G-1 obtained in (1) above, 0.33 parts by weight of the alkali-soluble resin α solution obtained in Preparation Example 1, 1.19 parts by weight of the multifunctional monomer (trade name ARONIX M-403; manufactured by Toa Synthetic Co., Ltd.), 0.06 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (photoinitiator: trade name IRGACURE907; manufactured by BASF Corporation, Japan), 0.06 parts by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE 369; manufactured by BASF Corporation, Japan), 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (photoinitiator: trade name IRGACURE) 0.03 parts by weight of OXE01 (manufactured by BASF Corporation, Japan), 0.07 parts by weight of fluorinated surfactant (trade name MEGAFAC R-08MH; manufactured by DIC Corporation), and 9.95 parts by weight of PGMEA were used to obtain a photosensitive coloring resin composition G-1.

[0622] (Examples 17-22)

[0623] (1) Manufacturing of colorant dispersions G-2 to G-7

[0624] In Example 16(1), as shown in Tables 5 and 6, dispersants D, E, N, O, P and Q were used instead of dispersant C, and the color material dispersions G-2 to G-7 were prepared in the same manner as in Example 16.

[0625] (2) Manufacturing of photosensitive coloring resin compositions G-2 to G-7

[0626] In Example (2), the above-mentioned color material dispersions G-2 to G-7 were used instead of color material dispersion G-1. Otherwise, the photosensitive coloring resin compositions G-2 to G-7 were obtained in the same manner as in Example 16 (2).

[0627] (Comparative Examples 6-10)

[0628] (1) Comparison of the manufacturing of colorant dispersions CG-1 to CG-5

[0629] In Example 16(1), as shown in Tables 5 and 6, comparative graft copolymers L and M, comparative block copolymers R and S, and comparative random copolymer T were used instead of dispersant C. Otherwise, comparative colorant dispersions CG-1 to CG-5 were obtained in the same manner as in the Example.

[0630] (2) Comparison of the manufacturing processes of photosensitive coloring resin compositions CG-1 to CG-5

[0631] In Example 16(2), the comparative color material dispersions CG-1 to CG-5 were used instead of color material dispersion G-1, and the comparative photosensitive coloring resin compositions CG-1 to CG-5 were obtained in the same manner as in Example 16(2).

[0632] (Example 23)

[0633] (1) Manufacturing of colorant dispersion B-1

[0634] 6.5 parts by mass of the graft copolymer C (used as dispersant C in Manufacturing Example 3), 10.4 parts by mass of CI pigment blue (PB15:6) and 2.6 parts by mass of CI pigment violet 23 (PV23) (used as colorant), 80.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were placed into a mayonnaise bottle and shaken for 1 hour using a paint shaker (manufactured by Asada Tetsuko Co., Ltd.) as pre-crushing. Then, the zirconia beads with a particle size of 2.0 mm were removed, and 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added. Similarly, the mixture was dispersed for 4 hours using a paint shaker as formal crushing to obtain colorant dispersion B-1.

[0635] (2) Preparation of photosensitive coloring resin composition B-1

[0636] Add 6.03 parts by weight of the color material dispersion B-1 obtained in (1) above, 1.39 parts by weight of the alkali-soluble resin α solution obtained in Preparation Example 1, 1.30 parts by weight of the multifunctional monomer (trade name ARONIX M-403; manufactured by Toa Synthetic Co., Ltd.), 0.08 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one (photoinitiator: trade name IRGACURE907; manufactured by BASF Corporation, Japan), 0.08 parts by weight of 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE 369; manufactured by BASF Corporation, Japan), 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (photoinitiator: trade name IRGACURE) 0.04 parts by weight of OXE01 (manufactured by BASF Corporation, Japan), 0.07 parts by weight of fluorinated surfactant (trade name MEGAFAC R-08MH; manufactured by DIC Corporation), and 11.00 parts by weight of PGMEA were used to obtain photosensitive coloring resin composition B-1.

