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

Abstract

The present application provides a photosensitive colored resin composition containing a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the dispersant contains a (meth)acrylate copolymer dispersant, and the photoinitiator contains a compound represented by general formula (A). Each symbol in general formula (A) is as described in the specification.

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive colored resin composition, a cured product, a color filter, and a display device. BACKGROUND

[0002] In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has been increasing. The popularity of mobile displays (mobile phones, smartphones, tablet PCs (personal computers)) is also increasing, and the market for liquid crystal displays is expanding. Organic light emitting display devices such as organic EL (Electroluminescence) displays, which have high visibility due to self-emission, are also attracting attention as next-generation image display devices.

[0003] These liquid crystal display devices, organic light emitting display devices use a color filter. For example, regarding the formation of a color image of a liquid crystal display device, light passing through the color filter is directly colored to the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. As a light source at this time, in addition to the conventional cold cathode tube, an organic light emitting element that emits white light, an inorganic light emitting element that emits white light are sometimes used. In an organic light emitting display device, a color filter is used for color adjustment and the like.

[0004] Here, the color filter generally has a substrate, a colored layer formed on the substrate and including a colored pattern of red, green, and blue three primary colors, and a light-shielding portion formed on the substrate in a manner of dividing each colored pattern.

[0005] As a method of forming the colored layer in the color filter, for example, a color material dispersion liquid in which a color material is dispersed by a dispersant or the like is added with a binder resin, a photopolymerizable compound, and a photoinitiator, the formed colored resin composition is coated on a glass substrate and dried, then exposed using a photomask, developed to form a colored pattern, and heated to fix the pattern, thereby forming the colored layer. These procedures are repeated for each color to form the color filter.

[0006] In recent years, in the case where the demand for high brightness of the color filter and the like is increasing, the concentration of the color material in the colored layer of the color filter is higher than in the past, and thus the components required for photopolymerization are relatively less, and patterning is difficult to perform. Furthermore, in order to improve the productivity of the color filter, it is required to reduce the cumulative exposure amount required for patterning, and how to ensure the curability required for patterning becomes a big problem.

[0007] In order to ensure the curability required for patterning of the colored layer, in a color filter colored resin composition, a photoinitiator having a relatively small molecular weight such as Irgacure 907 is used as a high-sensitivity photoinitiator, but sublimates to cause contamination of photomasks, heating ovens, and the like.

[0008] Therefore, in Patent Literature 1, as a high-sensitivity photopolymerization initiator which is excellent in stability, has low sublimation, and activates with high efficiency by absorbing near-ultraviolet light such as 365 nm, a specific oxime ester compound is disclosed.

[0009] In addition, as a high-sensitivity photoinitiator, for example, in Patent Literature 2, as a photoinitiator which is high in reactivity, easy to synthesize, and easy to handle, a specific o-acyl oxime compound is disclosed.

[0010] Further, in Patent Literature 3, as a high-sensitivity photoinitiator, a specific oxime ester compound is disclosed.

[0011] Prior Art Documents

[0012] Patent Literature

[0013] Patent Literature 1: International Publication No. 2015 / 152153

[0014] Patent Literature 2: Japanese Patent Application Laid-Open (JP-A) No. 2000-80068

[0015] Patent Literature 3: Japanese Patent Application Laid-Open (JP-A) No. 2006-516246 SUMMARY

[0016] PROBLEMS TO BE SOLVED BY THE INVENTION

[0017] Conventionally, a color filter is formed on a glass substrate, but in recent years, it is required to directly form a color filter on a device substrate.

[0018] A device such as an organic light-emitting device has low heat resistance, and therefore heating treatment in the manufacturing process of a color filter directly formed on a device substrate is preferably performed at 90°C or lower. In a conventional color filter manufacturing process, heating treatment at around 230°C is performed on a glass substrate to cure a colored layer, and in contrast to this, in heating treatment at 90°C or lower, it is difficult to cure the colored layer by heat. Therefore, in order to impart the colored layer with solvent resistance required in a subsequent process, it is necessary to sufficiently cure the colored layer by exposure. In order to promote the curing of the colored layer by exposure, it is considered to use a high-sensitivity initiator. However, a high-sensitivity initiator has a tendency that the line width deviation also becomes large, and in the case of producing a fine line pattern, there is a problem that it becomes larger than the assumed pattern size. Furthermore, even if the colored layer contains a high-sensitivity initiator, it is not necessarily possible to obtain the required solvent resistance by curing by exposure and heating treatment at 90°C or lower.

[0019] The present application has been achieved in view of the above-described circumstances, and aims to provide a photosensitive colored resin composition capable of forming a colored layer which is excellent in line width deviation and solvent resistance under low-temperature heating treatment. In addition, the present application aims to provide a color filter and a display device formed using the photosensitive colored resin composition.

[0020] Means for solving the problem

[0021] The photosensitive colored resin composition of the present application contains a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and

[0022] The above-described dispersant contains a (meth)acrylate copolymer-based dispersant,

[0023] The above-described photoinitiator contains a compound represented by the following general formula (A).

[0024] [Chemical Formula 1]

[0025]

[0026] (In the formula, R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 , or CN,

[0027] R 11 , R 12 , and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0028] R 11 , R 12 , and R 13 represented by the above-described groups are optionally further substituted with R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , NR 22 COR21 OCOR 21 COOR 21 SCOR 21 OCSR 21 COSR 21 CSOR 21 hydroxyl, nitro, CN or halogen atom

[0029] R 21 R 22 and R 23 Each of the following can be independently represented: a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0030] R 21 R 22 and R 23 The hydrogen atoms of the represented groups may optionally be further substituted with hydroxyl, nitro, CN, halogen atoms, or carboxyl groups.

[0031] R 11 R 12 R 13 R 21 R 22 and R 23 The alkylene moiety of the indicated group may optionally contain 1 to 5 -O-, -S-, -COO-, -OCO-, or -NR atoms, provided that the oxygen atoms are not adjacent. 24 -、-NR 24 CO-, -NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO-,

[0032] R 24 The group represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0033] R 11 R 12 R 13 R 21 R 22 R 23 and R 24 The alkyl moiety of the indicated group optionally has branched side chains, and optionally is a cyclic alkyl group.

[0034] R 3 R represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.3 The alkyl moiety of the group represented is optionally substituted with one or more substituents selected from the group consisting of R 3 R 7 , and R 3 R 8 are each optionally taken together to form a ring,

[0035] R 3 The hydrogen atom of the group represented is optionally further substituted with R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, or a halogen atom,

[0036] R 4 , R 5 , R 6 , and R 7 each independently represent R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN, or a halogen atom, R 4 R 5 , R 5 R 6 , and R 6 R 7 are each optionally taken together to form a ring,

[0037] R 14R 15 and R 16 R represents an alkyl group having 1 to 20 hydrogen atoms or carbon atoms. 14 R 15 and R 16 The alkyl moiety of the indicated group optionally has branched side chains, optionally is a cyclic alkyl group, R 8 R represents 11 OR 11 SR 11 COR 11 CONR 12 R 13 NR 12 COR 11 OCOR 11 COOR 11 SCOR 11 OCSR 11 COSR 11 CSOR 11 hydroxyl, CN or halogen atom,

[0038] k represents 0 or 1.

[0039] 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 coloring curable composition of the present invention described above.

[0040] The display device of the present invention has the color filter of the present invention described above.

[0041] The effects of the invention

[0042] According to the present invention, a photosensitive coloring resin composition capable of forming a coloring layer that suppresses linewidth offset and exhibits good solvent resistance even under low-temperature heat treatment can be provided. Furthermore, according to the present invention, a color filter and a display device formed using the photosensitive coloring resin composition can be provided. Attached Figure Description

[0043] Figure 1 This is a schematic diagram illustrating an example of the color filter of the present invention.

[0044] Figure 2 This is a schematic diagram illustrating an example of the liquid crystal display device of the present invention.

[0045] Figure 3 This is a schematic diagram illustrating an example of the organic light-emitting display device of the present invention.

[0046] Figure 4 This is a partial diagram illustrating, in a schematic manner, an example of the structure of the graft copolymer used in this invention.

[0047] Figure 5 is a schematic diagram illustrating an inclination angle (θ1) of a cross-sectional shape of a colored layer of a fine line pattern.

[0048] Figure 6 is a schematic diagram illustrating an inclination angle (θ2) of a cross-sectional shape of a micropore in a colored layer. DETAILED DESCRIPTION

[0049] Hereinafter, the photosensitive colored resin composition, the cured product, the color filter, and the display device of the present application are described in detail.

[0050] Note that, in the present application, light includes electromagnetic waves of wavelengths in the visible and non-visible regions, and also includes radiation, which includes, for example, microwaves, electron beams. Specifically, it refers to electromagnetic waves of wavelengths of 5 μm or less and electron beams.

[0051] In the present application, (meth)acryl group represents acryl group and methacryl group, (meth)acrylic acid represents acrylic acid and methacrylic acid, and (meth)acrylate represents acrylate and methacrylate.

[0052] In addition, in the present specification, "~" indicating a numerical range is used with the meaning that the numerical values recited before and after it are included as lower limit values and upper limit values.

[0053] I. Photosensitive Colored Resin Composition

[0054] The photosensitive colored resin composition of the present application contains a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and

[0055] The above dispersant contains a (meth)acrylate copolymer-based dispersant,

[0056] The above photoinitiator contains a compound represented by the following general formula (A).

[0057] [Chemical Formula 2]

[0058]

[0059] (In the formula, R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 , or CN,

[0060] R 11 , R 12 , and R 13each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0061] R 11 , R 12 , and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, 21 21 21 21 22 23 22 23 22 23 22 23 22 21 21 21 21 21 21 21 a hydroxyl group, a nitro group, CN, or a halogen atom,

[0062] R 21 , R 22 , and R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0063] R 21 , R 22 , and R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0064] R 11 , R 12 , R 13 , R 21 , R 22 , and R 23 each independently represent an alkylene moiety optionally containing 1 to 5 -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 ​​​​​​​​​​​​​​​​​​​-, -SCO-, -COS-, -OCS-, or -CSO-,

[0065] R 24 The group represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0066] R 11 R 12 R 13 R 21 R 22 R 23 and R 24 The alkyl moiety of the indicated group optionally has branched side chains, and optionally is a cyclic alkyl group.

[0067] R 3 R represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. 3 The alkyl moiety of the indicated group optionally has branched side chains, optionally is a cyclic alkyl group, and R 3 With R 7 and R 3 With R 8 Choose any two to form a ring.

[0068] R 3 The hydrogen atoms of the represented group may optionally be further substituted with R. 21 OR 21 COR 21 SR 21 NR 22 R 23 CONR 22 R 23 -NR 22 -OR 23 -NCOR 22 -OCOR 23 NR 22 COR 21 OCOR 21 COOR 21 SCOR 21 OCSR 21 COSR 21 CSOR 21 hydroxyl, nitro, CN or halogen atom

[0069] R 4 R 5 R 6 and R 7 Represent R independently11 11 11 14 15 16 12 11 11 14 11 11 14 11 4 5 5 6 6 7

[0070] 14 15 16 14 15 16 8 11 11 11 11 12 13 12 11 11 11 11 11 11 11

[0071] k represents 0 or 1.

[0072] The photosensitive colored resin composition of the present application uses the above-mentioned (meth)acrylate copolymer-based dispersant as a dispersant, and contains the compound represented by the above-mentioned general formula (A) as a photoinitiator, and thus can form a colored layer which suppresses line width deviation, and which is also excellent in solvent resistance even in the case where low-temperature heating treatment is performed after exposure. Although the mechanism of exerting such an effect is not clear, it is presumed as follows.

[0073] ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​It is considered that, in order to form a colored layer which is excellent in solvent resistance even under low-temperature heat treatment, it is necessary to make the state of curing uniform in the colored layer, but the compatibility of the initiator with other components affects the state of curing. In a photosensitive resin coloring composition, a dispersing agent is generally contained in order to disperse color materials uniformly. Even if the initiator used in the present application is used, sometimes the line width deviation becomes large due to the dispersing agent used, or a colored layer having sufficient solvent resistance cannot be obtained by low-temperature heat treatment. It is considered that, if the compatibility of the initiator with other components is low, the initiator easily exists preferentially on the surface of the colored layer, and further curing proceeds on the surface of the colored layer, thereby the line width deviation becomes large.

[0074] In the photosensitive resin composition of the present application, in contrast, the above-described (meth)acrylate copolymer dispersant is used as a dispersant, and the compound represented by the above-described general formula (A) is contained as a photoinitiator, and therefore the compatibility of the initiator with other components is excellent, and the initiator easily exists uniformly in the colored layer. Therefore, it is presumed that the curing proceeds only on the surface, thereby the line width deviation is suppressed, the colored layer is cured uniformly, thereby the unreacted components are reduced, the internal stress of the colored layer is also reduced, and therefore the change of the colored layer when immersed in a solvent is small. By combining the above-described dispersant and photoinitiator, sufficient solvent resistance can be obtained even by low-temperature heat treatment, and it is presumed that the main reason is that the compatibility of the photoinitiator with the photopolymerizable compound and the dispersant, and the compatibility of the dispersant with the photopolymerizable compound are high.

[0075] It is further presumed that, in the case where the above-described (meth)acrylate copolymer dispersant is a graft copolymer in which a solvent-affinity moiety is branched, or a copolymer having an acid value, the compatibility with the initiator and other components is further improved, the initiator can be uniformly and stably maintained in the film, and the solvent resistance is also improved.

[0076] The photosensitive coloring resin composition of the present application contains at least a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and can further contain other components within a range not impairing the effects of the present application.

[0077] Hereinafter, each component of the photosensitive coloring resin composition of the present application will be described in detail in order from the dispersant and the photoinitiator which are the characteristic combination of the present application.

[0078] <Dispersant>

[0079] In the present application, a (meth)acrylate copolymer dispersant is used as a dispersant.

[0080] The (meth)acrylate copolymer dispersant refers to a dispersant which is a copolymer and contains at least a structural unit derived from a (meth)acrylate.

[0081] The (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a color material adsorption site and a structural unit that functions as a solvent affinity site, and preferably contains at least a structural unit derived from a (meth)acrylate in the structural unit that functions as a solvent affinity site.

[0082] The structural unit that functions as a color material adsorption site can be exemplified by a structural unit derived from an ethylenically unsaturated monomer that can be copolymerized with a structural unit derived from a (meth)acrylate. As the color material adsorption site, there can be a structural unit derived from an acid group-containing ethylenically unsaturated monomer, or a structural unit derived from a basic group-containing ethylenically unsaturated monomer.

[0083] As the structural unit derived from a basic group-containing ethylenically unsaturated monomer, from the viewpoint of excellent dispersibility, a structural unit represented by the following general formula (I) is preferred.

[0084] [Chemical Formula 3]

[0085]

[0086] (In general formula (I), R 41 represents a hydrogen atom or a methyl group, A 1 represents a divalent linking group, R 42 and R 43 each independently represent a hydrogen atom or a hydrocarbon group optionally containing a hetero atom, R 42 and R 43 are optionally bonded to each other to form a ring structure.)

[0087] In general formula (I), A 1 is a divalent linking group. As the divalent linking group, there can be exemplified, for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, a -COO- group, a -NHCOO- group, an ether group (-O- group), a thioether group (-S- group), and combinations thereof. Note that in the present application, the bonding direction of the divalent linking group is arbitrary. That is, in the case where the divalent linking group contains -CONH-, it can be that -CO is on the side of the carbon atom of the main chain and -NH is on the side of the nitrogen atom of the side chain, or conversely, -NH can be on the side of the carbon atom of the main chain and -CO can be on the side of the nitrogen atom of the side chain.

[0088] Among them, from the viewpoint of dispersibility, A 1 in general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a divalent linking group containing a -CONH- group or a -COO- group, and an alkylene group having 1 to 10 carbon atoms.

[0089] R 42 and R 43 The hydrocarbon groups that may be selected to contain heteroatoms include, for example, alkyl, aralkyl, aryl, etc.

[0090] Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclopentyl, and cyclohexyl. The number of carbon atoms in the alkyl group is preferably 1 to 18, and more preferably methyl or ethyl.

[0091] Examples of aralkyl groups include benzyl, phenethyl, naphthylmethyl, and biphenylmethyl. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 14.

[0092] Other examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylylyl. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12. It should be noted that the preferred number of carbon atoms mentioned above does not include the number of carbon atoms in the substituents.

[0093] The hydrocarbon group containing heteroatoms has a structure in which the carbon atom in the aforementioned hydrocarbon group is replaced by a heteroatom, or has 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 included in the hydrocarbon group include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, etc.

[0094] In addition, the hydrogen atoms in the hydrocarbon group can be optionally replaced by halogen atoms such as fluorine, chlorine, and bromine.

[0095] R 42 With R 43 The ring structure formed by mutual bonding refers to R 42 With R 43 A ring structure is formed via nitrogen atoms. R 42 With R 43 The resulting ring structure may optionally contain heteroatoms. The ring structure is not particularly limited; examples include pyrrolidine rings, piperidine rings, and morpholine rings.

[0096] In this invention, R is preferred. 42 and R 43 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an R group. 42 With R 43 They bond together to form pyrrolidine rings, piperidine rings, and morpholine rings.

[0097] As the monomer derived from the structural unit represented by the above general formula (I), mention can be made of: (meth)acrylate esters such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like containing an alkyl-substituted amino group; (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and the like containing an alkyl-substituted amino group. Of these, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to use dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide.

[0098] In the polymer, the structural unit represented by general formula (I) can be contained in one kind, or two or more kinds.

[0099] In addition, at least a portion of the nitrogen sites possessed by the structural unit represented by the above general formula (I) can form a salt with at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon, as a color material adsorption site (hereinafter, such a copolymer is sometimes referred to as a salt-type copolymer).

[0100] As the above organic acid compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable, and as the above halogenated hydrocarbon, a compound represented by the following general formula (2) is particularly preferable. That is, as the at least one selected from the group consisting of the above organic acid compound and the halogenated hydrocarbon, one or more kinds of compounds selected from the group consisting of the above general formulae (1) to (3) can be preferably used.