[0637] (Examples 24-29)

[0638] (1) Manufacturing of color material dispersions B-2 to B-7

[0639] In Example 23(1), as shown in Tables 7 and 8, dispersants D, E, N, O, P and Q were used instead of dispersant C, and the color material dispersions B-2 to B-7 were prepared in the same manner as in Example 23.

[0640] (2) Manufacturing of photosensitive coloring resin compositions B-2 to B-7

[0641] In Example 23 (2), the above-mentioned color material dispersions B-2 to B-7 were used instead of color material dispersion B-1. Otherwise, the photosensitive coloring resin compositions B-2 to B-7 were obtained in the same manner as in Example 23 (2).

[0642] (Comparative Examples 11-15)

[0643] (1) Comparison of the manufacturing of colorant dispersions CB-1 to CB-5

[0644] In Example 23(1), as shown in Tables 7 and 8, comparative graft copolymers L and M, comparative block copolymers R and S, and comparative random copolymer T were used instead of dispersant C. Otherwise, comparative colorant dispersions CB-1 to CB-5 were obtained in the same manner as in the Example.

[0645] (2) Comparison of the manufacture of photosensitive coloring resin compositions CB-1 to CB-5

[0646] In Example 23(2), the comparative colorant dispersions CB-1 to CB-5 were used instead of colorant dispersion B-1, and otherwise, the comparative photosensitive colorant resin compositions CB-1 to CB-5 were obtained in the same manner as in Example 23(2).

[0647] [Evaluation Method]

[0648] <Evaluation of the dispersibility and stability of pigment dispersions>

[0649] For the colorant dispersions obtained in the examples and comparative examples, the viscosity was measured immediately after preparation and after storage at 25°C for 30 days. The viscosity change rate was calculated based on the viscosity before and after storage, and the viscosity stability was evaluated. Viscosity was measured using a vibratory viscometer at 25.0 ± 0.5°C.

[0650] (Dispersion stability evaluation benchmark)

[0651] A: The viscosity change rate before and after storage is less than 10%.

[0652] B: The viscosity change rate before and after storage is greater than 10% but less than 20%.

[0653] C: The change in viscosity before and after storage is greater than 20% but less than 40%.

[0654] D: The viscosity change rate before and after storage is over 40%.

[0655] E: Gelation during dispersion or storage

[0656] This value is set when the total mass of the colorant relative to the solvent containing the colorant dispersion is 13% by mass.

[0657] 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 colorant dispersion is excellent.

[0658] Solvent Resolvability

[0659] 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 coloring resin composition for color filters obtained in the examples and comparative examples, coating a 1 cm length portion of the glass substrate. The pulled-out glass substrate was placed horizontally into a constant temperature and humidity chamber and dried at 23°C and 80% RH for 30 minutes. Subsequently, the glass substrate with the dried coating was immersed in PGMEA for 15 seconds. At this time, the redissolution state of the dried coating was visually assessed and evaluated.

[0660] (Solvent redissolvability evaluation criteria)

[0661] A: The dried coating has completely dissolved.

[0662] B: A thin film of dried coating is formed in a solvent, which dissolves shortly thereafter.

[0663] C: A thin film of dried coating is produced in a solvent; solution coloring.

[0664] D: A thin film of dried coating is formed in the solvent, and the solution is not colored.

[0665] E: Thin films that do not form a dried coating in the solvent, and the solution is not colored.

[0666] 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.

[0667] <Substrate Adhesion>

[0668] Using a spin coater, the photosensitive coloring resin compositions obtained in the examples and comparative examples were coated onto glass substrates (NH TECHNO GLASS Co., Ltd., "NA35") to form a coloring layer with a thickness of 2.0 μm after post-baking. The substrates were then dried at 80°C for 3 minutes using a hot plate, thereby forming a coloring layer on the glass substrates. The coloring layer was then irradiated with an ultra-high pressure mercury lamp at 60 mJ / cm². 2 Ultraviolet rays.