[0101] [Chemical Formula 4]

[0102]

[0103] (In general formula (1), R a represents a linear, branched, or cyclic alkyl group having a carbon number of 1 to 20, a vinyl group, a phenyl group or a benzyl group optionally having a substituent, or -O-R e , R e represents a linear, branched, or cyclic alkyl group having a carbon number of 1 to 20, a vinyl group, a phenyl group or a benzyl group optionally having a substituent, or a (meth)acryl group via an alkylene group having a carbon number of 1 to 4. In general formula (2), R b , R b' , and R b'' independently represent a hydrogen atom, an acidic group or an ester thereof, a linear, branched, or cyclic alkyl group having a carbon number of 1 to 20 optionally having a substituent, a vinyl group optionally having a substituent, a phenyl group or a benzyl group optionally having a substituent, or -O-R f , R frepresents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms optionally having a substituent, a vinyl group optionally having a substituent, a phenyl group or a benzyl group optionally having a substituent, or a (meth)acryl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom or an iodine atom. In General Formula (3), R c and R d each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group optionally having a substituent, or -O-R e , R e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group optionally having a substituent, or a (meth)acryl group via an alkylene group having 1 to 4 carbon atoms. At least one of R c and R d contains a carbon atom.

[0104] As for each symbol of General Formulas (1) to (3) described above, the same can be as described in International Publication No. 2016 / 104493.

[0105] From the viewpoint of excellent dispersibility and dispersion stability of the color material, the aforementioned organic acid compound is preferably an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. As a specific example of the organic acid compound used for such a dispersant, for example, an organic acid compound described in Japanese Patent Application Publication No. 2012-236882 or the like is suitably cited.

[0106] In addition, as the aforementioned halogenated hydrocarbon, from the viewpoint of excellent dispersibility and dispersion stability of the color material, at least one of an allyl halide such as allyl bromide or benzyl chloride and a haloaralkyl is preferred.

[0107] In the salt-type copolymer, the content of at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is preferably 0.01 mol or more, more preferably 0.05 mol or more, further preferably 0.1 mol or more, and particularly preferably 0.2 mol or more, with respect to the terminal nitrogen site possessed by the structural unit represented by General Formula (I), from the viewpoint of forming a salt with the terminal nitrogen site possessed by the structural unit represented by General Formula (I). If it is 0.01 mol or more, an effect of improving the dispersibility of the color material by forming a salt is easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. If it is 1 mol or less, the development adhesion and the solvent redissolution properties are excellent.

[0108] Note that at least one selected from the organic acid compound and the halogenated hydrocarbon can be used singly or in combination of two or more. In the case of combination of two or more, the total content is preferably within the above range.

[0109] As a method for producing the salt-type copolymer, a method in which at least one selected from the organic acid compound and the halogenated hydrocarbon is added to a solvent in which the copolymer before salt formation is dissolved or dispersed, and stirring is performed, and further heating is performed as necessary, can be exemplified.

[0110] Note that the salt formation of the terminal nitrogen site of the structural unit represented by the above general formula (I) of the copolymer with at least one selected from the organic acid compound and the halogenated hydrocarbon and the ratio thereof can be confirmed by a publicly known method such as NMR (nuclear magnetic resonance).

[0111] From the viewpoints of dispersibility and dispersion stability, the copolymer having the structural unit represented by the above general formula (I) is more preferably at least one of a graft copolymer having the structural unit represented by the above general formula (I) and a graft polymer chain having a structural unit derived from a (meth)acrylate ester, and a block copolymer having an A block containing the structural unit represented by the above general formula (I) and a B block containing a structural unit derived from a (meth)acrylate ester.

[0112] Hereinafter, the above graft copolymer and the above block copolymer will be described in order.

[0113] As the graft copolymer having the structural unit represented by the above general formula (I) and the graft polymer chain having a structural unit derived from a (meth)acrylate ester, at least one of a graft copolymer having the structural unit represented by the above general formula (I) and the structural unit represented by the following general formula (II), and a salt-type graft copolymer obtained by forming a salt of at least a part of the nitrogen site of the structural unit represented by the above general formula (I) of the graft copolymer with at least one selected from an organic acid compound and a halogenated hydrocarbon can be exemplified.

[0114] [Chemical Formula 5]

[0115]

[0116] (In the general formula (II), R 41' represents a hydrogen atom or a methyl group, A 2 represents a direct bond or a divalent linking group, and Polymer represents a polymer chain containing a structural unit derived from a (meth)acrylate ester in the structural unit of the polymer chain.)

[0117] In the above general formula (II), A 2 is a direct bond or a divalent linking group. As the divalent linking group in A 2 there is no particular limitation as long as it can connect a carbon atom derived from an ethylenically unsaturated double bond to a polymer chain. As the divalent linking group in A 2 , the same linking groups as those in the above A 1 may be exemplified.

[0118] In the above general formula (II), A 2 is preferably a divalent linking group containing a -CONH- group or a -COO- group, and more preferably a divalent linking group containing a -CONH- group or a -COO- group and an alkylene group having 1 to 10 carbon atoms.

[0119] In the above general formula (II), Polymer represents a polymer chain, and the structural unit of this polymer chain contains a structural unit derived from a (meth)acrylate ester. By grafting the structural unit represented by the above general formula (II) having a specific polymer chain, the solvent affinity becomes good, the dispersibility and dispersion stability of the color material become good, and the compatibility with the following photoinitiator also becomes good.

[0120] As the structural unit of this polymer chain, the structural unit represented by the following general formula (IV) can be exemplified.

[0121] [Chemical Formula 6]

[0122]

[0123] (In general formula (IV), R 44'' is a hydrogen atom or a methyl group, A 4 is a divalent linking group, and R 50 is a hydrogen atom or a hydrocarbon group optionally containing a hetero atom.)

[0124] As the divalent linking group A 4 , the same linking groups as those in the above A 1 may be exemplified. In the present application, as the structural unit derived from a (meth)acrylate ester, at least the structural unit represented by general formula (IV) in which A 4 is a divalent linking group containing a -COO- group. From the viewpoint of solubility in an organic solvent used for a color filter application, A 4 in general formula (IV) can contain a divalent linking group containing a -CONH- group.

[0125] R 50The hydrocarbon group in the optional heteroatom-containing hydrocarbon group in the above R 50 The hydrocarbon group in the optional heteroatom-containing hydrocarbon group in the above R

[0126] The above alkyl group having a carbon number of 1 to 18 can be any of linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, menthyl, isomenthyl, dicyclopentyl, adamantyl, lower alkyl-substituted adamantyl, and the like. The carbon number of the alkyl group is preferably 1 to 12, and more preferably 1 to 6.

[0127] The above alkyl group having a carbon number of 1 to 18 can be any of linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-nonyl, n-lauryl, n-stearyl, cyclopentyl, cyclohexyl, menthyl, isomenthyl, dicyclopentyl, adamantyl, lower alkyl-substituted adamantyl, and the like. The carbon number of the alkyl group is preferably 1 to 12, and more preferably 1 to 6.

[0128] As the aryl group, phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like can be mentioned. The carbon number of the aryl group is preferably 6 to 24, and more preferably 6 to 12.

[0129] Further, as the aralkyl group, benzyl, phenylethyl, naphthylmethyl, biphenylmethyl, and the like can be mentioned, and can further have a substituent. The carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.

[0130] Further, a linear or branched alkyl group having a carbon number of 1 to 30 can be bonded to the aromatic ring of the above aryl group, aralkyl group, and the like as a substituent.

[0131] The hydrocarbon group in the optional heteroatom-containing hydrocarbon group in the above R 50 The hydrocarbon group in the optional heteroatom-containing hydrocarbon group in the above R

[0132] As the hetero atom optionally contained in the hydrocarbon group, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and the like can be exemplified. As the hydrocarbon group optionally containing a hetero atom, for example, a structure in which a linking group is contained in the carbon chain of the hydrocarbon group, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, and the like can be exemplified.

[0133] In addition, the hydrocarbon group can have a substituent within a range not to hinder the dispersing properties and the like of the graft copolymer described above, and as the substituent, for example, a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, a nitro group, a cyano group, an epoxy group, an isocyanate group, a thiol group, and the like can be exemplified.

[0134] In addition, as the hydrocarbon group optionally containing a hetero atom in R 50 , a structure in which a polymerizable group such as an alkenyl group is added to the terminal via a linking group containing a hetero atom in the hydrocarbon group can be exemplified. For example, the structural unit represented by General Formula (IV) can be a structure in which a structural unit derived from a (meth)acrylic acid is reacted with a (meth)acrylic acid glycidyl ester. That is, the structure of -A 4 -R 50 in General Formula (IV) can be a structure represented by -COO-CH2CH(OH)CH2-OCO-CR=CH2 (here, R is a hydrogen atom or a methyl group). In addition, the structural unit represented by General Formula (IV) can be a structure in which a structural unit derived from a (meth)acrylic acid hydroxyalkyl ester is reacted with a (meth)acrylic acid 2-isocyanate alkyl ester. That is, R 50 in General Formula (IV) can be a structure represented by -R'-OCONH-R''-OCO-CR=CH2 (here, R' and R'' are each independently an alkylene group, and R is a hydrogen atom or a methyl group).

[0135] As the monomer derived from the structural unit represented by General Formula (IV), for example, a monomer having a structural unit derived from a compound such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid, 2-methylpropylene acryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate having a repeating unit number of an oxirane chain of less than 19, and polyethylene glycol (meth)acrylate, phenoxy glycol (meth)acrylate, and the like is preferable. However, the present application is not limited to these.

[0136] In the present application, as the above R 50 is preferably used, provided that the solubility in the organic solvent to be used is appropriate. Specifically, for example, in the case where the above organic solvent is an ether alcohol acetate-based, ether-based, ester-based, alcohol-based, or the like, which is generally used as an organic solvent for a color material dispersion liquid, the above R 50 is preferably methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, cyclohexyl, dicyclopentyl, hydroxyethyl, phenoxyethyl, adamantyl, methoxypolyethylene glycol, methoxypolypropylene glycol, polyethylene glycol, or the like.

[0137] In the above graft copolymer, from the viewpoint of shortening the development time of the photosensitive resin composition and further improving the solvent resistance of the cured product of the photosensitive colored resin composition, it is preferable that the structural unit of the polymer chain in the above structural unit represented by General Formula (II) contain at least one structural unit selected from the structural unit represented by General Formula (III) and the structural unit represented by General Formula (III').

[0138] The structural unit represented by General Formula (III) and the structural unit represented by General Formula (III') are contained in the structural unit represented by General Formula (IV).

[0139] [Chemical Formula 7]

[0140]

[0141]

[0142] (in General Formula (III), R 44 is a hydrogen atom or a methyl group, A 3 is a divalent linking group, R 45 is an ethylene group or a propylene group, R 46 is a hydrogen atom or a hydrocarbon group, and m represents a number of 3 or more and 80 or less.

[0143] (in General Formula (III'), R 44' is a hydrogen atom or a methyl group, A 3' is a divalent linking group, R 47 is an alkylene group having a carbon number of 1 to 10, R 48 is an alkylene group having a carbon number of 3 to 7, R 49 is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less.

[0144] As the divalent linking group A 3 , the same linking groups as those in A 1 described above can be exemplified. Among them, from the viewpoint of solubility in an organic solvent used for a color filter, A 3 in General Formula (III) is preferably a divalent linking group containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group, and still more preferably a -COO- group.

[0145] The above m represents the number of repeating units of the oxirane chain or the oxetane chain, and represents a number of 3 or more, wherein, from the viewpoint of suppressing the occurrence of water stains, it is preferably 19 or more, and more preferably 21 or more. Note that the water stains refer to a phenomenon in which, after alkaline development, traces like water penetration are produced after washing with pure water. Such water stains disappear after post-baking, and thus are not a problem for products, but are detected as unevenness in appearance inspection after patterning after development, and cause a problem in that normal products and abnormal products cannot be distinguished. Thus, if the inspection sensitivity of the inspection device is reduced in appearance inspection, the result is a reduction in yield of the final color filter product, which becomes a problem. As a cause of the occurrence of water stains in the cured film of the photosensitive resin composition, water absorption into the cured film can be cited. The alkali-soluble resin in the cured film has an acidic group such as a carboxyl group, and thus readily absorbs water. In addition, it is believed that the acidic group forms a metal salt with an alkali metal typically contained in the alkaline developer at the time of development, and thus the water absorbency is further increased. The oxygen atoms contained in the polyethylene oxide chain or the polypropylene oxide chain can be captured by complexation with a metal such as an alkali metal. It is presumed that, as the number of repeating units of the polyethylene oxide chain or the polypropylene oxide chain increases, the complexation constant increases, and the metal molecule capture ability increases, and thus the formation of the alkali metal salt of the alkali-soluble resin can be suppressed, and water absorption into the cured film can be suppressed. In addition, it is presumed that the oxygen atoms contained in the polyethylene oxide chain or the polypropylene oxide chain interact with the acidic group such as the carboxyl group of the alkali-soluble resin contained in the photosensitive resin composition through hydrogen bonding, and thus the formation of the alkali metal salt of the acidic group can be suppressed, and water absorption into the cured film can be suppressed.

[0146] In the case where the above m is 19 or more, as shown in Figure 4 the above graft copolymer 11 contains a main chain portion 12 having a structural unit 21 represented by general formula (I) and a structural unit 22 represented by general formula (II), and at least a part of the nitrogen sites of the above structural unit 21 represented by general formula (I) can form a salt with at least one selected from an organic acid compound and a halogenated hydrocarbon 23, and the above structural unit 22 represented by general formula (II) is a structural unit 25 represented by general formula (III) containing a polyethylene oxide chain or a polypropylene oxide chain 26 having a specific number of repetitions in a polymer chain 24. In the specific graft copolymer used in the present application, the structural unit of the thus grafted polymer chain 24 contains the structural unit 25 containing a polyethylene oxide chain or a polypropylene oxide chain having a specific number of repetitions, and the grafted polymer chain 24 itself has a branched structure. It is presumed that, as a result, the specific surface area of the metal capture portion of the dispersant increases, and, in interaction therewith, the metal capture action by the oxygen atoms contained in the polyethylene oxide chain or the polypropylene oxide chain is significant, and the water absorption suppression effect can be improved, and the occurrence of water stains due to water absorption can be suppressed. It is presumed that, by these water absorption suppression effects into the cured film, the occurrence of water stains due to water absorption can be suppressed.

[0147] On the other hand, the upper limit value of m is 80 or less, and preferably 50 or less from the viewpoint of solubility in an organic solvent used for a color filter application.

[0148] As the hydrocarbon group in R 46 , the same hydrocarbon group as in the above R 50 may be used.

[0149] As the hydrocarbon group in R 46 , from the viewpoint of dispersion stability and compatibility, one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms optionally substituted with an alkyl group, and an aralkyl group having 7 to 14 carbon atoms optionally substituted with an alkyl group is preferred, and one or more selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-nonyl group, an n-lauryl group, an n-stearyl group, a phenyl group optionally substituted with an alkyl group, and a benzyl group is more preferred.

[0150] In the above general formula (III'), as the divalent linking group of A 3' , the same linking group as in the above A 1 may be used. Among them, from the viewpoint of solubility in an organic solvent used for a color filter application, A 3' in general formula (III') is preferably a divalent linking group containing a -CONH- group or a -COO- group, more preferably a -CONH- group or a -COO- group, and still more preferably a -COO- group.

[0151] In the above general formula (III'), R 47 is an alkylene group having 1 to 10 carbon atoms, and from the viewpoint of solvent redissolution, an alkylene group having 2 to 8 carbon atoms is preferred.

[0152] R 48 is an alkylene group having 3 to 7 carbon atoms, and from the viewpoint of adhesion to a substrate, an alkylene group having 3 to 5 carbon atoms is preferred, and an alkylene group having 5 carbon atoms is further preferred.

[0153] R 49 is a hydrogen atom or a hydrocarbon group, and the same hydrocarbon group as in the above R 49 may be used as the hydrocarbon group in the above R 46 .

[0154] The above n in general formula (III') represents the number of repeating units of the ester chain, and represents a number of 1 or more, and from the viewpoint of shortening the development time while satisfying excellent solvent resistance, a number of 2 or more is preferred, and a number of 3 or more is further preferred.

[0155] On the other hand, the upper limit of n is 40 or less, and is preferably 20 or less from the viewpoint of solubility in an organic solvent used for color filter applications.

[0156] In the polymer chain, at least one of the structural units represented by the aforementioned general formula (III) and the structural units represented by the aforementioned general formula (III') can be used alone or two or more kinds can be mixed.

[0157] From the viewpoint of more obvious effects of the solvent affinity part caused by the oxygen atom, shortening of the development time of the photosensitive resin composition, and improvement of the solvent resistance, it is preferable that the aforementioned polymer chain contain the structural unit represented by the aforementioned general formula (III).

[0158] Among the structural units of the polymer chain in the aforementioned general formula (II), from the viewpoint of improving the water stain suppression effect, improving the solvent resistance, and improving the development residue suppression effect, it is more preferable that the combination contain at least one of the structural units represented by the aforementioned general formula (III) in which m is 19 or more and 80 or less, and at least one of the structural units represented by the aforementioned general formula (III) in which m is 3 or more and 10 or less, and it is further preferable that the combination contain at least one of the structural units represented by the aforementioned general formula (III) in which m is 19 or more and 50 or less, and at least one of the structural units represented by the aforementioned general formula (III) in which m is 3 or more and 8 or less.

[0159] In the case where at least one of the structural units represented by the aforementioned general formula (III) in which m is 19 or more and 80 or less is contained in the structural units of the polymer chain in the aforementioned general formula (II), from the viewpoint of the water stain suppression effect, the total proportion of the structural units represented by the aforementioned general formula (III) in which m is 19 or more and 80 or less is preferably 1% by mass or more, more preferably 2% by mass or more, and further more preferably 4% by mass or more, when all of the structural units of the aforementioned polymer chain are taken as 100% by mass, on the other hand, from the viewpoint of the solvent redissolvability and the water stain suppression effect, it is preferably 75% by mass or less, more preferably 65% by mass or less, and further more preferably 50% by mass or less.

[0160] In the case where the combination of the structural units of the polymer chain in the above structural unit represented by General Formula (II) contains at least one of the structural units represented by the above General Formula (III) in which m is 19 or more and 80 or less and at least one of the structural units represented by the above General Formula (III) in which m is 3 or more and 10 or less, the total proportion of the structural units represented by the above General Formula (III) in which m is 3 or more and 10 or less is preferably 20% by mass or more, based on 100% by mass of all the structural units of the above polymer chain. On the other hand, from the viewpoint of solvent redissolvability, the total proportion of the structural units represented by the above General Formula (III) in which m is 3 or more and 10 or less in the above polymer chain is preferably 80% by mass or less, more preferably 60% by mass or less, based on 100% by mass of all the structural units of the polymer chain.

[0161] In addition, regarding the mixing ratio of the structural units represented by the above General Formula (III) in which m is 19 or more and 80 or less and the structural units represented by the above General Formula (III) in which m is 3 or more and 10 or less in the above polymer chain, from the viewpoint of improving the development residue suppression effect, the total of the structural units represented by the above General Formula (III) in which m is 19 or more and 80 or less is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, and is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the total of the structural units represented by the above General Formula (III) in which m is 19 or more and 80 or less and the structural units represented by the above General Formula (III) in which m is 3 or more and 10 or less.

[0162] From the viewpoint of simultaneously satisfying dispersion stability, high contrast, shortening of development time, and excellent solvent resistance, the total proportion of at least one of the structural units represented by the above General Formula (III) and the structural units represented by the above General Formula (III') is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 4% by mass or more, based on 100% by mass of all the structural units of the above polymer chain. From the viewpoint of solvent redissolvability, the total proportion of at least one of the structural units represented by the above General Formula (III) and the structural units represented by the above General Formula (III') is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less, based on 100% by mass of all the structural units of the above polymer chain.

[0163] In the above polymer chain, the structural units represented by the above General Formula (IV) that contain the structural units represented by the above General Formula (III) and the structural units represented by the above General Formula (III') can be used singly or in a mixture of two or more kinds.

[0164] From the viewpoint of dispersibility and dispersion stability of the color material, the total proportion of the structural units represented by the above general formula (IV) is preferably 70% by mass or more, more preferably 90% by mass or more, based on 100% by mass of all the structural units of the polymer chain. On the other hand, from the viewpoint of simultaneously satisfying dispersion stability and excellent solvent resistance, the total proportion of the structural units represented by the above general formula (IV) in the above polymer chain can be 100% by mass, based on 100% by mass of all the structural units of the polymer chain.

[0165] wherein, from the viewpoint of dispersion stability and solvent resistance, and compatibility with an initiator, the total proportion of the structural units derived from (meth)acrylate is preferably 60% by mass or more, more preferably 80% by mass or more, based on 100% by mass of all the structural units of the polymer chain. On the other hand, from the viewpoint of simultaneously satisfying dispersion stability and excellent solvent resistance, the total proportion of the structural units derived from (meth)acrylate in the above polymer chain can be 100% by mass, based on 100% by mass of all the structural units of the polymer chain.

[0166] In the structural units of the polymer chain in the structural units represented by the above general formula (II) of the above graft copolymer, other structural units can be included in addition to the structural units represented by the above general formula (IV) which include the structural units represented by the above general formula (III) and the structural units represented by the above general formula (III').

[0167] As the other structural units, structural units derived from a monomer having an unsaturated double bond which is copolymerizable with the monomer from which the structural units represented by the above general formula (IV) are derived can be exemplified.

[0168] As the monomer from which the other structural units are derived, styrene-based monomers such as styrene, α-methylstyrene, vinyl ether-based monomers such as phenyl vinyl ether, and the like can be exemplified.

[0169] In the polymer chain in the structural units represented by the above general formula (II) of the above graft copolymer, from the viewpoint of the effects of the present application, the total proportion of the other structural units is preferably 30% by mass or less, more preferably 10% by mass or less, based on 100% by mass of all the structural units of the polymer chain.

[0170] From the viewpoint of dispersibility and dispersion stability of the color material, the weight average molecular weight Mw of the polymer chain in Polymer is preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, and more preferably 15000 or less, still more preferably 12000 or less.

[0171] By being within the above range, sufficient steric repulsion as a dispersant can be maintained, and the specific surface area of the solvent affinity portion of the dispersant becomes large, whereby penetration of a solvent into a coating film or to a color material can be suppressed, and in the case of containing a polyethylene oxide chain or a polypropylene oxide chain, the interaction brought about by the oxygen atom is significant, the developing time can be shortened, the effect of improving solvent resistance is good, and furthermore, the effects of suppressing water mark generation and developing residue generation are good.

[0172] Further, regarding the polymer chain in the Polymer, as a standard, the solubility in the organic solvent used in combination at 23°C is preferably 20 (g / 100 g of solvent) or more.

[0173] The solubility of the polymer chain can be standardized by the raw material from which the polymer chain is introduced at the time of preparing the graft copolymer having the above solubility. For example, in order to introduce the polymer chain to the graft copolymer, in the case where a polymerizable oligomer (macromonomer) containing a group having an ethylenic unsaturated double bond at the terminal thereof is used, it is only necessary that the polymerizable oligomer has the above solubility. Further, in the case where the polymer chain is introduced after forming a copolymer from a monomer containing a group having an ethylenic unsaturated double bond, using a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer, it is only necessary that the polymer chain containing the reactive group has the above solubility.

[0174] In the above graft copolymer, the structural unit represented by the above general formula (I) is preferably contained at a ratio of 3 to 60% by mass, more preferably 6 to 45% by mass, and further preferably 9 to 30% by mass. If the structural unit represented by general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion to the color material in the graft copolymer is appropriate, and its solubility in an organic solvent can be suppressed from decreasing, and thus its adsorptivity to the color material is good, and excellent dispersibility and dispersion stability can be obtained.

[0175] On the other hand, in the above graft copolymer, the structural unit represented by the above general formula (II) is preferably contained at a ratio of 40 to 97% by mass, more preferably 55 to 94% by mass, and further preferably 70 to 91% by mass. If the structural unit represented by general formula (II) in the graft copolymer is within the above range, the ratio of the solvent affinity portion in the graft copolymer is appropriate, sufficient steric repulsion as a dispersant can be maintained, and the specific surface area of the solvent affinity portion of the dispersant becomes large, whereby penetration of a solvent into a coating film or to a color material can be suppressed, and in the case of containing a polyethylene oxide chain or a polypropylene oxide chain, the interaction brought about by the oxygen atom is significant, the developing time can be shortened, the effect of improving solvent resistance is good, and furthermore, the effects of suppressing water mark generation and developing residue generation are good.

[0176] The graft copolymer used in the present application can further have other structural units in addition to the structural units represented by the above general formula (I) and the structural units represented by the above general formula (II) within a range not impairing the effects of the present application. As the other structural units, a monomer containing an ethylenically unsaturated double bond, which is copolymerizable with a monomer containing an ethylenically unsaturated double bond derived to the structural units represented by the above general formula (I) and the like, can be appropriately selected and copolymerized to introduce the other structural units.

[0177] As the other structural units copolymerizable with the structural units represented by the above general formula (I), the structural units represented by the above general formula (IV) and the like can be exemplified.

[0178] Note that the content ratio of the above structural units is calculated based on the amount of the monomers derived to the structural units represented by the above general formula (I), the structural units represented by the above general formula (II), the structural units represented by the above general formula (IV), and the like, which are added at the time of synthesizing the graft copolymer at the time of production.

[0179] In addition, from the viewpoint of dispersibility and dispersion stability, the mass average molecular weight Mw of the above graft copolymer is preferably 4000 or more, more preferably 6000 or more, and still more preferably 8000 or more. On the other hand, from the viewpoint of solvent redissolution, it is preferably 50000 or less, and more preferably 30000 or less.

[0180] Note that in the present application, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). The measurement is performed under the following conditions: using HLC-8120 GPC manufactured by Tosoh, setting the elution solvent to N-methylpyrrolidone to which 0.01 mole / liter of lithium bromide is added, setting the calibration curve with polystyrene standards to Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh), and setting the measurement column to TSK-GEL ALPHA-M x 2 (manufactured by Tosoh).

[0181] (Method for producing graft copolymer)

[0182] In the present application, the method for producing the graft copolymer described above is not particularly limited, and any method can be used as long as it is a method for producing a graft copolymer having the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) described above. In the case of producing a graft copolymer having the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) described above, for example, a method in which a monomer represented by the general formula (la) described below, and a polymer chain and a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated double bond at the terminal thereof as a copolymerization component are copolymerized to produce a graft copolymer can be exemplified.

[0183] Other monomers can also be further used as needed, and a graft copolymer can be produced using a publicly known polymerization method.

[0184] [Chemical Formula 8]

[0185]

[0186] (In the general formula (la), R 41 , A 1 , R 42 , and R 43 are the same as in the general formula (I).)

[0187] In the case of producing a graft copolymer having the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) described above, the monomer represented by the general formula (la) described above can be addition-polymerized with other monomers containing a group having an ethylenically unsaturated double bond to form a copolymer, and then a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer can be used to introduce the polymer chain. Specifically, for example, after a copolymer having an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a hydrogen bond-forming group, or the like as a substituent is synthesized, the copolymer can be reacted with a polymer chain containing a functional group that reacts with the substituent to introduce the polymer chain.

[0188] For example, a copolymer having a glycidyl group in the side chain can be reacted with a polymer chain having a carboxyl group at the terminal thereof, or a copolymer having an isocyanate group in the side chain can be reacted with a polymer chain having a hydroxyl group at the terminal thereof to introduce the polymer chain.

[0189] Note that in the polymerization described above, additives generally used for polymerization, such as a polymerization initiator, a dispersion stabilizer, a chain transfer agent, and the like, can be used.

[0190] Next, a block copolymer having an A block containing the structural unit represented by the general formula (I) described above, and a B block containing a structural unit derived from a (meth)acrylate will be described.

[0191] In the present application, the configuration of each block of the block copolymer is not particularly limited, and for example, it can be an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like. Among them, from the viewpoint of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

[0192] The A block is a block that functions as a color material adsorption site, and contains at least a structural unit represented by the above general formula (I). It can be a salt type block copolymer in which at least a part of the nitrogen sites of the structural unit represented by the above general formula (I) of the block copolymer forms a salt with at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon.

[0193] The A block can have a structural unit other than the structural unit represented by the general formula (I) within a range that achieves the object of the present application, and can contain a structural unit that can be copolymerized with the structural unit represented by the general formula (I). Specifically, for example, the structural unit represented by the above general formula (IV) or the like can be mentioned.

[0194] In the A block in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) with respect to the total mass of all structural units of the A block is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and most preferably 100% by mass. The reason for this is that the higher the proportion of the structural unit represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. Note that the content ratio of the above structural unit is calculated from the added mass at the time of synthesizing the A block having the structural unit represented by the general formula (I).

[0195] In addition, in the block copolymer before salt formation, from the viewpoint of becoming good in dispersibility and dispersion stability, the content ratio of the structural unit represented by the general formula (I) with respect to the total mass of all structural units of the block copolymer is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass. Note that the content ratio of each structural unit in the above block copolymer is calculated from the added mass at the time of synthesizing the block copolymer before salt formation.

[0196] Note that the structural unit represented by the general formula (I) can contain one kind or two or more kinds as long as it has an affinity with the color material.

[0197] The B block is a block that functions as a solvent affinity site, and contains at least a structural unit derived from a (meth)acrylate ester.

[0198] As the structural unit derived from a (meth)acrylate ester, the same as described above can be mentioned.

[0199] As the B block, it is preferable to use, in a manner having solvent affinity, from among monomers having an unsaturated double bond which are copolymerizable with the monomers derived from the structural unit represented by General Formula (I), in accordance with the solvent. As a standard, it is preferable to introduce the B block in a manner such that the solubility of the copolymer in the solvent used in combination at 23°C is 20 (g / 100 g solvent) or more. The structural unit constituting the B block portion can include one kind, or two or more kinds.

[0200] As the structural unit included in the B block, for example, the structural unit represented by General Formula (IV) described above can be cited.

[0201] In the block copolymer used as the dispersant of the present application, the ratio m / n of the number of units m of the structural unit represented by General Formula (I) described above to the number of units n of the other structural unit constituting the solvent-affinity block portion is preferably in the range of 0.01 or more and 1 or less, and from the viewpoint of the dispersibility and dispersion stability of the color material, it is more preferably in the range of 0.05 or more and 0.7 or less.

[0202] From the viewpoint of improving the solvent resistance in combination with the specific initiator used in the present application, and suppressing the generation of development residue, it is preferable that the block copolymer used as the dispersant of the present application contains at least one of a block copolymer containing an A block including the structural unit represented by General Formula (I) described above, and a B block including a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a (meth)acrylate ester, and a salt-type block copolymer obtained by forming a salt of at least a part of the nitrogen site of the structural unit represented by General Formula (I) of the block copolymer with at least one selected from an organic acid compound and a halogenated hydrocarbon. The acid value of the at least one of the block copolymer and the salt-type block copolymer is 1 to 18 mgKOH / g, and the glass transition temperature is 30°C or more.

[0203] The B block in this case includes a structural unit derived from a (meth)acrylate ester as an essential component, and can be the same as the B block of International Publication No. 2016 / 104493.

[0204] As the carboxyl group-containing monomer, a monomer capable of copolymerizing with the monomer derived from the structural unit represented by General Formula (I) and containing an unsaturated double bond and a carboxyl group can be used. As such a monomer, for example, (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like can be exemplified. In addition, an adduct of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, and the like, ω-carboxy-polycaprolactone mono(meth)acrylate, and the like can also be used. In addition, as a precursor of a carboxyl group, a monomer containing an anhydride group such as maleic anhydride, itaconic anhydride, citraconic anhydride, and the like can be used. Among these, from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like, (meth)acrylic acid is particularly preferable.

[0205] In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxyl group-containing monomer is not particularly limited, and is preferably 0.05% by mass or more and 4.5% by mass or less, more preferably 0.07% by mass or more and 3.7% by mass or less, with respect to the total mass of all the structural units of the block copolymer, in a manner that the acid value of the block copolymer is within the range of the above specific acid value.

[0206] By the content ratio of the structural unit derived from the carboxyl group-containing monomer being the above lower limit value or more, a development residue inhibitory effect can be exhibited, and by being the above upper limit value or less, a decrease in development adhesion and a decrease in solvent redissolvability can be prevented.

[0207] Note that the structural unit derived from the carboxyl group-containing monomer can include one kind or two or more kinds as long as it is the above specific acid value.

[0208] In addition, from the viewpoint of improving development adhesion, it is preferable that the B block of the block copolymer contain a structural unit derived from a hydroxyl group-containing monomer. In the case where the B block contains a structural unit derived from a hydroxyl group-containing monomer, the development speed is further improved. Note that the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

[0209] As the structural unit derived from a hydroxyl group-containing monomer, a monomer capable of copolymerizing with the monomer derived from the structural unit represented by General Formula (I) and containing an unsaturated double bond and a hydroxyl group can be used. As such a monomer, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, ε-caprolactone 1 mole adduct of 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and the like can be exemplified.

[0210] From the viewpoint of improving the development adhesion, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate is preferred.

[0211] In the block copolymer before salt formation, the content ratio of the structural unit derived from the hydroxyl group-containing monomer is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more, relative to the total mass of all the structural units of the block copolymer. If it is equal to or greater than the above lower limit value, it becomes a block copolymer preferred in terms of development adhesion. Also, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is equal to or less than the above upper limit value, the introduction ratio of other useful monomers can be increased, and thus it is preferred. Note that the content ratio of the above structural unit is calculated based on the added mass at the time of synthesizing the block copolymer before salt formation.

[0212] The acid value of at least one of the above block copolymer and the salt-type block copolymer is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more, as a lower limit value, from the viewpoint of the development residue suppression effect. Also, the acid value of at least one of the above block copolymer and the salt-type block copolymer is preferably 18 mgKOH / g or less, and more preferably 16 mgKOH / g or less, and still more preferably 14 mgKOH / g or less, as an upper limit value, from the viewpoint of being able to prevent the development adhesion or the solvent redissolution property from deteriorating.

[0213] The acid value of at least one of the above block copolymer and the salt-type block copolymer can be found by the method described in International Publication No. 2016 / 104493.

[0214] From the viewpoint of the development adhesion, the glass transition temperature of at least one of the above block copolymer and the salt-type block copolymer is preferably 30°C or more, and particularly preferably 32°C or more, and more preferably 35°C or more. On the other hand, from the viewpoint of the operability at the time of use, such as easy accurate weighing, it is preferably 200°C or less.

[0215] The glass transition temperature of at least one of the above block copolymer and the salt-type block copolymer is found by measuring with differential scanning calorimetry (DSC) based on JIS K7121. In the case where two or more peaks indicating the glass transition temperature are observed, the peak having the largest peak area, that is, the area of the portion protruding from the baseline of the obtained graph, is set as the representative value of the glass transition temperature.

[0216] The mass average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, and is preferably 1000 or more and 20000 or less, more preferably 2000 or more and 15000 or less, and still more preferably 3000 or more and 12000 or less from the viewpoint of good color material dispersibility and dispersion stability.

[0217] Here, the mass average molecular weight (Mw) can be measured in the same manner as described above.

[0218] In addition, from the viewpoints of dispersion stability and solvent resistance, and compatibility with an initiator, the total proportion of the structural units derived from (meth)acrylate is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, when all of the structural units in the B block of the block copolymer are taken as 100% by mass. On the other hand, from the viewpoints of simultaneously satisfying dispersion stability and excellent solvent resistance, the total proportion of the structural units derived from (meth)acrylate can be 100% by mass, when all of the structural units in the B block are taken as 100% by mass. In the case where the B block contains structural units derived from the above-mentioned carboxyl group-containing monomer, the total proportion of the structural units derived from (meth)acrylate can be 100% by mass, when all of the structural units in the B block other than the structural units derived from the above-mentioned carboxyl group-containing monomer are taken as 100% by mass.

[0219] In addition, in the block copolymer before the salt is formed, the proportion of the structural units represented by the above-mentioned general formula (IV) is preferably 40 to 95% by mass, and more preferably 50 to 90% by mass, with respect to the total mass of all of the structural units of the block copolymer, from the viewpoint of improving color material dispersibility. Note that the proportion of the above-mentioned structural units is calculated based on the added mass at the time of synthesizing the block copolymer before the salt is formed.

[0220] From the viewpoints of good dispersibility, no foreign matter being deposited when a coating film is formed, and improved brightness and contrast, the (meth)acrylate-based copolymer containing the structural units represented by the above-mentioned general formula (I) is preferably a copolymer having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less.

[0221] By having the amine value within the above-mentioned range, the viscosity has excellent stability over time, heat resistance, and also excellent alkaline development and solvent redissolution. In the present application, the (meth)acrylate-based copolymer containing the structural units represented by the above-mentioned general formula (I) is particularly preferably an amine value of 80 mgKOH / g or more, and more preferably 90 mgKOH / g or more. On the other hand, from the viewpoint of solvent redissolution, the (meth)acrylate-based copolymer containing the structural units represented by the above-mentioned general formula (I) is preferably an amine value of 110 mgKOH / g or less, and more preferably 105 mgKOH / g or less.

[0222] The amine value is the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. In the case of measurement by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound is usually dissociated, and thus the amine value of the block copolymer itself used as the dispersant can be measured.