[0669] Subsequently, the colored substrate was baked in a clean oven at 230°C for 30 minutes to produce the colored substrate. Following the same method as JIS K5400, 100 slits were made on the obtained colored substrate, and celluloid tape was applied and then immediately peeled off. The changes in the 100 slits before and after the experiment using celluloid tape were observed using an optical microscope.

[0670] (Substrate Adhesion Evaluation Criteria)

[0671] A: After the test, it was confirmed that 100 pieces were found, and the condition of the incision site did not change before and after the test.

[0672] B: After the test, it was confirmed that 100 pieces were found, and the width of the cut changed significantly before and after the test.

[0673] C: Confirmed after testing to be more than 70 pieces but less than 100 pieces.

[0674] D: Confirmed after testing to be between 30 and 70 pieces.

[0675] E: Confirmed after testing to be less than 30 pieces. Or, the entire coloring layer has peeled off.

[0676] 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.

[0677] <Development Time Evaluation>

[0678] Using a spin coater, the photosensitive coloring resin compositions obtained in the examples and comparative examples were coated onto glass substrates (NH TECHNO GLASS Co., Ltd., "NA35") to form a coloring layer with a thickness of 2.0 μm after post-baking. The substrates were then dried at 80°C for 3 minutes using a hot plate, thereby forming a coloring layer on the glass substrates. The coloring layer was irradiated with 60 mJ / cm² using an ultra-high pressure mercury lamp and a dielectric photomask. 2The ultraviolet light was then used. Subsequently, a 0.05% by mass potassium hydroxide aqueous solution was used as an alkaline developer to spray and develop the glass substrate on which the above-mentioned colored layer was formed for 60 seconds. The development time was measured until the above-mentioned colored layer was completely dissolved and the glass surface of the area where the above-mentioned colored layer was formed was exposed.

[0679] (Evaluation Criteria)

[0680] A: The time until the glass surface is exposed is less than 15 seconds.

[0681] B: The time until the glass surface is exposed is more than 15 seconds but less than 30 seconds.

[0682] C: The time until the glass surface is exposed is more than 30 seconds but less than 45 seconds.

[0683] D: The time until the glass surface is exposed is more than 45 seconds but less than 60 seconds.

[0684] E: Glass surface not exposed

[0685] The colorant dispersions and photosensitive coloring resin compositions obtained in the above-described examples and comparative examples were evaluated as described above. The evaluation results are shown in Tables 3 to 8.

[0686] [Table 3]

[0687]

[0688] [Table 4]

[0689]

[0690] [Table 5]

[0691] Table 5

[0692]

[0693] [Table 6]

[0694]

[0695] [Table 7]

[0696] Table 7

[0697]

[0698] [Table 8]

[0699]

[0700] (Example 30)

[0701] Add 0.07 parts by weight of a polyfunctional thiol compound (trade name: KARENZ MTPE1; pentaerythritol tetra(3-mercaptobutyrate); manufactured by Showa Denko Co., Ltd.; effective solids content 40%) to the photosensitive coloring resin composition R-3 obtained in Example 3 to obtain photosensitive coloring resin composition R-3a.

[0702] (Comparative Example 16)

[0703] (1) Comparison of the manufacturing of dispersant U (amine graft copolymer)

[0704] A B-block copolymer was prepared by adding 150.0 parts by weight of PGMEA, 3.0 parts by weight of iodine, 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile) (trade name: V-70; manufactured by Wako Pure Chemical Industries, Ltd.), 46.6 parts by weight of MMA, 7.8 parts by weight of BMA, 23.3 parts by weight of BzMA, and 0.04 parts by weight of succinimide to a reactor equipped with a cooling pipe, a funnel for adding, a nitrogen inlet, a mechanical stirrer, and a digital thermometer. The mixture was stirred under a nitrogen stream at 40°C for 5 hours. The calculated Tg of the obtained copolymer was 78°C.