[0223] The content ratio (mole %) of each structural unit in the copolymer in the dispersant can be calculated from the amount of the raw material added at the time of production, and can be measured using an analysis device such as NMR. In addition, the structure of the dispersant can be measured using NMR, various mass spectrometry, and the like. In addition, the dispersant can be decomposed by thermal decomposition or the like as needed, and for the obtained decomposition product, high performance liquid chromatography, gas chromatography mass spectrometer, NMR, elemental analysis, XPS / ESCA (X-ray photoelectron spectroscopy / Electron Spectroscopy for Chemical Analysis), TOF-SIMS (time of flight secondary ion mass spectrometer), and the like are used.

[0224] In the present application, as the dispersant, at least one kind of the above-mentioned (meth)acrylate copolymer-based dispersant is used, and the content thereof is appropriately selected depending on the kind of the color material used, and further depending on the solid content concentration and the like in the photosensitive colored resin composition described below.

[0225] Regarding the content of the dispersant, it is preferably adjusted to 2 to 30 mass% with respect to the total amount of the solid content of the photosensitive colored resin composition, and particularly preferably adjusted to 3 to 25 mass%. If it is equal to or more than the above lower limit value, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition is more excellent. In addition, if it is equal to or less than the above upper limit value, the developability is good. Especially, in the case of forming a colored layer having a high color material concentration, the content of the dispersant is preferably adjusted to 2 to 25 mass% with respect to the total amount of the solid content of the photosensitive colored resin composition, and more preferably adjusted to 3 to 20 mass%.

[0226] Note that, in the present application, the solid content is all components other than the following solvent, and also includes monomers and the like dissolved in the solvent.

[0227] <Photoinitiator>

[0228] The photoinitiator in the photosensitive colored resin composition of the present application contains a compound represented by the following general formula (A). It is considered that, due to the photoinitiator containing a compound represented by the following general formula (A), by the combination thereof with the above-mentioned specific dispersant, the initiator is easily present uniformly in the colored layer, only the surface is cured so that the line width shift is inhibited from becoming large, the colored layer is uniformly cured so that the curability of the coating film is improved, and thus the solvent resistance of the cured product of the photosensitive colored resin composition becomes good.

[0229] (the compound represented by the following general formula (A))

[0230] The oxime ester compound represented by the following general formula (A) used in the present application has geometric isomers caused by the double bond of the oxime, but they are not distinguished. That is, in the present specification, the compound represented by the following general formula (A), and the preferred form of the above-mentioned compound, that is, the compound represented by the following general formula (B) and the exemplified compounds thereof represent a mixture of both or either one, and are not limited to the structure of the represented isomer.

[0231] [Chemical Formula 9]

[0232]

[0233] (In the formula, R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN,

[0234] R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0235] R 11 , R 12 and R 13 represented by the above-mentioned groups are optionally further substituted with R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22-OCOR 23 NR 22 COR 21 OCOR 21 COOR 21 SCOR 21 OCSR 21 COSR 21 CSOR 21 hydroxyl, nitro, CN or halogen atom

[0236] R 21 R 22 and R 23 Each of the following can be independently represented: a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0237] R 21 R 22 and R 23 The hydrogen atoms of the represented groups may optionally be further substituted with hydroxyl, nitro, CN, halogen atoms, or carboxyl groups.

[0238] R 11 R 12 R 13 R 21 R 22 and R 23 The alkylene moiety of the indicated group may optionally contain 1 to 5 -O-, -S-, -COO-, -OCO-, or -NR atoms, provided that the oxygen atoms are not adjacent. 24 -、-NR 24 CO-, -NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO-,

[0239] R 24 The group represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0240] R 11 R 12 R 13 R 21 R 22 R 23 and R 24 The alkyl moiety of the indicated group optionally has branched side chains, and optionally is a cyclic alkyl group.

[0241] R 3represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 3 The alkyl moiety of the group represented is optionally branched, is optionally a cyclic alkyl group, and in addition, R 3 R 7 , and R 3 R 8 are each optionally taken together to form a ring,

[0242] R 3 The hydrogen atom of the group represented is optionally further substituted with R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, or a halogen atom,

[0243] R 4 , R 5 , R 6 , and R 7 each independently represent R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN, or a halogen atom, R 4 R 5 , R 5 R 6 , and R 6 R7 each optionally forms a ring, together with

[0244] R 14 , R 15 and R 16 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 14 , R 15 and R 16 represent an alkyl group having 1 to 20 carbon atoms, R 8 represents R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , a hydroxyl group, CN or a halogen atom,

[0245] k represents 0 or 1.

[0246] As the alkyl group having 1 to 20 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 and R 24 in the above general formula (A), there can be mentioned, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

[0247] As the alkyl group having 1 to 20 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24The aryl group represented by the symbol of the number of carbon atoms of 6 to 30 can be exemplified by, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, phenyl substituted by one or more of the above-mentioned alkyl groups, biphenyl, naphthyl, anthryl, and the like.

[0248] The R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , and R 24 represented by the symbol of the number of carbon atoms of 7 to 30 can be exemplified by, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, and the like.

[0249] The R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , and R 24 represented by the symbol of the number of carbon atoms of 2 to 20 can be exemplified by, for example, 5- to 7-membered heterocyclic groups such as pyridyl, pyrimidinyl, furanyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazolidinyl, oxazolidinyl, isoxazolidinyl, piperidinyl, piperazinyl, morpholinyl, and the like.

[0250] The R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 3 and R 7 , and R 3 and R 8 may form a ring together, for example, 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring, and the like can be preferably exemplified.

[0251] In addition, the halogen atom represented by the symbol of R 4 , R 5 , R 6 , R 7 , and R 8 in the above-mentioned general formula (A), and the optionally substituted R 3 , R 11 , R 12 , R 13R 21 R 22 and R 23 Halogen atoms can be listed as: fluorine, chlorine, bromine, and iodine.

[0252] R in the above general formula (A) 11 R 12 R 13 R 21 R 22 and R 23 The alkylene moiety of the represented group may contain 1 to 5 -O-, -S-, -COO-, -OCO-, or -NR atoms, provided that the oxygen atoms are not adjacent. 24 -、-NR 24 CO-, -NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO-, where the divalent group can be one or more groups, and in the case of groups that can be continuously included, more than two groups can be continuously included.

[0253] In addition, R in the above general formula (A) 11 R 12 R 13 R 21 R 22 R 23 and R 24 The alkyl (alkylene) portion of the represented group optionally has branched side chains, and optionally is cyclic alkyl.

[0254] In the compounds represented by the above general formula (A), R 3 Compounds of condensable aromatic rings or those represented by the following general formula (B) are preferred because they are highly sensitive and easy to manufacture.

[0255] [Chemical Formula 10]

[0256] General formula (B)

[0257]

[0258] (where R is in the formula) 1 R 2 R 4 R 5 R 6 R 7 R 8 And k is the same as in the above general formula (A), R 31 R 32 R 33 R 34 and R 35 Represent R independently11 OR 11 SR 11 COR 11 CONR 15 R 16 NR 12 COR 11 OCOR 11 COOR 14 SCOR 11 OCSR 11 COSR 14 CSOR 11 hydroxyl, nitro, CN or halogen atom, R 31 With R 32 R 32 With R 33 R 33 With R 34 and R 34 With R 35 (Choose any two pairs to form a ring.)

[0259] As R 31 With R 32 R 32 With R 33 R 33 With R 34 and R 34 With R 35 Examples of rings formed together can be listed above as R. 4 With R 5 R 5 With R 6 R 6 With R 7 R 3 With R 7 and R 3 With R 8 Examples of rings that can be formed together are the same as the examples listed.

[0260] In the above general formulas (A) and (B), R 1 It is an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 15 carbon atoms and R 11 Compounds with aryl groups having 6 to 12 carbon atoms or alkyl groups having 1 to 8 carbon atoms are preferred due to their high solvent solubility. 2 Compounds that are methyl, ethyl, or phenyl are preferred due to their high reactivity. 4 ~R 7 Compounds containing hydrogen atoms or cyano groups, especially hydrogen atoms, are readily synthesized and are therefore preferred. 8The compound in which at least one of R 31 ~R 35 is a nitro group, CN, a halogen atom, COR 11 and R 11 is an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms is preferred because of higher sensitivity, and more preferred is a compound in which at least one of R 31 ~R 35 is a nitro group, CN, or a halogen atom, and particularly preferred is a compound in which R 33 is a nitro group, CN, or a halogen atom.

[0261] As the preferred specific examples of the compound represented by the above general formula (A), for example, the following compounds can be given. In addition, the compounds No. 1 to No. 212 described in International Publication No. 2015 / 152153 can be given.

[0262] [Chemical Formula 11]

[0263]

[0264] The compound represented by the above general formula (A) can be synthesized, for example, by referring to International Publication No. 2015 / 152153, and appropriately selecting a solvent, a reaction temperature, a reaction time, a purification method, and the like according to the material used. In addition, it is also possible to appropriately obtain a commercially available product.

[0265] (Other photoinitiators)

[0266] The photoinitiator in the photosensitive colored resin composition of the present application contains the oxime ester-based photoinitiator represented by the above general formula (A), and from the viewpoint of more favorably adjusting the sensitivity, it can further contain a photoinitiator different from the compound represented by the above general formula (A). Note that, among the other photoinitiators used in the photosensitive colored resin composition of the present application, in addition to the photopolymerization initiator, a chain transfer agent is also included.

[0267] In view of the fact that the development residue in the micro-holes is suppressed when the colored layer is patterned and the micro-holes are formed at the same time, and the cross-sectional shape of the micro-holes becomes good, the photoinitiator in the photosensitive colored resin composition of the present application preferably contains, in addition to the compound represented by the above general formula (A), at least one selected from the group consisting of oxime ester-based photoinitiators, α-amino ketone-based photoinitiators, bisimidazole-based photoinitiators, thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and mercapto-based chain transfer agents, other than the compound represented by the above general formula (A). That is, in the case where a higher sensitivity photoinitiator is used to form the colored layer, after the radicals are generated, the radicals are transferred to the unexposed part, it is difficult to maintain the shape of the unexposed part inside the exposed part, and it is difficult to form the unexposed part peripheral part without the dimensional accuracy being deteriorated. At least one selected from the group consisting of oxime ester-based photoinitiators, α-amino ketone-based photoinitiators, bisimidazole-based photoinitiators, thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and mercapto-based chain transfer agents, other than the compound represented by the above general formula (A), has the property of curing the deep part from the coating film, and it is easy to suppress the curing only at the surface of the coating film.

[0268] Therefore, if at least one selected from the group consisting of oxime ester-based photoinitiators, α-amino ketone-based photoinitiators, bisimidazole-based photoinitiators, thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and mercapto-based chain transfer agents, other than the compound represented by the above general formula (A), is further combined, the sensitivity is maintained to be good, and the curing occurs from the surface to the deep part of the coating film in good balance, the cross-sectional shape of the micro-holes can be controlled, the inclination angle (θ2) of the cross-sectional shape of the micro-holes (see FIG. 2) is less than 90°, and becomes good. Figure 6 ) less than 90°, and becomes good.

[0269] In addition, if at least one selected from the group consisting of oxime ester-based photoinitiators, α-amino ketone-based photoinitiators, bisimidazole-based photoinitiators, thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and mercapto-based chain transfer agents, other than the compound represented by the above general formula (A), is further combined, the sensitivity of the unexposed part can be controlled to be good, and the development residue suppressing effect in the micro-holes becomes high.

[0270] In the case where an oxime ester-based photoinitiator other than the compound represented by the above general formula (A) is used as the other photoinitiator, the cross-sectional shape of the above micro-holes is good, has the effect of suppressing the development residue, and in the case of forming a fine line pattern, it is easy to make the cross-sectional shape good, and is preferred from this point of view.

[0271] As the oxime ester-based photoinitiator different from the compound represented by the above general formula (A), for example, oxime ester-based photoinitiators described in Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Laid-Open No. 2010-527339, Japanese Patent Application Laid-Open No. 2010-527338, Japanese Patent Application Laid-Open No. 2013-041153, and the like can be appropriately selected.

[0272] As the oxime ester-based photoinitiator different from the compound represented by the above general formula (A), from the viewpoint of improving sensitivity, it is preferable to have a carbazole skeleton, a diphenyl sulfide skeleton, or a fluorene skeleton. The oxime ester-based photoinitiator having a carbazole skeleton or a diphenyl sulfide skeleton is easy to improve sensitivity by being combined with the compound represented by the above general formula (A), and is also preferable from the viewpoint of the cross-sectional shape of the colored layer.

[0273] As the oxime ester-based photoinitiator having a carbazole skeleton, for example, the following can be mentioned: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (e.g., Irgacure OXE02, manufactured by BASF), methanone, [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (e.g., Irgacure OXE-03, manufactured by BASF), ethanone, 1-[9-ethyl-6-(1,3-dioxolan-4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(orthoacetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, orthoacetyloxime, 1-propanone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(orthoacetyloxime) (e.g., TR-PBG-304, manufactured by Changzhou Qiangli Electronics New Materials Co., Ltd.), 1-propanone, 3-cyclopentyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(orthoacetyloxime), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(orthoacetyloxime), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-, 1-(orthoacetyloxime), 1-octanone, 1-[4-[3-[1-[(acetyloxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)thio]-2-methylbenzoyl]-9H-carbazol-9-yl]phenyl]-, 1-(orthoacetyloxime) (e.g., EXTA-9, manufactured by UNION Chemical), ADEKA OPT-N-1919 (manufactured by ADEKA), Adeka Arkles NCI-831 (manufactured by ADEKA), and the like as commercially available products.

[0274] As the oxime ester-based photoinitiator having a fluorene skeleton, the oxime ester compound represented by General Formula (1) described in International Publication No. 2018 / 062105 (the oxime ester compound represented by General Formula (D) described below) can be exemplified. The oxime ester compound represented by General Formula (D) described below can be the same as the oxime ester compound represented by General Formula (1) described in International Publication No. 2018 / 062105.

[0275] As the oxime ester-based photoinitiator having a diphenyl sulfide skeleton, the oxime ester compound represented by the following Chemical Formula (C-1), 1,2-octanedione, 1-[4- (phenylthio)phenyl]-, 2-(o-toluyl oxime) (for example, Irgacure OXE01, manufactured by BASF Corporation), 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-, 2-(o- toluyl oxime) (for example, TR-PBG-305, manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 1,2-propanedione, 3-cyclopentyl-1-[4-[(2-hydroxyethoxy)phenylthio]phenyl]-, 2-(o-acetyl oxime), 1-pentanone, 1-[4-[4-(2-benzofuranylcarbonyl)phenylthio]phenyl]-4-methyl, 1-(o-acetyl oxime), TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), Adeka Arkles NCI-930 (manufactured by ADEKA Corporation), Irgacure OXE04 (manufactured by BASF Corporation), and the like can be exemplified.

[0276] [Chemical Formula 12]

[0277] Chemical Formula (C-1)

[0278]

[0279] As the oxime ester-based photoinitiator having a fluorene skeleton, the oxime ester compound represented by General Formula (1) described in International Publication No. 2018 / 062105 (the oxime ester compound represented by General Formula (D) described below) can be exemplified. The oxime ester compound represented by General Formula (D) described below can be the same as the oxime ester compound represented by General Formula (1) described in International Publication No. 2018 / 062105.

[0280] [Chemical Formula 13]

[0281] General Formula (D)

[0282]

[0283] (in General Formula (D), R a and R b are each independently a hydrogen atom or an alkyl group, R c is a hydrocarbon group optionally containing at least one divalent linking group selected from a sulfide bond (-S-), an ether bond (-0-), and a carbonyl bond (-CO-), and Z is a hydrogen atom or -(C=0)R d , R d is a hydrocarbon group optionally containing at least one selected from an oxygen atom and a sulfur atom, or a heterocyclic group not containing a nitrogen atom and containing at least one selected from an oxygen atom and a sulfur atom, and R e is a hydrocarbon group having a carbon number of 1 to 10.)

[0284] As the oxime ester-based photoinitiator having a fluorene skeleton, a compound represented by the following compound (D-1) can be exemplified as a more preferable oxime ester-based photoinitiator having a fluorene skeleton. In addition, as a commercial product, for example, TR-PBG-365 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) can be exemplified.

[0285] [Chemical Formula 14]

[0286]

[0287] As the α-amino ketone-based photoinitiator, for example, 2-methyl-l-(4- methylthiophenyl)-2-morpholinopropan-l-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-l-(4-morpholinophenyl)-l-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-l-[4-(4-morpholinyl)phenyl]-l-butanone (Irgacure 379EG, manufactured by BASF Corporation), and the like can be exemplified.

[0288] As the α-amino ketone-based photoinitiator, two or more kinds can be used alone or in combination, of which, from the viewpoint of inhibiting development residue in the fine pores and making the cross-sectional shape of the fine pores good, 2-methyl-l-(4-methylthiophenyl)-2-morpholinopropan-l-one and 2-benzyl-2-(dimethylamino)-l-(4-morpholinophenyl)-l-butanone are more preferable.

[0289] As the bisimidazole-based photoinitiator, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and the like can be exemplified.

[0290] As the bisimidazole-based photoinitiator, two or more kinds can be used alone or in combination, and among them, from the viewpoint of inhibiting development residue in the fine pores and making the cross-sectional shape of the fine pores good, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferably used.

[0291] As the thioxanthone-based photoinitiator, for example, 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone, and the like can be exemplified.

[0292] As the thioxanthone-based photoinitiator, two or more kinds can be used alone or in combination, and among them, from the viewpoint of inhibiting development residue in the fine pores and making the cross-sectional shape of the fine pores good, 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone are preferably used.

[0293] The acylphosphine oxide-based photoinitiator has a property of less yellowing caused by heat, and is thus suitable for improving the brightness, but generally has a low sensitivity, and sometimes sufficient curability cannot be obtained. However, when combined with the compound represented by the general formula (A) described above, the overall coating film curability is improved, development residue in the fine pores is inhibited, and the cross-sectional shape of the fine pores is made good, and from this point of view, it is preferable.

[0294] As the acylphosphine oxide-based photoinitiator, for example, benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 3,4-dimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,6-dimethylbenzoyl)-ethylphosphine oxide, and the like can be exemplified.

[0295] As the acylphosphine oxide-based photoinitiator, two or more kinds can be used alone or in combination, and among them, from the viewpoint of improving the curing property of the coating film, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred.

[0296] The mercapto-based chain transfer agent has a property of receiving a radical from a radical that reacts slowly and accelerating the reaction, and is preferred from the viewpoint of improving the overall coating film curing property, suppressing the development residue in the fine pores, and making the cross-sectional shape of the fine pores good.