[0705] Subsequently, 22.4 parts by mass of dimethylaminoethyl methacrylate (DMMA) were added, and the mixture was stirred at 40°C for 5 hours. The solid composition was determined and converted to non-volatile content, resulting in a polymerization conversion rate of 99%. The reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 99.0 parts by mass of AB block comparative copolymer U. The comparative copolymer U obtained in this manner has a weight-average molecular weight (Mw) of 9600, an Mw / Mn ratio of 1.2, and an amine value of 80 mg KOH / g.

[0706] (2) Comparison of the manufacturing of colorant dispersion CR-6

[0707] In Example 1(1), comparative dispersant U was used instead of dispersant A, otherwise, the comparative colorant dispersion CR-6 was obtained in the same manner as in Example 1.

[0708] (3) Comparison of the manufacturing of photosensitive coloring resin composition CR-6

[0709] In Example 30, the comparative colorant dispersion CR-6 was used instead of the colorant dispersion R-3. Otherwise, the comparative photosensitive colorant resin composition CR-6 with added polyfunctional thiol compounds was obtained in the same manner as in Example 30.

[0710] [Evaluation Method]

[0711] Notch resistance of photosensitive coloring resin compositions

[0712] The photosensitive coloring resin compositions obtained in Examples 3, 30, and Comparative Example 16 were stored at room temperature for 3 days. Then, using a spin coater, a coloring layer with a thickness of 2.0 μm was coated onto a glass substrate (NH TECHNO GLASS Co., Ltd., "NA35"), which would form a coloring layer after post-baking. The substrate was then dried at 60°C for 3 minutes using a hot plate to form the coloring layer. The coloring layer was then irradiated with 30 mJ / cm² using an ultra-high pressure mercury lamp through a photomask having a mask opening width of 80 μm and a mask blocking width of 160 μm. 2 Ultraviolet light was used. A 0.05% (w / w) potassium hydroxide aqueous solution was used as an alkaline developer to spray-develop the glass plate with the above-mentioned colored layer for 100 seconds. The developed substrate was observed using an optical microscope at 10x magnification, and the number of notches at the edges of the colored layer within a 50mm × 50mm area was measured. Furthermore, in the desired 80μm wide linear colored pattern, areas with a cutout of 5μm or more were considered as edge notches.

[0713] (Notch resistance evaluation criteria)

[0714] A: No gap

[0715] B: Less than 20

[0716] C: 20 or more but less than 50

[0717] D: More than 50

[0718] If the notch resistance evaluation criteria are A, B, or C, it can be used in practice; if the evaluation result is B, or even A, the effect is even better.

[0719] <Storage stability of photosensitive coloring resin compositions>

[0720] For the photosensitive coloring resin compositions obtained in Examples 3, 30, and Comparative Example 16, the viscosity was measured immediately after preparation and after storage at 40°C for 30 days. The viscosity change rate was calculated based on the viscosity before and after storage, and the viscosity stability was evaluated. Viscosity was measured using a vibratory viscometer at 25.0 ± 0.5°C.

[0721] (Dispersion stability evaluation benchmark)

[0722] A: The viscosity change rate before and after storage is less than 10%.

[0723] B: The viscosity change rate before and after storage is greater than 10% but less than 20%.

[0724] C: The change in viscosity before and after storage is greater than 20% but less than 40%.

[0725] D: The viscosity change rate before and after storage is over 40%.

[0726] 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 is excellent.

[0727] The evaluation results are shown in Table 9.

[0728] [Table 9]

[0729] Table 9

[0730] Example 3 Example 30 Comparative Example 16 Photosensitive coloring resin composition R-3 R-3a CR-6 dispersant C C U Multifunctional thiols - ○ ○ Notch resistance C A B Preservation stability A A D

[0731] [Summary of Results of the First Invention]

[0732] According to the comparison of the embodiments and comparative examples of the first invention, in Examples 1 to 29 of the first invention using the graft copolymer or block copolymer specified in the invention, a photosensitive coloring resin composition that simultaneously satisfies excellent dispersion stability, solvent resolubility and substrate adhesion can be obtained.