[0297] As the mercapto-based chain transfer agent, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl ester, 3-mercaptopropionic acid ethyl ester, 3-mercaptopropionic acid octyl ester, 1,4-bis(3-mercaptopropionyloxy)butane, 1,3,5-tris(3-mercaptopropoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate), and the like can be exemplified.

[0298] As the mercapto-based chain transfer agent, two or more kinds can be used alone or in combination, and among them, from the viewpoint of improving the reaction speed, 2-mercaptobenzothiazole is preferred.

[0299] The total content of the photoinitiator used in the photosensitive colored resin composition of the present application is not particularly limited as long as the effect of the present application is not impaired, and it is preferably 0.1% by mass or more and 12.0% by mass or less, and further preferably 1.0% by mass or more and 8.0% by mass or less, with respect to the total amount of the solid components of the photosensitive colored resin composition. If the content is the above lower limit value or more, the photocuring sufficiently proceeds, the exposure portion is inhibited from dissolving out at the time of development, and the solvent resistance is good, and on the other hand, if it is the above upper limit value or less, the line width shift is inhibited, and the decrease in brightness caused by yellowing of the obtained colored layer can be inhibited.

[0300] Note that the solid content is all components other than the solvent, and includes liquid multifunctional monomers and the like.

[0301] In addition, the total content of the photoinitiator used in the photosensitive colored resin composition of the present application is preferably 1% by mass or more and 20% by mass or less, and further preferably in a range of 2% by mass or more and 15% by mass or less, relative to the total of the alkali-soluble resin, the multifunctional monomer, and the initiator. If the content is the above lower limit value or more, the photocuring sufficiently proceeds, the exposure portion is inhibited from dissolving out at the time of development, and the solvent resistance is good, and on the other hand, if it is the above upper limit value or less, the line width shift is inhibited, and the decrease in brightness caused by yellowing of the obtained colored layer can be inhibited.

[0302] In the case where the above photoinitiator contains the compound represented by the above general formula (A) and the above other photoinitiator, the content of the compound represented by the above general formula (A) is preferably 10% by mass or more and 98% by mass or less, more preferably 20% by mass or more and 95% by mass or less, and further preferably 30% by mass or more and 95% by mass or less, relative to the total amount of the photoinitiator, from the viewpoint of inhibiting the line width shift, improving the solvent resistance, inhibiting the development residue in the micro-holes, and the cross-sectional shape of the micro-holes, and still further preferably 50% by mass or more and 90% by mass or less, and particularly preferably 60% by mass or more and 90% by mass or less, from the viewpoint of inhibiting the line width shift, improving the solvent resistance, inhibiting the development residue in the micro-holes, and the cross-sectional shape of the micro-holes.

[0303] <Colorant>

[0304] In the present application, the colorant is not particularly limited as long as it can exhibit a desired color at the time of forming a colored layer of a color filter, and can be used alone or in combination with two or more kinds of various organic pigments, inorganic pigments, dispersible dyes, salted compounds of dyes, and the like. Among them, the organic pigments are preferable because they have high color development and high heat resistance. As the organic pigments, compounds classified as pigments (Pigment) in the pigment index (C.I.; published by The Society of Dyers and Colourists) can be exemplified, and specifically, pigments labeled with the pigment index (C.I.) numbers described below can be exemplified.

[0305] C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185 and derivative pigments of C.I. Pigment Yellow 150;

[0306] C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;

[0307] C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;

[0308] C.I. 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, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272, 291;

[0309] C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;

[0310] C.I. Pigment Green 7, 36, 58, 59, 62, 63;

[0311] C.I. Pigment Brown 23, 25;

[0312] C.I. Pigment Black 1, 7.

[0313] Further, as specific examples of the above-mentioned inorganic pigments, there can be mentioned titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow ochre, zinc yellow, red iron oxide (III), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, brown earth, titanium black, synthetic iron black, carbon black, and the like.

[0314] For example, in the case of forming a pattern of a light-shielding layer using the color material dispersion liquid of the present application on a substrate of a color filter, a black pigment having a high light-shielding property is formulated in the ink. As the black pigment having a high light-shielding property, for example, there can be used an inorganic pigment such as carbon black or magnetite; or an organic pigment such as cyanine black.

[0315] As the above-mentioned dispersible dye, there can be mentioned a dye which is capable of being dispersed by imparting various substituents to the dye, or by being used in combination with a solvent having a low solubility.

[0316] As the salt-forming compound of the dye, there can be mentioned a compound in which a dye forms a salt with a counter ion, and there can be mentioned, for example, a salt-forming compound of a basic dye with an acid, a salt-forming compound of an acid dye with a base, and a lake pigment which is obtained by insolubilizing a dye which is soluble in a solvent using a publicly known lake-forming (salt-forming) method.

[0317] In the present application, by using in combination the color material containing at least one selected from the group consisting of a dye and a salt-forming compound of a dye, and the above-mentioned dispersant of the present application, the dispersibility and the dispersion stability of the color material can be improved.

[0318] As the above-mentioned dye, there can be appropriately selected from publicly known dyes. As such a dye, there can be mentioned, for example, an azo dye, a metal complex azo dye, an anthraquinone dye, a triphenylmethane dye, a xanthene dye, a cyanine dye, a naphthoquinone dye, a quinoline imine dye, a methine dye, a phthalocyanine dye, and the like.

[0319] Note that, as a standard, if the amount of the dye dissolved is 10 mg or less with respect to 10 g of the solvent (or the mixed solvent), it can be determined that the dye is capable of being dispersed in the solvent (or the mixed solvent).

[0320] Among them, in the case where the color material contains at least one selected from the group consisting of diketopyrrolopyrrole pigment, quinophthalone pigment, copper phthalocyanine pigment, zinc phthalocyanine pigment, quinophthalone dye, coumarin dye, cyanine dye, and a salt-forming compound of these dyes, the effect of suppressing sublimation or precipitation of the color material is high by using the above-mentioned dispersant, and a colored layer having a high brightness can be formed, and it is preferred from this point of view. Further, as the above-mentioned color material, among them, it is preferred to contain at least one selected from the group consisting of diketopyrrolopyrrole pigment, quinophthalone pigment, copper phthalocyanine pigment, zinc phthalocyanine pigment, quinophthalone dye.

[0321] As diketopyrrolopyrrole pigments, for example, C.I. Pigment Red 254, 255, 264, 272, 291, and a diketopyrrolopyrrole pigment represented by the following general formula (i) can be exemplified, wherein, preferably, it is selected from the group consisting of C.I. Pigment Red 254, 272, 291, and a diketopyrrolopyrrole pigment of the following general formula (i) in which R 21 and R 22 are each 4-bromophenyl.

[0322] [Chemical Formula 15]

[0323] General Formula (i)

[0324]

[0325] (General Formula (i), R 51 and R 52 are each independently 4-chlorophenyl or 4-bromophenyl.)

[0326] As quinophthalone pigments, for example, C.I. Pigment Yellow 138 and the like can be exemplified.

[0327] As phthalocyanine copper pigments, for example, C.I. Pigment Blue 15, 15: 1, 15:2, 15:3, 15:4, 15:5, 15:6, C.I. Pigment Green 7, 36, and the like can be exemplified, wherein, preferably, it is C.I. Pigment Blue 15:6.

[0328] As phthalocyanine zinc pigments, for example, C.I. Pigment Green 58, 59, and the like can be exemplified.

[0329] As quinophthalone dyes, for example, C.I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. Solvent Yellow 114, 157, and the like can be exemplified, wherein, preferably, it is C.I. Disperse Yellow 54.

[0330] The average primary particle diameter of the color material used in the present application is not particularly limited as long as it can exhibit a desired color in the case where a color layer of a color filter is produced, and differs depending on the kind of the color material used, but is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. By making the average primary particle diameter of the color material in the above range, a display device provided with a color filter produced using the photosensitive colored resin composition of the present application can be made high in contrast and high in quality.

[0331] In addition, the average dispersed particle diameter of the color material in the photosensitive colored resin composition differs depending on the kind of the color material used, and is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm.

[0332] The average dispersed particle diameter of the color material in the photosensitive colored resin composition is the dispersed particle diameter of the color material particles dispersed in the dispersion medium containing at least a solvent, and is measured by a laser scattering particle size distribution meter. As the measurement of the particle diameter by the laser scattering particle size distribution meter, the photosensitive colored resin composition can be appropriately diluted (for example, 1000 times or the like) to a concentration that can be measured by the laser scattering particle size distribution meter using a solvent used for the photosensitive colored resin composition, and the measurement can be performed by a dynamic light scattering method at 23°C using a laser scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle diameter herein is a volume average particle diameter.

[0333] The color material used in the present application can be produced by a known method such as a recrystallization method or a solvent salt milling method. Alternatively, a commercially available color material can be subjected to a fine processing and used.

[0334] In the photosensitive colored resin composition of the present application, the content of the color material is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the color material is preferably blended at a proportion of 3% by mass to 65% by mass, more preferably 4% by mass to 60% by mass, with respect to the total amount of the solid components of the photosensitive colored resin composition. If it is equal to or greater than the lower limit of the above range, the colored layer when the photosensitive colored resin composition is applied to a specific film thickness (typically, 1.0 μm to 5.0 μm) has sufficient color density. In addition, if it is equal to or less than the upper limit of the above range, a colored layer having excellent storage stability and sufficient hardness and adhesion to a substrate can be obtained. In particular, in the case of forming a colored layer having a high color material concentration, the total content of the color material is preferably blended at a proportion of 15% by mass to 65% by mass, more preferably 25% by mass to 60% by mass, with respect to the total amount of the solid components of the photosensitive colored resin composition.

[0335] <Alkali-soluble resin>

[0336] The alkali-soluble resin in the present application has an acidic group, and can be appropriately selected from among alkali-soluble resins that function as a binder resin and are soluble in an alkaline developer used when a pattern is formed.

[0337] In the present application, the alkali-soluble resin can be selected as a standard with an acid value of 40 mgKOH / g or more.

[0338] As the alkali-soluble resin, a conventionally known alkali-soluble resin can be appropriately selected and used, and for example, an alkali-soluble resin described in International Publication No. 2016 / 104493 can be appropriately selected and used.

[0339] The preferred alkali-soluble resin in the present application is a resin having an acid group, typically a carboxyl group, specifically, an acrylic resin such as an acrylic copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group, and the like, an epoxy (meth) acrylate resin having a carboxyl group, and the like, can be suitably used. Among these, particularly preferred is a resin having a carboxyl group in the side chain, and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. The reason for this is that, by containing a photopolymerizable functional group, the film strength of the cured film formed is improved. In addition, these acrylic copolymers and styrene-acrylic copolymers and the like, and epoxy acrylate resins can be used in a mixture of two or more.

[0340] The alkali-soluble resin used in the photosensitive colored resin composition can be used alone or in combination of two or more. There is no particular limitation on the content thereof, and the alkali-soluble resin is preferably in the range of 5 to 60% by mass, and further preferably in the range of 10 to 40% by mass, relative to the total amount of the solid components of the photosensitive colored resin composition. If the content of the alkali-soluble resin is equal to or greater than the lower limit value described above, sufficient alkali development can be obtained, and if the content of the alkali-soluble resin is equal to or less than the upper limit value described above, film roughness and pattern defects at the time of development can be suppressed.

[0341] <Photopolymerizable compound>

[0342] The photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, as long as it can be polymerized by the above-described photoinitiator, and typically, a compound having two or more ethylenically unsaturated double bonds is suitably used, and a multifunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferred.

[0343] As such a multifunctional (meth) acrylate, any of the multifunctional (meth) acrylates known in the art can be appropriately selected and used. As specific examples, multifunctional (meth) acrylates described in Japanese Patent Application Publication No. 2013-029832, and the like can be mentioned.

[0344] These multifunctional (meth) acrylates can be used alone or in combination with two or more. In addition, in the case where excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present application, the multifunctional (meth) acrylate preferably has three or more (trifunctional or more) polymerizable double bonds, and is preferably a polyol having three or more valences, a poly(meth) acrylate thereof, or a dicarboxylic acid-modified product thereof, and specifically, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, a succinic acid-modified product of pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta(meth) acrylate, a succinic acid-modified product of dipentaerythritol penta(meth) acrylate, dipentaerythritol hexa(meth) acrylate, and the like.

[0345] The content of the above-mentioned photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, and the photopolymerizable compound is preferably in the range of 5 to 60 mass% and further preferably in the range of 10 to 40 mass% with respect to the total amount of the solid components of the photosensitive colored resin composition. If the content of the photopolymerizable compound is equal to or more than the above-mentioned lower limit, photocuring sufficiently proceeds, the exposure portion is inhibited from dissolving out at the time of development, line width shift is inhibited, solvent resistance becomes good, and further, if the content of the photopolymerizable compound is equal to or less than the above-mentioned upper limit, alkali development is sufficient.

[0346] With respect to the content of the above-mentioned photopolymerizable compound and the containing ratio of the above-mentioned photoinitiator used in the photosensitive colored resin composition, from the viewpoint of inhibiting line width shift, making solvent resistance good, and further improving development residue inhibition effect and cross-sectional shape of the fine pores, the total containing ratio of the above-mentioned photoinitiator is preferably equal to or more than 5 parts by mass and further preferably equal to or more than 10 parts by mass with respect to 100 parts by mass of the above-mentioned photopolymerizable compound, and is preferably equal to or less than 40 parts by mass and further preferably equal to or less than 30 parts by mass.

[0347] < Solvent >

[0348] The solvent used in the present application is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive colored resin composition and can dissolve or disperse them, and can be used alone or in combination with two or more.

[0349] As specific examples of the solvent, there can be mentioned, for example, alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, ethoxy alcohol and the like; carbitol-based solvents such as methoxyethoxyethanol, ethoxyethoxyethanol and the like; ester-based 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, cyclohexyl acetate and the like; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like; glycol ether acetate-based solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-l-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate and the like; carbitol acetate-based solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA) and the like; diacetate-based solvents such as propylene glycol diacetate, 1,3-butanediol diacetate and the like; glycol ether-based 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, dipropylene glycol dimethyl ether and the like; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like; lactone-based solvents such as γ-butyrolactone and the like; cyclic ether-based solvents such as tetrahydrofuran and the like; unsaturated hydrocarbon-based solvents such as benzene, toluene, xylene, naphthalene and the like; saturated hydrocarbon-based solvents such as n-heptane, n-hexane, n-octane and the like; and organic solvents such as aromatic hydrocarbons such as toluene, xylene and the like. Among these solvents, from the viewpoint of solubility of other components, it is appropriate to use glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, ester-based solvents. Among these, from the viewpoint of solubility of other components and coating adaptability, it is preferable to use one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-l-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate.

[0350] In the photosensitive colored resin composition of the present application, the content of the solvent is appropriately set within a range in which a colored layer can be formed with high precision. In general, it is preferable that the content of the solvent is in a range of 55 to 95% by mass, and more preferably in a range of 65 to 88% by mass, with respect to the total amount of the photosensitive colored resin composition including the solvent. By setting the content of the solvent within the above range, the coating property can be made excellent.

[0351] <Other Components>

[0352] In the photosensitive colored resin composition of the present application, various additives can be included as necessary. As the additives, for example, antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like can be exemplified.

[0353] As specific examples of the surfactants and plasticizers, for example, the surfactants and plasticizers described in Japanese Patent Application Publication No. 2013-029832 can be exemplified.

[0354] From the viewpoint of inhibiting line width deviation, the photosensitive colored resin composition of the present application preferably further includes an antioxidant. The photosensitive colored resin composition of the present application includes an antioxidant in combination with the compound represented by the above general formula (A), and does not impair the curability at the time of forming a cured film, and can control excessive radical chain reaction, and thus the straightness is further improved at the time of forming a fine line pattern, or the ability to form a fine line pattern according to the design of the mask line width is improved. In addition, the heat resistance can be improved, and the reduction in brightness after exposure and post-baking can be inhibited, and thus the brightness can be improved.

[0355] As the antioxidant used in the present application, there is no particular limitation, and an antioxidant known in the art can be appropriately selected. As specific examples of the antioxidant, for example, hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like can be exemplified, and from the viewpoint of improving the ability to form a fine line pattern according to the design of the mask line width and the viewpoint of heat resistance, a hindered phenol-based antioxidant is preferably used. It can also be a latent antioxidant as described in International Publication No. 2014 / 021023.

[0356] As the hindered phenol-based antioxidant, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), isocyanuric acid 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) ester (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxybenzyl diethylphosphonate (trade name: Irgamod 195, manufactured by BASF), and the like can be exemplified. Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation) is preferred.

[0357] As the blending amount of the antioxidant, relative to 100 parts by mass of all solid components in the colored resin composition, the antioxidant is preferably 0.1 parts by mass to 10.0 parts by mass, more preferably 0.5 parts by mass to 5.0 parts by mass. If it is equal to or more than the above lower limit value, the ability to form a fine line pattern according to the design of the mask line width is improved, and the heat resistance is excellent. On the other hand, if it is equal to or less than the above upper limit value, the colored resin composition of the present application can be a high-sensitivity photosensitive resin composition.

[0358] In addition, as the blending amount of the antioxidant, relative to 100 parts by mass of the total amount of the oxime ester-based photoinitiator including the compound represented by the above general formula (A), the antioxidant is preferably 1 part by mass to 250 parts by mass, more preferably 3 parts by mass to 80 parts by mass, and further more preferably 5 parts by mass to 45 parts by mass. If it is within the above range, the effect of the above combination is excellent.

[0359] Further, as the silane coupling agent, for example, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be exemplified. Among them, from the viewpoint of adhesion to the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacryl group, an acryl group are preferable.

[0360] As the content of the silane coupling agent, relative to 100 parts by mass of all the solid components in the photosensitive colored resin composition, the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 5.0 parts by mass or less. If it is the above lower limit value or more and the above upper limit value or less, the substrate adhesion is excellent.

[0361] <Method for producing the photosensitive colored resin composition>

[0362] From the viewpoint of improving the contrast, the method for producing the photosensitive colored resin composition of the present application is preferably a method in which a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additive ingredients used as necessary are contained, and the color material is uniformly dispersed in the solvent by the dispersant, and the photosensitive colored resin composition of the present application can be produced by mixing using a publicly known mixing method.

[0363] As the method for producing the resin composition, for example, the following methods can be exemplified: (1) first, a color material dispersing solution is prepared by adding a color material and a dispersant in a solvent, and an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive ingredients used as necessary are mixed in the dispersing solution; (2) a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive ingredients used as necessary are simultaneously put in a solvent and mixed; (3) a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive ingredients used as necessary are added in a solvent, mixed, and then a color material is added and dispersed; (4) a color material, a dispersant, and an alkali-soluble resin are added in a solvent to prepare a color material dispersing solution, and further an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additive ingredients used as necessary are added in the dispersing solution and mixed.

[0364] Among these methods, from the viewpoint of effectively preventing the color material from aggregating and being able to be uniformly dispersed, the methods of the above (1) and (4) are preferable.

[0365] The method for preparing the color material dispersion liquid can be appropriately selected from among publicly known dispersion methods. Examples include: (1) a method in which a dispersant is mixed in advance in a solvent, stirring is performed, a dispersant solution is prepared, an organic acid compound is mixed as necessary so that the amino group possessed by the dispersant forms a salt with the organic acid compound, the color material and other components used as necessary are mixed, and a publicly known stirrer or disperser is used to disperse them; (2) a method in which a dispersant is mixed in a solvent, stirring is performed, a dispersant solution is prepared, the color material and an organic acid compound used as necessary are mixed, and other components used as necessary are further mixed, and a publicly known stirrer or disperser is used to disperse them; and (3) a method in which a dispersant is mixed in a solvent, stirring is performed, a dispersant solution is prepared, the color material and other components used as necessary are mixed, a publicly known stirrer or disperser is used to prepare a dispersion liquid, and an organic acid compound is added as necessary.

[0366] As the disperser used to perform the dispersion treatment, examples include: roll mills such as double roll mills and triple roll mills; ball mills such as a ball mill and a vibration ball mill; and bead mills such as a paint conditioner, a continuous disk-type bead mill, and a continuous ring-type bead mill. As the preferred dispersion conditions for the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

[0367] <Usage>

[0368] The photosensitive colored resin composition of the present application is excellent in the line width deviation and the solvent resistance under low-temperature heating treatment, and is therefore suitably used for a color filter application, and in particular, is suitably used for an application in which a color filter is directly formed on a substrate on which an organic EL element or the like having low heat resistance is formed.

[0369] III. Color Filter

[0370] The color filter of the present application has at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition of the present application.

[0371] The color filter of the present application is described with reference to the accompanying drawings. Figure 1 is a schematic cross-sectional view showing an example of the color filter of the present application. According to Figure 1 , the color filter 10 of the present application has a substrate 1, a light-shielding portion 2, and a colored layer 3.

[0372] <Colored Layer>

[0373] At least one of the colored layers used in the color filter of the present application is a cured product of the photosensitive colored resin composition of the present application.

[0374] The colored layer is formed in an opening of the light-shielding portion on the substrate and is generally composed of three or more colored patterns.

[0375] Further, the arrangement of the colored layer is not particularly limited and, for example, a stripe type, a mosaic type, a triangle type, a 4-pixel arrangement type, or the like can be used. Further, the width, area, or the like of the colored layer can be arbitrarily set.

[0376] The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, or the like of the photosensitive colored resin composition, and is generally preferably in the range of 1 to 5 μm.

[0377] The colored layer can be formed, for example, by the following method.

[0378] First, the photosensitive colored resin composition of the present application is coated on the substrate using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method, to form a wet coating film. Among them, the spin coating method or the die coating method can be preferably used.

[0379] Subsequently, the wet coating film is dried using a hot plate or an oven, and then exposed through a mask having a predetermined pattern to cause a photopolymerization reaction of the alkali-soluble resin and the multifunctional monomer, and the like, thereby forming a cured coating film. As a light source for the exposure, ultraviolet rays of a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or the like, an electron beam, or the like can be used. The exposure amount can be appropriately adjusted depending on the light source used, the thickness of the coating film, or the like.

[0380] Further, after the exposure, a heating treatment can be performed in order to promote the polymerization reaction. The heating conditions can be appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition used, the thickness of the coating film, or the like.

[0381] Next, a developing treatment is performed using a developing solution to dissolve and remove the unexposed portions, thereby forming a coating film in a desired pattern. As the developing solution, a solution in which an alkali is dissolved in water or a water-soluble solvent is generally used. In the alkali solution, a surfactant or the like can be appropriately added. Further, the developing method can be a general method.

[0382] After the developing treatment, a cleaning of the developing solution, a drying of the cured coating film of the photosensitive colored resin composition, and the formation of the colored layer are generally performed. Note that, after the developing treatment, a heating treatment can be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and can be appropriately selected depending on the use of the coating film.

[0383] <Light-shielding portion>

[0384] The light-shielding portion in the color filter of the present application is formed in a pattern on the substrate and can be the same as that used in a general color filter.

[0385] The pattern shape of the light-shielding portion is not particularly limited, and examples include a stripe shape, a matrix shape, and the like. The light-shielding portion can be a metal thin film such as chromium formed by a sputtering method, a vacuum evaporation method, or the like. Alternatively, the light-shielding portion can be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, organic pigments, and the like in a resin binder. In the case of the resin layer containing light-shielding particles, there are methods such as a method of using a photosensitive resist, patterning by development, a method of using inkjet ink containing light-shielding particles to perform patterning, a method of thermally transferring a photosensitive resist, and the like.

[0386] The film thickness of the light-shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and is set to about 0.5 to 2 μm in the case of dispersing or dissolving a black pigment in a binder resin.

[0387] <Substrate>

[0388] As the substrate, a transparent substrate, a silicon substrate, and a substrate in which a thin film of aluminum, silver, silver / copper / palladium alloy, or the like is formed on a transparent substrate or a silicon substrate can be used. On these substrates, other color filter layers, resin layers, transistors such as thin-film transistors (TFTs), circuits, and the like can be formed.

[0389] The transparent substrate in the color filter of the present application is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used in general color filters can be used. Specifically, examples include transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates that do not have flexibility, and transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass that have flexibility.

[0390] The thickness of the transparent substrate is not particularly limited, and a transparent substrate having a thickness of about 100 μm to 1 mm can be used depending on the use of the color filter of the present application.

[0391] Note that the color filter of the present application can be formed with a cover layer, a transparent electrode layer, and further formed with an alignment film, columnar spacers, and the like in addition to the above-described substrate, light-shielding portion, and colored layer.

[0392] IV. Display device

[0393] The display device of the present application is characterized by having the above-described color filter of the present application. The configuration of the display device is not particularly limited in the present application, and can be appropriately selected from conventionally known display devices, and examples include liquid crystal display devices, organic light-emitting display devices, and the like.

[0394] [liquid crystal display device]

[0395] As the liquid crystal display device of the present application, for example, a liquid crystal display device having the above-mentioned color filter of the present application, a counter substrate, and a liquid crystal layer formed between the above-mentioned color filter and the above-mentioned counter substrate can be exemplified.

[0396] The liquid crystal display device of the present application is described with reference to the drawings. Figure 2 is a schematic diagram showing an example of the liquid crystal display device of the present application. As exemplified in Figure 2 the liquid crystal display device 40 of the present application has a color filter 10, a counter substrate 20 having a TFT array substrate or the like, and a liquid crystal layer 30 formed between the above-mentioned color filter 10 and the above-mentioned counter substrate 20.

[0397] Note that the liquid crystal display device of the present application is not limited to the configuration shown in Figure 2 the drawing, and can be configured as a configuration generally known for a liquid crystal display device using a color filter.

[0398] As the driving mode of the liquid crystal display device of the present application, there is no particular limitation, and a driving mode generally used for a liquid crystal display device can be adopted. As such a driving mode, for example, a TN (Twisted Nematic) mode, an IPS (in-plane switching) mode, an OCB (optically compensated bend) mode, and an MVA (Multi-Domain Vertical Alignment) mode, or the like can be exemplified. In the present application, any of these modes can be suitably used.

[0399] In addition, as the counter substrate, a material can be appropriately selected and used depending on the driving mode of the liquid crystal display device of the present application or the like.

[0400] Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals and mixtures thereof having different dielectric anisotropies can be used depending on the driving mode of the liquid crystal display device of the present application or the like.

[0401] As the method of forming the liquid crystal layer, a method generally used as a method of manufacturing a liquid crystal cell can be used, and for example, a vacuum injection method, a liquid crystal dropping method, or the like can be exemplified. After the liquid crystal layer is formed by the above-mentioned method, the liquid crystal cell is slowly cooled to room temperature, whereby the enclosed liquid crystal is oriented.

[0402] [Organic light emitting display device]

[0403] As the organic light emitting display device of the present application, for example, an organic light emitting display device having the above-mentioned color filter of the present application and an organic light emitting body can be exemplified.

[0404] An organic light emitting display device according to the present application will be described with reference to the accompanying drawings. Figure 3 is a schematic diagram showing an example of the organic light emitting display device according to the present application. As shown in the figure, the organic light emitting display device 100 according to the present application has a color filter 10 and an organic light emitting body 80. Between the color filter 10 and the organic light emitting body 80, there can be an organic protective layer 50 and an inorganic oxide film 60. Figure 3 As illustrated, the organic light emitting display device 100 according to the present application has the color filter 10 and the organic light emitting body 80. Between the color filter 10 and the organic light emitting body 80, there can be the organic protective layer 50 and the inorganic oxide film 60.

[0405] As a method of laminating the organic light emitting body 80, there can be mentioned, for example, a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter; a method of attaching the organic light emitting body 80 formed on another substrate to the inorganic oxide film 60; and the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76, and other components of the organic light emitting body 80 can be appropriately used with known components. The organic light emitting display device 100 produced in this way can be applied, for example, to an organic EL display of a passive drive type, and can also be applied to an organic EL display of an active drive type.

[0406] Note that the organic light emitting display device according to the present application is not limited to the configuration shown in the figure, and can employ a configuration known for an organic light emitting display device in general use of a color filter. Figure 3

[0407] Example

[0408] Hereinafter, the present application will be specifically described with reference to examples. The present application is not limited by these descriptions.

[0409] The weight average molecular weight (Mw) of the copolymer before salt formation was determined by GPC (gel permeation chromatography) according to the measurement method described in the above description of the present application, and was calculated as a standard polystyrene conversion value.

[0410] (Synthesis Example 1: Synthesis of Block Copolymer 1)

[0411] ​In a 500 mL round-bottom four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.75 parts by mass of lithium chloride were placed, and nitrogen was sufficiently introduced. After the reaction flask was cooled to -60°C, 6.1 parts by mass of butyllithium (15 mass% hexane solution), 1.4 parts by mass of diisopropylamine, and 1.2 parts by mass of methyl isobutyrate were injected using a syringe. Using the addition funnel, 9 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.4 parts by mass of n-butyl methacrylate (BMA), 7.5 parts by mass of benzyl methacrylate (BzMA), and 47.5 parts by mass of methyl methacrylate (MMA) were added dropwise as monomers for the B block over 60 minutes. After 30 minutes, 22.6 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise as a monomer for the A block over 20 minutes. After 30 minutes of reaction, 1.5 parts by mass of methanol was added to terminate the reaction. The product was reprecipitated in hexane, purified by filtration and vacuum drying, and a block copolymer 1 containing the structural unit represented by the above general formula (I) was obtained. (Amine value: 95 mgKOH / g, acid value: 0 mgKOH / g) The weight average molecular weight Mw was 7600.

[0412] (Synthesis Example 2: Synthesis of block copolymer 2)

[0413] In a 500 mL round-bottom four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were placed, and nitrogen was sufficiently introduced. After the reaction flask was cooled to -60°C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. Using the addition funnel, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 29.1 parts by mass of 2-(trimethylsilyloxy)ethyl methacrylate (TMSMA), 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise over 60 minutes as monomers for the B block. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 20 minutes as a monomer for the A block. After 30 minutes of reaction, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, refined by filtration and vacuum drying, and diluted with PGMEA to prepare a 30 mass% solid content solution. After 32.5 parts by mass of water was added, the temperature was increased to 100°C, and the reaction was performed for 7 hours to deprotect the structural units derived from EEMA to structural units derived from methacrylic acid (MAA) and deprotect the structural units derived from TMSMA to structural units derived from 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, refined by filtration and vacuum drying, and a block copolymer 2 containing the structural units represented by the above general formula (I) was obtained (amine value: 95 mgKOH / g, acid value: 8 mgKOH / g, Tg: 38°C). The weight average molecular weight Mw was 7730.

[0414] (Synthesis Example 3: Synthesis of salt-type block copolymer 3)

[0415] The block copolymer 1 was synthesized in the same manner as in Synthesis Example 1.

[0416] 50 parts by mass of the obtained block copolymer 1 was dissolved in 102 parts by mass of PGMEA. To this, 3.2 parts by mass of benzyl chloride was added, and the reaction was performed at 90°C for 12 hours to obtain a PGMEA solution of the salt-type block copolymer 3 (solid content: 35%).

[0417] (Synthesis Example 4: Synthesis of salt-type block copolymer 4)

[0418] The block copolymer 2 was synthesized in the same manner as in Synthesis Example 2.

[0419] A solution of 50 parts by mass of the obtained block copolymer 2 was dissolved in PGMEA 102 parts by mass. To this, 3.2 parts by mass of benzyl chloride was added, and the reaction was carried out at 90°C for 12 hours to obtain a PGMEA solution of the salt-type block copolymer 4 (solid content 35%).

[0420] (Synthesis Example 5: Synthesis of Graft Copolymer 5)

[0421] (1) Production of Macromonomer A

[0422] In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was added, and while stirring under a nitrogen stream, the temperature was raised to 90°C. A mixed solution of 2.0 parts by mass of a monomer having a PEG chain derived from the structural unit represented by General Formula (III) (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R 44 is CH3, A 3 is COO, R 45 is ethylene, R 46 is CH3, m = 22) 98.0 parts by mass, 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 parts by mass of α,α'-azobisisobutyronitrile (AIBN) was added dropwise over a period of 1.5 hours, and the reaction was further carried out for 3 hours. Next, the nitrogen stream was stopped, and the reaction solution was cooled to 80°C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko K.K.), 0.125 g of dioctyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 30 parts by mass of PGMEA were added, and stirring was carried out for 3 hours, thereby obtaining a 50% solution of macromonomer A. The obtained macromonomer A was confirmed by GPC (gel permeation chromatography) under conditions of 0.01 mol / L lithium bromide-added N-methylpyrrolidone / poly-styrene standard, and the result was a weight average molecular weight (Mw) of 4000 and a molecular weight distribution (Mw / Mn) of 1.6.

[0423] (2) Synthesis of Graft Copolymer 5

[0424] In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 63.1 parts by mass of PGMEA was added, and while stirring under a stream of nitrogen, the temperature was raised to 85°C. A mixed solution of 141 parts by mass (effective solid content: 70.5 parts by mass) of the above-described macromer A solution, 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecyl mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN was added dropwise over a period of 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over a period of 10 minutes, and further, the temperature was maintained for 1 hour at the same temperature, thereby obtaining a 35.0 mass% solution of the graft copolymer A. The obtained graft copolymer 5 was subjected to GPC measurement, and the result was a weight average molecular weight (Mw) of 10500. Note that the amine value was 105 mgKOH / g.

[0425] (Synthesis Example 6: Synthesis of Graft Copolymer 6)

[0426] (1) Production of Macromer B

[0427] In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was added, and while stirring under a stream of nitrogen, the temperature was raised to 90°C. A monomer having a PEG chain derived from the structural unit represented by General Formula (III) (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R 44 is CH3, A 3 is COO, R 45 is ethylene, R 46A mixed solution of 6.0 parts by mass of triethylene glycol monoethyl ether methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., m = 3), 69.0 parts by mass of methyl methacrylate (MMA), 25.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 part by mass of α,α'-azobisisobutyronitrile (AIBN) was further reacted for 3 hours. Next, the nitrogen flow was stopped, and the reaction solution was cooled to 80°C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko K.K.), 0.125 g of dioctyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 30 parts by mass of PGMEA were added, and stirred for 3 hours, whereby a 50% solution of macromer B was obtained. The macromer B obtained was confirmed by GPC (gel permeation chromatography) under conditions of N-methylpyrrolidone / polystyrene standard added with 0.01 mol / L lithium bromide, and the result was that the weight average molecular weight (Mw) was 5800, and the molecular weight distribution (Mw / Mn) was 1.6.

[0428] (2) Synthesis of graft copolymer 6

[0429] In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 63.1 parts by mass of PGMEA was added, and while stirring under a nitrogen stream, the temperature was increased to 85°C. A mixed solution of 141 parts by mass (effective solid content: 70.5 parts by mass) of the macromer B solution described above, 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecyl mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN was added dropwise over a period of 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over a period of 10 minutes, and further aged at the same temperature for 1 hour, whereby a 35.0% solution of graft copolymer 6 was obtained. The graft copolymer 6 obtained was subjected to GPC measurement, and the result was that the weight average molecular weight (Mw) was 10000. Note that the amine value was 105 mgKOH / g.

[0430] (Synthesis Example 7: Synthesis of graft copolymer 7)

[0431] (1) Manufacture of macromer C

[0432] In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 63.1 parts by mass of PGMEA was added, and the temperature was raised to 85°C while stirring under a stream of nitrogen. A solution in which 141 parts by mass of the graft copolymer 7 (effective solid content: 70.5 parts by mass) obtained in the above step, 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecyl mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN were dissolved in PGMEA was added dropwise over a period of 1.5 hours. 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 a period of 10 minutes, and the temperature was maintained for 1 hour to obtain a 35.0 mass% solution of the graft copolymer 7. The obtained graft copolymer 7 was subjected to GPC measurement, and the result was a weight average molecular weight (Mw) of 13000. Note that the amine value was 105 mgKOH / g.

[0433] The weight average molecular weight (Mw) of the obtained graft copolymer 7 was 13000, and the molecular weight distribution (Mw / Mn) was 1.6.

[0434] (2) Synthesis of graft copolymer 7

[0435] In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 63.1 parts by mass of PGMEA was added, and the temperature was raised to 85°C while stirring under a stream of nitrogen. A solution in which 141 parts by mass of the graft copolymer 7 (effective solid content: 70.5 parts by mass) obtained in the above step, 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecyl mercaptan, 49.4 parts by mass of PGMEA, and 1.0 part by mass of AIBN were dissolved in PGMEA was added dropwise over a period of 1.5 hours. 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 a period of 10 minutes, and the temperature was maintained for 1 hour to obtain a 35.0 mass% solution of the graft copolymer 7. The obtained graft copolymer 7 was subjected to GPC measurement, and the result was a weight average molecular weight (Mw) of 13000. Note that the amine value was 105 mgKOH / g.

[0436] (Synthesis Example 8: Synthesis of salt-type graft copolymer 8)

[0437] The graft copolymer 5 was synthesized in the same manner as in Synthesis Example 5.

[0438] 50 parts by mass of the obtained graft copolymer 5 was dissolved in 102 parts by mass of PGMEA. To this, 3.2 parts by mass of benzyl chloride was added, and the reaction was carried out at 90°C for 12 hours to obtain a PGMEA solution of the salt-type block copolymer 8 (solid content 35%).