[0733] In contrast, in Comparative Examples 1-4, 6-9, 11-14, which use dispersants that are graft copolymers or block copolymers containing only structural units represented by general formula (I) and general formula (II), the solvent resolubility deteriorates. In Comparative Examples 2, 4, 7, 9, 12, 14, which contain only structural units represented by general formula (II), the dispersion stability and substrate adhesion deteriorate further.

[0734] In Comparative Examples 5, 10, and 15, which used random copolymers with the same monomer ratio as block copolymer N in Example 12 as dispersants, gelation occurred during the dispersion process when preparing the color material dispersion, making it impossible to recover the color material dispersion and thus impossible to evaluate it as a photosensitive coloring resin composition.

[0735] As also clearly stated in the embodiments, if a dispersant containing the structural unit represented by the above general formula (IV) and having a glass transition temperature of 85°C or less is used in the polymer chain, or if a dispersant containing the B block of the structural unit represented by the above general formula (IV) and having a glass transition temperature of 85°C or less is used, then the development time can be shortened.

[0736] Furthermore, it is also clear in the embodiments that if a dispersant containing at least one structural unit selected from the structural units represented by the above general formula (V) and the structural units represented by the above general formula (V′) is used in the polymer chain or B block, the substrate adhesion is improved, and the development time can be shortened.

[0737] Furthermore, as shown in Table 9, it is also evident in the examples that if a dispersant having a structural unit containing an acidic group and a polyfunctional thiol compound are used in combination in the photosensitive coloring resin composition, the notch resistance is improved, and the storage stability of the photosensitive coloring resin composition becomes good.

[0738] Example II Series: Second Invention

[0739] (Manufacturing Examples II-1 to II-3: Manufacturing of Graft Copolymers II-A to II-C)

[0740] The macromonomers m2 and m3 were prepared in the same manner as in Synthesis Examples 2 and 3 of Example I series.

[0741] In Manufacturing Example 1 of the Example I series, as shown in Table 10, the type of macromonomer and the mass ratio of macromonomer to carboxyl-containing olefinic unsaturated monomer were changed, replacing 92.9 parts by mass of macromonomer m1, 4.2 parts by mass of MAA, and 2.9 parts by mass of 2-MOES. Otherwise, the graft copolymers II-A to II-C were manufactured in the same manner as in Manufacturing Example 1 of the Example I series. The weight-average molecular weight (Mw), Mw / Mn, and acid value of the obtained graft copolymers II-A to II-C are shown in Table 10.

[0742] (Examples II-1 to II-3)

[0743] (1) Manufacturing of color material dispersions II-R-1 to II-R-3

[0744] In Example 1 of the Example I series (1), as shown in Table 10, graft copolymers II-A to II-C, which are used as dispersants, were used instead of dispersant A. Otherwise, color material dispersions II-R-1 to II-R-3 were prepared in the same manner as in Example 1 of the Example I series.

[0745] (2) Manufacturing of photosensitive coloring resin compositions II-R-1 to II-R-3

[0746] In Example 1 (2) of the Example I series, the above-mentioned color material dispersions II-R-1 to II-R-3 were used instead of color material dispersion R-1. Otherwise, the photosensitive coloring resin compositions II-R-1 to II-R-3 were obtained in the same manner as in Example 1 (2) of the Example I series.

[0747] The evaluation was conducted in the same manner as the evaluation of substrate adhesion and development time in the series of Examples I. The results are presented together with those of Comparative Examples 6 and 7 of the series of Examples I.

[0748] [Table 10]

[0749] Table 10

[0750]

[0751] [Summary of Results of the Second Invention]

[0752] As can be clearly seen from the comparison of Examples II-1 to II-3 and the comparative examples, in Examples II-1 to II-3 using the graft copolymers or block copolymers specified in the second invention, a photosensitive coloring resin composition that simultaneously satisfies excellent substrate adhesion and developability (shortened development time) can be obtained.