[0439] (Synthesis Example 9: Synthesis of salt-type graft copolymer 9)

[0440] The graft copolymer 6 was synthesized in the same manner as in Synthesis Example 6.

[0441] 50 parts by mass of the obtained graft copolymer 6 was dissolved in 102 parts by mass of PGMEA. To this, 3.2 parts by mass of benzyl chloride was added, and the reaction was carried out at 90°C for 12 hours to obtain a PGMEA solution of the salt-type block copolymer 9 (solid content 35%).

[0442] (Synthesis Example 10: Synthesis of salt-type graft copolymer 10)

[0443] The graft copolymer 7 was synthesized in the same manner as in Synthesis Example 7.

[0444] 50 parts by mass of the obtained graft copolymer 7 was dissolved in 102 parts by mass of PGMEA. To this, 3.2 parts by mass of benzyl chloride was added, and the reaction was carried out at 90°C for 12 hours to obtain a PGMEA solution of the salt-type block copolymer 10 (solid content 35%).

[0445] (Preparation Example 1: Preparation of base-soluble resin A)

[0446] After the polymerization tank was warmed 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), and 6 parts by mass of PERBUTYL O (manufactured by Nippon Seiro Co., Ltd.) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over a period of 1.5 hours. Thereafter, the temperature was maintained at 100°C, and 0.1 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropwise addition of the above mixture for main chain formation, to terminate the polymerization.

[0447] Next, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added while blowing in air, and the temperature was warmed to 110°C. Then, 0.8 parts by mass of triethylamine was added, and the addition reaction was carried out at 110°C for 15 hours to obtain a base-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH / g, solid content 40% by mass).

[0448] Note that, regarding the method for measuring the weight average molecular weight, the weight average molecular weight was measured by a Shodex GPC system-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent. In addition, regarding the method for measuring the acid value, the measurement was performed based on JIS K 0070.

[0449] (Production Example 1: Production of Color Material Dispersion R(1))

[0450] In a 225 mL mayonnaise jar, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the solution of the alkali-soluble resin A of Preparation Example 1 (solid content 40 mass%), and 9.2 parts by mass of the PGMEA solution of the block copolymer 1 of Synthesis Example 1 (solid content 35 mass%) were added and stirred. To this, 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nippon Shokubai Co., Ltd.) was added, and stirring was performed at room temperature for 30 minutes.

[0451] To this, 9.6 parts by mass of C.I. Pigment Red 177 (PR177), 2.4 parts by mass of C.I. Pigment Red 254 (PR254), and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were added, and pre-crushing was performed by a paint shaker (manufactured by Hatta Tekko Co., Ltd.) for 1 hour. Subsequently, the zirconia beads were changed to 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm, and main crushing was performed by the paint shaker for 4 hours to obtain the color material dispersion R(1). Note that the block copolymer 1 was salted with phenylphosphonic acid to become the salt-type block copolymer 1.

[0452] (Production Example 2: Production of Color Material Dispersion R(2))

[0453] In the production of the color material dispersion R(1) of Production Example 1, the block copolymer 1 of Synthesis Example 1 was changed to the block copolymer 2 of Synthesis Example 2, and otherwise, the color material dispersion R(2) was obtained in the same manner as the color material dispersion R(1) of Production Example 1. Note that, in the color material dispersion R(2), the block copolymer 2 was salted with phenylphosphonic acid to become the salt-type block copolymer 2.

[0454] (Production Example 3: Production of Color Material Dispersion R(3))

[0455] In the production of the color material dispersion R(1) of Production Example 1, the block copolymer 1 of Synthesis Example 1 was changed to the graft copolymer 5 of Synthesis Example 5, and otherwise, the color material dispersion R(3) was obtained in the same manner as the color material dispersion R(1) of Production Example 1. Note that, in the color material dispersion R(3), the graft copolymer 5 was salted with phenylphosphonic acid to become the salt-type graft copolymer 5.

[0456] (Production Example 4: Production of Color Material Dispersion R(4))

[0457] The block copolymer 1 of Synthesis Example 1 in the production of the color material dispersion R(1) of Production Example 1 was changed to the graft copolymer 6 of Synthesis Example 6, and otherwise, the color material dispersion R(4) was obtained in the same manner as the color material dispersion R(1) of Production Example 1. Note that in the color material dispersion R(4), the graft copolymer 6 forms a salt with phenylphosphonic acid to become the salt-type graft copolymer 6.

[0458] (Production Example 5: Production of Color Material Dispersion R(5))

[0459] The block copolymer 1 of Synthesis Example 1 in the production of the color material dispersion R(1) of Production Example 1 was changed to the graft copolymer 7 of Synthesis Example 7, and otherwise, the color material dispersion R(5) was obtained in the same manner as the color material dispersion R(1) of Production Example 1. Note that in the color material dispersion R(5), the graft copolymer 7 forms a salt with phenylphosphonic acid to become the salt-type graft copolymer 7.

[0460] (Production Example 6: Production of Color Material Dispersion R(6))

[0461] The color material dispersion R(1) obtained in Production Example 1, 35.7 parts by mass, the alkali-soluble resin A solution (solid content 40 mass%) obtained in Preparation Example 1, 3.52 parts by mass, a multifunctional monomer (trade name ARONIX M-305, manufactured by TOAGOSEI CO., LTD.), 5.64 parts by mass, the oxime ester compound represented by the above formula (A-1), 0.45 parts by mass (6 mass% relative to the total of the alkali-soluble resin, the multifunctional monomer, and the initiator), a fluorine-based surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Corporation), 0.03 parts by mass, and PGMEA, 54.66 parts by mass, were added, and a photosensitive colored resin composition R-1 was obtained.

[0462] (Production Examples 2 to 8: Production of Photosensitive Colored Resin Compositions R-2 to R-8)

[0463] The photosensitive colored resin compositions R-2 to R-8 were obtained in the same manner as the photosensitive colored resin composition R-1, except that the kind and amount of the initiator in Production Example 1 were changed as shown in Table 1.

[0464] (Production Examples 9 to 12: Production of Photosensitive Colored Resin Compositions R-9 to R-12)

[0465] As shown in Table 1, the color material dispersion liquid R (1) in Example 1 was changed to color material dispersion liquids R (2), R (3), R (4), or R (5), and otherwise, the photosensitive colored resin composition R-9 to R-12 was obtained in the same manner as the photosensitive colored resin composition R-1.

[0466] (Example 13: Production of Photosensitive Colored Resin Composition R-13)

[0467] The color material dispersion liquid R (1) obtained in Production Example 1 was added at 35.7 parts by mass, the alkali-soluble resin A solution obtained in Preparation Example 1 was added at 3.49 parts by mass, a multifunctional monomer (trade name ARONIX M-305, manufactured by TOAGOSEI CO., LTD.) was added at 5.58 parts by mass, an oxime ester compound represented by Formula (A-1) was added at 0.45 parts by mass, a fluorine-based surfactant (trade name MEGAFAC R-08MH, manufactured by DIC Corporation) was added at 0.03 parts by mass, an antioxidant Irganox 1010 was added at 0.07 parts by mass (1.0 mass% relative to the total of the alkali-soluble resin, the multifunctional monomer, and the initiator), and PGMEA was added at 54.68 parts by mass, to obtain the photosensitive colored resin composition R-13.

[0468] (Production Example 6: Production of Color Material Dispersion Liquid G (1))

[0469] A color material dispersion liquid G (1) was obtained in the same manner as the color material dispersion liquid R (1) of Production Example 1, except that C.I. Pigment Green 58 (PG58) 8.4 parts by mass and C.I. Pigment Yellow 138 (PY138) 3.6 parts by mass were used instead of C.I. Pigment Red 177 (PR177) 9.6 parts by mass and C.I. Pigment Red 254 (PR254) 2.4 parts by mass in the production of the color material dispersion liquid R (1) of Production Example 1. Note that, in the color material dispersion liquid G (1), the block copolymer 1 was salted by phenylphosphonic acid to become a salt-type block copolymer 1.

[0470] (Production Examples 7 to 10: Production of Color Material Dispersion Liquids G (2) to G (5))

[0471] A color material dispersion liquid G (2), G (3), G (4), or G (5) was obtained in the same manner as the color material dispersion liquid G (1) of Production Example 6, except that the block copolymer 1 of Synthesis Example 1 in the production of the color material dispersion liquid G (1) of Production Example 6 was changed to the block copolymer 2 of Synthesis Example 2, the graft copolymer 5 of Synthesis Example 5, the graft copolymer 6 of Synthesis Example 6, or the graft copolymer 7 of Synthesis Example 7, respectively.

[0472] Note that in the color material dispersions G (2) to G (5), the block copolymer 2, the graft copolymers 5, 6, and 7 are each formed into a salt by forming a salt with phenylphosphonic acid, to become a salt-type block copolymer 2, a salt-type graft copolymer 5, 6, and 7.

[0473] (Example 14: Production of a photosensitive colored resin composition G-1)

[0474] The color material dispersion R (1) obtained in Production Example 1 in Example 1 was changed to the color material dispersion G (1) obtained in Production Example 6, and otherwise, a photosensitive colored resin composition G-1 was obtained in the same manner as the photosensitive colored resin composition R-1.

[0475] (Examples 15 to 21: Production of photosensitive colored resin compositions G-2 to G-8)

[0476] As shown in Table 2, the kind and amount of the initiator in Example 14 were changed, and otherwise, photosensitive colored resin compositions G-2 to G-8 were obtained in the same manner as the photosensitive colored resin composition G-1.

[0477] (Examples 22 to 25: Production of photosensitive colored resin compositions G-9 to G-12)

[0478] As shown in Table 2, the color material dispersion G (1) in Example 14 was changed to the color material dispersion G (2), G (3), G (4), or G (5), and otherwise, photosensitive colored resin compositions G-9 to G-12 were obtained in the same manner as the photosensitive colored resin composition G-1.

[0479] (Example 26: Production of a photosensitive colored resin composition G-13)

[0480] The color material dispersion R (1) obtained in Production Example 1 in Example 13 was changed to the color material dispersion G (1) obtained in Production Example 6, and otherwise, a photosensitive colored resin composition G-13 was obtained in the same manner as the photosensitive colored resin composition R-13.

[0481] (Production Example 11: Production of a color material dispersion B (1))

[0482] In a 225 mL mayonnaise jar, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution (solid content 40 mass%) of Production Example 1, and 9.2 parts by mass of the PGMEA solution (solid content 35 mass%) of the salt-type block copolymer 3 of Synthesis Example 3 were added and stirred.

[0483] To this, C.I. Pigment Blue 15:6 (PB15:6) 9.6 parts by mass, C.I. Pigment Violet 23 (PV23) 2.4 parts by mass, and zirconia beads having a particle diameter of 2.0 mm 100 parts by mass were added, and pre-crushing was performed by a paint shaker (manufactured by Shikido Iron Works Co., Ltd.) for 1 hour, and then the zirconia beads having a particle diameter of 0.1 mm 200 parts were changed, and formal crushing was performed by the paint shaker for 4 hours to obtain a color material dispersion liquid B(1).

[0484] (Production Examples 12 to 15: Production of color material dispersion liquids B(2) to B(5))

[0485] The PGMEA solution of the salt-type block copolymer 3 of Synthesis Example 3 in the production of the color material dispersion liquid B(1) of Production Example 11 was changed to the PGMEA solution of the salt-type block copolymer 4 of Synthesis Example 4, the PGMEA solution of the salt-type graft copolymer 8 of Synthesis Example 8, the PGMEA solution of the salt-type graft copolymer 9 of Synthesis Example 9, or the PGMEA solution of the salt-type graft copolymer 10 of Synthesis Example 10, respectively, and otherwise, the color material dispersion liquids B(2), B(3), B(4), or B(5) were obtained in the same manner as the color material dispersion liquid B(1) of Production Example 11.

[0486] (Example 27: Production of a photosensitive colored resin composition B-1)

[0487] The color material dispersion liquid R(1) obtained in Production Example 1 in Example 1 was changed to the color material dispersion liquid B(1) obtained in Production Example 11, and otherwise, the photosensitive colored resin composition B-1 was obtained in the same manner as the photosensitive colored resin composition R-1.

[0488] (Examples 28 to 34: Production of photosensitive colored resin compositions B-2 to B-8)

[0489] The photosensitive colored resin compositions B-2 to B-8 were obtained in the same manner as the photosensitive colored resin composition B-1, except that the kind and amount of the initiator in Example 27 were changed as shown in Table 3.

[0490] (Examples 35 to 38: Production of photosensitive colored resin compositions B-9 to B-12)

[0491] The photosensitive colored resin compositions B-9 to B-12 were obtained in the same manner as the photosensitive colored resin composition B-1, except that the color material dispersion liquid B(1) in Example 27 was changed to the color material dispersion liquid B(2), B(3), B(4), or B(5) as shown in Table 3.

[0492] (Example 39: Production of a photosensitive colored resin composition B-13)

[0493] The color material dispersion liquid R (1) obtained in Production Example 1 in Example 1 was changed to the color material dispersion liquid B (1) obtained in Production Example 11, and otherwise, a photosensitive colored resin composition B-13 was obtained in the same manner as the photosensitive colored resin composition R-13.

[0494] (Production of photosensitive colored resin compositions R-14 to R-26 (Examples 40 to 52))

[0495] As shown in Table 4, the oxime ester compound represented by the above formula (A-1) in Examples 1 to 13 was changed to the oxime ester compound represented by the above formula (A-2), respectively, and otherwise, photosensitive colored resin compositions R-14 to R-26 were obtained in the same manner as the photosensitive colored resin compositions R-1 to R-13.

[0496] (Production of photosensitive colored resin compositions G-14 to G-26 (Examples 53 to 65))

[0497] As shown in Table 5, the oxime ester compound represented by the above formula (A-1) in Examples 14 to 26 was changed to the oxime ester compound represented by the above formula (A-2), respectively, and otherwise, photosensitive colored resin compositions G-14 to G-26 were obtained in the same manner as the photosensitive colored resin compositions G-1 to G-13.

[0498] (Production of photosensitive colored resin compositions B-14 to B-26 (Examples 66 to 78))

[0499] As shown in Table 6, the oxime ester compound represented by the above formula (A-1) in Examples 27 to 39 was changed to the oxime ester compound represented by the above formula (A-2), respectively, and otherwise, photosensitive colored resin compositions B-14 to B-26 were obtained in the same manner as the photosensitive colored resin compositions B-1 to B-13.

[0500] (Production of photosensitive colored resin compositions R-27 to R-32 (Examples 79 to 84))

[0501] As shown in Table 7, the oxime ester compound represented by the above formula (A-1) in Examples 1 and 9 to 13 was changed to the oxime ester compound represented by the above formula (A-3), respectively, and otherwise, photosensitive colored resin compositions R-27 to R-32 were obtained in the same manner as the photosensitive colored resin compositions R-1 and R-9 to R-13.

[0502] (Production of photosensitive colored resin compositions R-33 to R-38 (Examples 85 to 90))

[0503] As shown in Table 7, the oxime ester compound represented by the above formula (A-1) in Examples 1 and 9 to 13 was changed to the oxime ester compound represented by the above formula (A-4), and otherwise, the photosensitive colored resin composition R-33 to R-38 was obtained in the same manner as the photosensitive colored resin compositions R-1 and R-9 to R-13.

[0504] (Comparative Examples 1 to 3: Production of Photosensitive Colored Resin Compositions CR-1, CG-1 and CB-1)

[0505] As shown in Table 7, the oxime ester compound represented by the above formula (A-1) in Example 1, Example 14 or Example 27 was changed to the oxime ester photoinitiator having a carbazole skeleton, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name Irgacure OXE02, manufactured by BASF Corporation), and otherwise, the photosensitive colored resin compositions CR-1, CG-1 and CB-1 were produced in the same manner as Example 1, Example 14 or Example 27.

[0506] (Comparative Production Examples 1 and 2: Production of Color Material Dispersion Liquids CR(1) and CR(2))

[0507] As shown in Table 7, the block copolymer 1 of Synthesis Example 1 in the production of the color material dispersion liquid R(1) of Production Example 1 was changed to Ajisper PB821 (PB821, manufactured by Ajinomoto Fine-Techno Co., Ltd., polyester-based dispersant, solid content 30 mass%) or Disperbyk-161 (BYK-161, manufactured by BYK-Chemie, urethane-based dispersant, solid content 30 mass%) respectively, and was used in the same amount by mass of the solid content as the block copolymer 1, and phenylphosphonic acid was not added, and the amount of PGMEA was adjusted so that the solid content of the dispersion liquid was the same as that of Production Example 1, and otherwise, the color material dispersion liquids CR(1) and CR(2) were obtained in the same manner as the color material dispersion liquid R(1) of Production Example 1.

[0508] (Comparative Production Examples 3 and 4: Production of Color Material Dispersion Liquids CG(1) and CG(2))

[0509] As shown in Table 7, the PGMEA solution (solid content 35 mass%) of the salt-type block copolymer 3 of Synthesis Example 3 in the production of the color material dispersion liquid B(l) of Production Example 11 was changed to Ajisper PB821 (PB821, manufactured by Ajinomoto Fine-Techno Co., Ltd., polyester-based dispersant, solid content 30 mass%) or Disperbyk-161 (BYK-161, manufactured by BYK-Chemie, urethane-based dispersant, solid content 30 mass%), respectively, was used in the same mass parts of the solid content as the block copolymer 1, the amount of PGMEA was adjusted so that the solid content of the dispersion liquid was the same as that of Production Example 11, and otherwise, the color material dispersion liquids CB(l) and CB(2) were obtained in the same manner as the color material dispersion liquid B(l) of Production Example 11.

[0510] (Production of color material dispersion liquids CB(l) and CB(2) (Comparative Production Examples 5 and 6))

[0511] As shown in Table 7, the PGMEA solution (solid content 35 mass%) of the salt-type block copolymer 3 of Synthesis Example 3 in the production of the color material dispersion liquid B(l) of Production Example 11 was changed to Ajisper PB821 (PB821, manufactured by Ajinomoto Fine-Techno Co., Ltd., polyester-based dispersant, solid content 30 mass%) or Disperbyk-161 (BYK-161, manufactured by BYK-Chemie, urethane-based dispersant, solid content 30 mass%), respectively, was used in the same mass parts of the solid content as the block copolymer 1, the amount of PGMEA was adjusted so that the solid content of the dispersion liquid was the same as that of Production Example 11, and otherwise, the color material dispersion liquids CB(l) and CB(2) were obtained in the same manner as the color material dispersion liquid B(l) of Production Example 11.