[0753] In Examples 3, 5, 13, 14, 16, 18, 20, 21, 23, 25, 27 and 28 of the series of Examples I of the Second Invention, the effects of excellent substrate adhesion and shortened development time are also clearly demonstrated.

[0754] Example III Series: The Third Invention

[0755] (Examples III-1 to III-2)

[0756] (1) Manufacturing of colorant dispersions III-R-1 to III-R-2

[0757] Graft copolymers L and M were prepared in the same manner as those in comparative manufacturing examples 1-2 of the Example I series.

[0758] In Example 1 of the Example I series (1), as shown in Table 11, graft copolymers L and M, which are used as dispersants, were used instead of dispersant A. Otherwise, the color material dispersions III-R-1 to III-R-2 were prepared in the same manner as in Example 1 of the Example I series.

[0759] (2) Manufacturing of photosensitive coloring resin compositions III-R-1 to III-R-2

[0760] In Example 30 of the Example I series, the above-mentioned color material dispersions III-R-1 to III-R-2 were used instead of color material dispersion R-3. Otherwise, the photosensitive coloring resin compositions III-R-1 to III-R-2 with added polyfunctional thiol compounds were obtained in the same manner as in Example 30 of the Example I series.

[0761] The evaluation was conducted in the same manner as the nick resistance and storage stability evaluations of the Example I series. The results are presented together with those of Comparative Example 16 of the Example I series.

[0762] [Table 11]

[0763] Table 11

[0764] Example III-1 Example III-2 Comparative Example 16 Photosensitive coloring resin composition III-R-1 III-R-2 CR-6 dispersant L M ∪ Multifunctional thiols ○ ○ ○ Notch resistance A A B Preservation stability A A D

[0765] [Summary of Results of the Third Invention]

[0766] A comparison of Examples III-1 to III-2 and the comparative examples clearly shows that in Examples III-1 to III-2, which combine a dispersant having an acidic structural unit as specified in the third invention with a polyfunctional thiol compound, notch resistance is improved, and the storage stability of the photosensitive coloring resin composition becomes good. In Example 30, which corresponds to the Example I series of the third invention, excellent notch resistance and storage stability are also clearly demonstrated.

[0767] Explanation of reference numerals in the attached figures

[0768] 1: Substrate

[0769] 2: Shading part

[0770] 3: Coloring layer

[0771] 10: Color Filter

[0772] 20: Opposing substrate

[0773] 30: Liquid crystal layer

[0774] 40: Liquid crystal display device

[0775] 50: Organic protective layer

[0776] 60: Inorganic oxide film

[0777] 71: Transparent Anode

[0778] 72: Hole Injection Layer

[0779] 73: Hole transport layer

[0780] 74: Emissive Layer

[0781] 75: Electron Injection Layer

[0782] 76: Cathode

[0783] 80: Organic light-emitting body

[0784] 100: Organic light-emitting display device

Claims

1. A color material dispersion liquid containing a color material, a dispersant, and a solvent, the dispersant contains at least one of a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and a block copolymer having an A block containing a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), the solvent contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, In general formula (I), R 1 represents a hydrogen atom or a methyl group, In General Formula (II), R 1' represents a hydrogen atom or a methyl group, R 2 represents an aliphatic hydrocarbon group optionally containing an oxygen atom, R 3 represents an aliphatic hydrocarbon group.

2. The color material dispersion liquid according to claim 1, wherein in the dispersant, the graft copolymer has a structural unit represented by the following general formula (III), a polymer chain in the structural unit represented by the general formula (III) contains a structural unit represented by the following general formula (IV), and a glass transition temperature of the polymer chain in the structural unit represented by the general formula (III) is 85°C or lower, the block copolymer has a B block containing a structural unit represented by the following general formula (IV), and a glass transition temperature of the B block is 85°C or lower, In 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 General Formula (IV), R 11 is a hydrogen atom or a methyl group, A 2 is a divalent linking group, R 4 is a hydrocarbon group optionally having a substituent and optionally containing a hetero atom.