[0512] (Production of photosensitive colored resin compositions CR-2 and CR-3 (Comparative Examples 4 and 5))

[0513] As shown in Table 7, the color material dispersion liquid R(l) in Example 1 was changed to the color material dispersion liquid CR(l) or CR(2), respectively, and otherwise, the photosensitive colored resin composition CR-2 or CR-3 was produced in the same manner as Example 1.

[0514] (Production of photosensitive colored resin compositions CG-2 and CG-3 (Comparative Examples 6 and 7))

[0515] As shown in Table 7, the color material dispersion liquid G(l) in Example 14 was changed to the color material dispersion liquid CG(l) or CG(2), respectively, and otherwise, the photosensitive colored resin composition CG-2 or CG-3 was produced in the same manner as Example 14.

[0516] (Comparative Examples 8 to 9: Production of photosensitive colored resin compositions CB-2, CB-3)

[0517] As shown in Table 7, the color material dispersion liquid B(l) in Example 27 was changed to color material dispersion liquid CB(l) or CB(2), respectively, and otherwise, the photosensitive colored resin composition CB-2 or CB-3 was produced in the same manner as in Example 27.

[0518] [Method of Evaluation]

[0519] After the photosensitive colored resin composition obtained in each of Examples and Comparative Examples was applied on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") in such a manner that the thickness of the cured coating film became 3.0 μm using a spin coater, a hot plate was used to dry the coating film at 80°C for 3 minutes to form a coating film on the glass substrate. The coating film was exposed to ultraviolet rays at 40 mJ / cm2using an ultrahigh pressure mercury lamp through a pattern photomask (chromium mask) in which a chromium mask of 20 μm x 20 μm was disposed in the center of an independent fine line of an opening size of 90 μm x 300 μm, thereby forming an exposed coating film on the glass substrate. Subsequently, a rotation development was performed with 0.05 wt% potassium hydroxide aqueous solution as a developing solution, and after the coating film was contacted with the developing solution for 60 seconds, it was washed with pure water, thereby performing a development treatment to obtain an independent fine line pattern coating film having micropores. Thereafter, a post-baking was performed in a dust-free oven at 90°C for 25 minutes, thereby forming an independent fine line pattern colored layer having micropores. The obtained colored layer was subjected to the following evaluations. 2

[0520] <Line Width Shift Amount Evaluation>

[0521] The width of the fine line pattern of the colored layer corresponding to the opening width of 90 μm of the chromium mask used at the time of exposure was measured at five points by an optical microscope, and the line width shift amount was evaluated based on the difference between the average value of the line width and the target line width.

[0522] (Line Width Shift Amount Evaluation Criteria)

[0523] A: The difference was within 1.5 μm with respect to the target line width

[0524] B: The difference was more than 1.5 μm and within 3.0 μm with respect to the target line width

[0525] C: The difference was more than 3.0 μm and within 4.0 μm with respect to the target line width

[0526] D: The difference was more than 4.0 μm with respect to the target line width

[0527] If the evaluation result was B, the line width shift amount was good, and if the evaluation result was A, the line width shift amount was excellent.​

[0528] < Solvent resistance (PGME resistance) evaluation >

[0529] After measuring the film thickness of the obtained colored layer, the film thickness was measured again after immersing in propylene glycol monomethyl ether (PGME) for 10 minutes and then air-drying. Note that in the film thickness measurement, a stylus-type step film thickness meter "P-15 Tencor" (manufactured by Instruments) was used. The film thickness after solvent immersion / film thickness before solvent immersion x 100 was calculated as the residual film rate.

[0530] ( Evaluation criteria for solvent resistance )

[0531] A: Residual film rate after solvent immersion is 98% or more

[0532] B: Residual film rate after solvent immersion is 96% or more and less than 98%

[0533] C: Residual film rate after solvent immersion is 94% or more and less than 96%

[0534] D: Residual film rate after solvent immersion is less than 94%

[0535] If the evaluation result is B, the solvent resistance is good, and if the evaluation result is A, the solvent resistance is excellent.

[0536] < Cross-sectional shape of fine line patterned colored layer >

[0537] The thickness direction cross-sectional shape of the obtained independent fine line patterned colored layer was observed by a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification 10000x), and the inclination angle (θ1) of the cross-sectional shape of the colored layer was evaluated with the following evaluation criteria. Figure 5 ) was evaluated.

[0538] ( Evaluation criteria for cross-sectional shape of patterned colored layer )

[0539] A: Inclination angle (θ1) is 15 degrees or more and less than 70 degrees

[0540] B: Inclination angle (θ1) is 70 degrees or more and less than 90 degrees

[0541] C: Inclination angle (θ1) is 90 degrees or more and less than 100 degrees

[0542] D: Inclination angle (θ1) is 100 degrees or more

[0543] If the evaluation result is B, the cross-sectional shape of the colored layer is good, and if the evaluation result is A, the cross-sectional shape of the colored layer is excellent.

[0544] < Cross-sectional shape of micropore >

[0545] The thickness direction cross-sectional shape of the colored layer of the micro-hole was observed by a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification 10000 times), and the inclination angle (θ2) of the cross-sectional shape of the micro-hole was evaluated based on the following evaluation criteria. Figure 6

[0546] (Evaluation Criteria of Cross-sectional Shape of Micro-hole)

[0547] A: Inclination angle (θ2) is 15 degrees or more and less than 70 degrees

[0548] B: Inclination angle (θ2) is 70 degrees or more and less than 90 degrees

[0549] C: Inclination angle (θ2) is 90 degrees or more and less than 100 degrees

[0550] D: Inclination angle (θ2) is 100 degrees or more

[0551] If the evaluation result is B, the cross-sectional shape of the micro-hole is good, and if the evaluation result is A, the cross-sectional shape of the micro-hole is excellent.

[0552] <Residue in Micro-hole>

[0553] The micro-hole was observed by a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification 5000 times), and the residue in the micro-hole was evaluated based on the following evaluation criteria.

[0554] (Evaluation Criteria of Residue in Micro-hole)

[0555] A: No residue was observed at all.

[0556] B: Only a little residue was observed at the end portion in the hole.

[0557] C: A little residue was observed in the whole hole

[0558] D: Much residue was observed in the whole hole

[0559] If the evaluation result is B, the residue in the micro-hole is good, and if the evaluation result is A, the residue in the micro-hole is excellent.

[0560] <Development Residue Inhibition Evaluation>

[0561] ​Using a spin coater, the photosensitive coloring resin compositions obtained in the examples and comparative examples, after baking to form a coloring layer with a thickness of 2.0 μm, were coated onto glass substrates (manufactured by NH TECHNO GLASS Co., Ltd., "NA35"). The substrates were then dried at 80°C for 3 minutes using a heated plate to form the coloring layer. For the glass substrate with the coloring layer formed, a 0.05% (w / w) potassium hydroxide aqueous solution was used as an alkaline developer for 60 seconds of spray development, followed by rinsing with pure water. After visually observing the formed portion of the coloring layer, the surface was thoroughly wiped with a lens cloth containing ethanol (manufactured by Toray Industries, Ltd., trade name Toraysee MK Clean Cloth) to visually observe the degree of coloring on the lens cloth.

[0562] (Evaluation criteria for suppressing developer residue)

[0563] A: No developer residue was visually detected, and the lens cleaning cloth was completely unstained.

[0564] B: No developer residue was visually detected, but the lens cleaning cloth was slightly stained.

[0565] C: Visually confirm the presence of a small amount of developing residue and the staining of the lens cleaning cloth.

[0566] D: Visually confirm the presence of developing residue and staining of the lens cleaning cloth.

[0567] If the evaluation result is B, the developer residue suppression effect is good; if the evaluation result is A, the developer residue suppression effect is excellent.

[0568] <Water Spot Suppression Evaluation>

[0569] Using a spin coater, the photosensitive coloring resin compositions obtained in the examples and comparative examples, after baking to form a coloring layer with a thickness of 2.0 μm, were coated onto glass substrates (manufactured by NH TECHNO GLASS Co., Ltd., "NA35", thickness 0.7 mm, 100 mm × 100 mm). The substrates were then dried at 60°C for 3 minutes using a heating plate, and the entire surface was irradiated with an ultra-high pressure mercury lamp at 30 mJ / cm² without a photomask. 2 Ultraviolet light is used to form a coloring layer on the glass substrate. Subsequently, after spray development with 0.05 wt% potassium (KOH) as the developer for 60 seconds, the substrate is rinsed with pure water and then developed. After rinsing, the substrate is rotated for 10 seconds, centrifuged to remove water, and the water spot is evaluated by measuring the contact angle of pure water immediately as follows.

[0570] As to the measurement of the contact angle of pure water, a droplet of 1.0 μL of pure water was dropped on the surface of the colored layer immediately after the removal of water by centrifugation, and the static contact angle after the adhesion of the droplet for 10 seconds was measured according to the θ / 2 method. The measurement was performed using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. as a measuring device.

[0571] (Water Spot Inhibition Evaluation Criteria)

[0572] A: Contact angle of 70 degrees or more

[0573] B: Contact angle of 50 degrees or more and less than 70 degrees

[0574] C: Contact angle of 30 degrees or more and less than 50 degrees

[0575] D: Contact angle of less than 30 degrees

[0576] If the water spot inhibition evaluation criteria is A or B, it is usable in terms of practicality, and if the evaluation result is A, the effect is more excellent.

[0577] Note that in Tables 1 to 7, the compound represented by the above general formula (A) and other initiators other than the compound represented by the above general formula (A) are as described below, respectively.

[0578] <Compound represented by the above general formula (A)>

[0579] • A-1: Compound represented by the above chemical formula (A-1)

[0580] • A-2: Compound represented by the above chemical formula (A-2)

[0581] • A-3: Compound represented by the above chemical formula (A-3)

[0582] • A-4: Compound represented by the above chemical formula (A-4)

[0583] <Other initiators>

[0584] • Initiator 1: oxime ester-based photoinitiator having a carbazole skeleton, trade name Adeka Arkles NCI-831, manufactured by ADEKA Co., Ltd.

[0585] • Initiator 2: α-amino ketone-based photoinitiator, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (trade name Irgacure 369, manufactured by BASF Co., Ltd.)

[0586] • Initiator 3: α-amino ketone-based photoinitiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by BASF Co., Ltd.)

[0587] • Initiator 4: Thiol chain transfer agent, 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0588] • Initiator 5: Bisimidazole is a photoinitiator, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- tetraphenyl-1,2'-biimidazole (manufactured by Kagaku Kogyo)

[0589] • Initiator 6: Thioxanthone-based photoinitiator, 2,4-diethylthioxanthone (trade name DOUBLE CURE DETX, manufactured by Double Bond Chemical)

[0590] • Initiator 7: Acylphosphine-based photoinitiator, phenyl bis(2,4,6- trimethylbenzoyl) phosphine oxide (trade name Irgacure 819, manufactured by BASF)

[0591] [Table 1]

[0592]

[0593] [Table 2]

[0594]

[0595] [Table 3]

[0596]

[0597] [Table 4]

[0598]

[0599] [Table 5]

[0600]

[0601] [Table 6]

[0602]

[0603] [Table 7]

[0604]

[0605] [Results]

[0606] In the comparative photosensitive coloring resin compositions of Comparative Examples 1 to 3 in which the compound represented by the specific general formula (A) of the present application is not used as a photoinitiator, the line width offset is large, and the solvent resistance obtained by low-temperature heat treatment is poor.

[0607] In Comparative Examples 4 to 9 in which a polyester-based dispersant or a urethane-based dispersant was used as a dispersant even though the compound represented by the specific general formula (A) of the present application was used as a photoinitiator, the line width offset amount became large, and the solvent resistance obtained by low-temperature heat treatment was poor.

[0608] It was shown that, in the photosensitive colored resin compositions of Examples 1 to 90 in which at least the compound represented by the general formula (A) was used as a photoinitiator and a (meth)acrylate copolymer-based dispersant was used as a dispersant, a colored layer in which the line width offset amount was suppressed and the solvent resistance under low-temperature heat treatment was also good could be formed.

[0609] It was shown in the examples that, if the photoinitiator further contained at least one selected from the group consisting of an oxime ester-based photoinitiator, an α-amino ketone-based photoinitiator, a bisimidazole-based photoinitiator, a thioxanthone-based photoinitiator, an acylphosphine oxide-based photoinitiator, and a mercapto-based chain transfer agent, in addition to the compound represented by the above general formula (A), the cross-sectional shape of the micropores was good, and the residue in the micropores was suppressed.

[0610] In addition, it was shown that, if a (meth)acrylate copolymer-based dispersant having an acid value of 1 to 18 mgKOH / g and a glass transition temperature of 30°C or higher was used as a dispersant, the solvent resistance was improved by combination with the compound represented by the above general formula (A), and the development residue was suppressed from being generated.

[0611] In addition, it was shown that, if a (meth)acrylate copolymer-based dispersant which was a graft copolymer and in which at least one structural unit selected from the group consisting of the structural unit represented by general formula (III) and the structural unit represented by the following general formula (III') was contained in the structural unit of the graft polymer chain was used as a dispersant, the solvent resistance was improved by combination with the compound represented by the above general formula (A). It was also shown that, if the structural unit represented by the above general formula (III) in which m represented a number of 19 or higher and 80 or lower was contained in the structural unit of the graft polymer chain, the water stain suppression effect was improved.

[0612] It was also shown that, if an antioxidant was further added, the line width offset amount was good.

[0613] Explanation of Reference Signs

[0614] 1: substrate

[0615] 2: light shielding portion

[0616] 3: colored layer

[0617] 5: micropore

[0618] 10: color filter

[0619] 20: counter substrate

[0620] 30: liquid crystal layer

[0621] 40: liquid crystal display device

[0622] 50: organic protective layer

[0623] 60: inorganic oxide film

[0624] 71: transparent anode

[0625] 72: hole injection layer

[0626] 73: hole transport layer

[0627] 74: light emitting layer

[0628] 75: electron injection layer

[0629] 76: cathode

[0630] 80: organic light emitting body

[0631] 100: organic light emitting display device

Claims

1. A photosensitive colored resin composition comprising a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and the dispersant comprises a (meth)acrylate copolymer dispersant, the photoinitiator comprises a compound represented by the following general formula (A), wherein R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN, R 11 , R 12 , and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 11 , R 12 and R 13 represent a group optionally further substituted by a hydrogen atom, a R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN or a halogen atom, R 21 , R 22 , and R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 21 , R 22 and R 23 represents a hydrogen atom optionally further substituted with a hydroxy group, a nitro group, CN, a halogen atom or a carboxyl group, R 11 , R 12 , R 13 , R 21 , R 22 and R 23 denote a group which optionally contains 1 to 5 -0-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- in such a way that oxygen atoms are not adjacent, R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The alkyl portion of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 optionally has a branched side chain, optionally is a cyclic alkyl group, R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 3 The alkyl moiety of the group represented by R 3 may optionally have a branched side chain, may optionally be a cyclic alkyl group, and in addition, R 7 may optionally form a ring together with R 3 may optionally form a ring together with R 8 may optionally form a ring together with R R 3 a hydrogen atom of the represented group is optionally further substituted with R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, or a halogen atom, R 4 , R 5 , R 6 and R 7 each independently represent R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN or a halogen atom, R 4 and R 5 , R 5 and R 6 , and R 6 and R 7 each optionally form a ring together, R 14 , R 15 and R 16 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R 14 , R 15 and R 16 the alkyl moiety of the group represented by R 8 represents R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , a hydroxyl group, CN or a halogen atom, k represents 0 or 1.

2. The photosensitive colored resin composition according to claim 1, wherein the photoinitiator further comprises at least one selected from the group consisting of an oxime ester photoinitiator, an α-amino ketone photoinitiator, a bisimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent, other than the compound represented by the general formula (A).

3. The photosensitive colored resin composition according to claim 1 or 2, wherein, the (meth)acrylate copolymer dispersant comprises 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 salt-type graft copolymer obtained by forming a salt of at least a part of a nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer with at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon, the structural unit of the polymer chain in the structural unit represented by the following general formula (II) comprises at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (III) and a structural unit represented by the following general formula (III'), In General Formula (I), R 41 represents a hydrogen atom or a methyl group, A 1 represents a divalent linking group, R 42 and R 43 each independently represent a hydrogen atom or a hydrocarbon group optionally containing a heteroatom, R 42 and R 43 are optionally bonded to each other to form a ring structure; In General Formula (II), R 41' represents a hydrogen atom or a methyl group, A 2 represents a direct bond or a divalent linking group, Polymer represents a polymer chain, and the structural unit of the polymer chain contains a structural unit derived from a (meth)acrylate ester, In General Formula (III), R 44 is a hydrogen atom or a methyl group, A 3 is a divalent linking group, R 45 is an ethylene group or a propylene group, R 46 is a hydrogen atom or a hydrocarbon group, and m represents a number of 3 or more and 80 or less. In General Formula (III), R 44' is a hydrogen atom or a methyl group, A 3' is a divalent linking group, R 47 is an alkylene group having a carbon number of 1 to 10, R 48 is an alkylene group having a carbon number of 3 to 7, R 49 is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less.

4. The photosensitive colored resin composition according to claim 1 or 2, wherein, the (meth)acrylate copolymer dispersant comprises at least one of a block copolymer comprising an A block comprising a structural unit represented by the following general formula (I) and a B block comprising a structural unit derived from a carboxyl group-containing monomer and a structural unit derived from a (meth)acrylate, and a salt-type block copolymer obtained by forming a salt of at least a part of a nitrogen site of the structural unit represented by the general formula (I) of the block copolymer with at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon, the at least one of the block copolymer and the salt-type block copolymer having an acid value of 1 to 18 mgKOH / g and a glass transition temperature of 30°C or higher, In General Formula (I), R 41 represents a hydrogen atom or a methyl group, A 1 represents a divalent linking group, R 42 and R 43 each independently represent a hydrogen atom or a hydrocarbon group optionally containing a heteroatom, R 42 and R 43 are optionally bonded to each other to form a ring structure.

5. The photosensitive colored resin composition according to claim 3, wherein in the (meth)acrylate copolymer dispersant, the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer comprises the structural unit represented by the general formula (III).

6. The photosensitive colored resin composition according to claim 3, wherein in the (meth)acrylate copolymer dispersant, the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer comprises the structural unit represented by the general formula (III), wherein m represents a number of 19 or higher and 80 or lower.

7. The photosensitive colored resin composition according to claim 1 or 2, further comprising an antioxidant.

8. A cured product of the photosensitive colored resin composition according to any one of claims 1 to 7.

9. 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 8.

10. A display device having the color filter according to claim 9.

Images