3. The color material dispersion liquid according to claim 1 or 2, wherein, in the dispersant, an acid value of at least one of the graft copolymer and the block copolymer is 30 mgKOH / g to 180 mgKOH / g.

4. The color material dispersion liquid according to claim 1 or 2, wherein, in the dispersant, the graft copolymer has a structural unit represented by the following general formula (III), a polymer chain in the structural unit represented by the general formula (III) 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'), the block copolymer has a B block containing 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'), In 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 General Formula (V), R 11' is a hydrogen atom or a methyl group, A 2' is a divalent linking group, R 5 is an ethylene group or a propylene group, R 6 is a hydrogen atom or a hydrocarbon group, and m represents a number of 2 or more and 80 or less. In 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 having 1 to 10 carbons, R 8 is an alkylene group having 3 to 7 carbons, R 9 is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less.

5. A dispersant which is at least one of a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and a block copolymer having an A block containing a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), In general formula (I), R 1 represents a hydrogen atom or a methyl group, In General Formula (II), R 1' represents a hydrogen atom or a methyl group, R 2 represents an aliphatic hydrocarbon group optionally containing an oxygen atom, R 3 represents an aliphatic hydrocarbon group.

6. The dispersant of claim 5 wherein, the graft copolymer has a structural unit represented by the following general formula (III), a polymer chain in the structural unit represented by the general formula (III) contains a structural unit represented by the following general formula (IV), and a glass transition temperature of the polymer chain in the structural unit represented by the general formula (III) is 85°C or lower, the block copolymer has a B block containing a structural unit represented by the following general formula (IV), and a glass transition temperature of the B block is 85°C or lower, In general formula (III), R 1'' represents a hydrogen atom or a methyl group, A 1 represents a direct bond or a divalent linking group, Polymer represents a polymer chain, In General Formula (IV), R 11 is a hydrogen atom or a methyl group, A 2 is a divalent linking group, R 4 is a hydrocarbon group which optionally has a substituent and optionally contains a hetero atom.

7. The dispersant according to claim 5 or 6, having an acid value of 30 mgKOH / g to 180 mgKOH / g.

8. The dispersant of claim 5 or 6 wherein, The graft copolymer has a structural unit represented by the following general formula (III), a polymer chain of which contains at least one structural unit selected from a structural unit represented by the following general formula (V) and a structural unit represented by the following general formula (V'), and the block copolymer has a B block containing at least one structural unit selected from a structural unit represented by the following general formula (V) and a structural unit represented by the following general formula (V'), In general formula (III), R 1'' represents a hydrogen atom or a methyl group, A 1 represents a direct bond or a divalent linking group, Polymer represents a polymer chain, In General Formula (V), R 11' is a hydrogen atom or a methyl group, A 2' is a divalent linking group, R 5 is an ethylene group or a propylene group, R 6 is a hydrogen atom or a hydrocarbon group, and m represents a number of 2 or more and 80 or less. In 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 having a carbon number of 1 to 10, R 8 is an alkylene group having a carbon number of 3 to 7, R 9 is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less.

9. A photosensitive colored resin composition comprising a color material, the dispersant according to any one of claims 5 to 8, a polyfunctional monomer, a photoinitiator, and a solvent.

10. The photosensitive colored resin composition according to claim 9, further comprising a polyfunctional mercaptan compound.

11. The photosensitive colored resin composition according to claim 10, wherein The polyfunctional mercaptan compound is a polyfunctional mercaptan compound represented by the following general formula (A), In General Formula (A), R a represents a hydrogen atom or an alkyl group having 1 to 6 carbons, R b represents an alkylene group having 1 to 6 carbons, Q represents a residue of a polyol having a hydroxyl group number of 2 to 6, and s is an integer of 2 to 6.

12. A cured product which is a cured product of the photosensitive colored resin composition according to any one of claims 9 to 11.

13. A color filter having at least a substrate and a colored layer provided on the substrate, at least one of the colored layers being a cured product of the photosensitive colored resin composition according to claim 12.

14. A display device having the color filter according to claim 13.

Images