Photosensitive coloring composition, cured product, image display panel, color filter, image display device, and method for manufacturing cured product

Abstract

The purpose of the present invention is to provide a photosensitive coloring composition, a cured product, an image display panel, a color filter, an image display device, and a method for producing a cured product, said photosensitive coloring composition having excellent storage stability and excellent sensitivity during pattern formation, and being capable of suppressing the generation of residues and gas escape. The photosensitive colored composition contains silsesquioxane having a structural unit (I) represented by formula (1), an alkali-soluble resin, a colorant, a radiation-sensitive radical polymerization initiator and an organic solvent, and the content of silanol groups relative to the total content of the structural units constituting the silsesquioxane is less than 0.3 in molar ratio. (In formula (1), X represents a group represented by formula (2); (In formula (2), each R1 independently represents a hydrogen atom or a methyl group; and each R2 independently represents an alkanediyl group having 2 to 10 carbon atoms). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition, a cured product, an image display panel, a color filter, an image display device, and a method for producing the cured product. Background Art

[0002] As a method for manufacturing color filters and black matrices possessed by display devices, photolithography has become mainstream in recent years. For example, in the case of manufacturing color filters by photolithography, the following method is generally adopted: after a photosensitive composition containing a color material such as a dye and a polymer is coated on a substrate to form a coating film, a photomask having a prescribed opening pattern is exposed, and then, the unexposed portion is dissolved and removed by development to form a hardened pattern (i.e., a colored pattern) (for example, with reference to patent document 1). After development, the following operation is generally performed: post-baking at a temperature of 200°C to 250°C for about 30 minutes to 60 minutes, thereby promoting the hardening of the coating film, thereby improving the solvent resistance or film hardness of the film.

[0003] In display devices using organic electroluminescent (EL) elements, the display area is divided by partitioning walls (also called banks), and an organic light-emitting material is applied between the partitions using an inkjet method or other method to form a light-emitting layer. In recent years, the partitions have been formed using a photosensitive composition containing a colorant and photolithography to impart light-shielding properties.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2-144502 Summary of the Invention

[0007] [Problems to be solved by the invention]

[0008] When the photosensitive composition contains a colorant, there are cases where the resolution deteriorates or residues are generated in the obtained cured product. In addition, when the photosensitive composition contains a colorant, the absorption of the colorant hinders light curing, so there is a problem that outgassing caused by uncured components is easily increased. In addition, by heating the cured product formed by the photosensitive composition at a high temperature (for example, above 200°C), outgassing is sometimes generated. When the cured product is used as a partition wall material, the partition wall material is adjacent to the light-emitting layer, so there is a problem that a local non-luminous area (hereinafter also referred to as a dark spot) is generated due to the generated outgassing. In addition, the photosensitive composition is also required to have a viscosity and the like that does not increase even when it is stored until actual use (that is, excellent storage stability).

[0009] Therefore, an object of the present invention is to provide a photosensitive coloring composition having excellent storage stability, excellent sensitivity during pattern formation, and suppressing the generation of residue and outgassing, a cured product, an image display panel, a color filter, an image display device, and a method for producing the cured product.

[0010] [Technical means to solve the problem]

[0011] The present inventors have diligently studied to solve the problem and, as a result, have found that the object can be achieved by adopting the following configuration, thereby completing the present invention.

[0012] In one embodiment, the present invention relates to a photosensitive coloring composition comprising:

[0013] Silsesquioxane having a structural unit (I) represented by the following formula (1);

[0014] Alkali soluble resin;

[0015] color materials;

[0016] Radiation-sensitive linear free radical polymerization initiator; and

[0017] organic solvents,

[0018] The content of the silanol group relative to the total content of the structural units constituting the silsesquioxane is less than 0.3 in terms of molar ratio.

[0019]

[0020] (In the formula (1), X is a group represented by the following formula (2);

[0021]

[0022] (In the formula (2), R 1 are independently a hydrogen atom or a methyl group; R2 are each independently an alkanediyl group having 2 to 10 carbon atoms)

[0023] In another embodiment, the present invention relates to a cured product obtained by curing the photosensitive coloring composition, an image display panel including the cured product as a color filter, an image display device including the image display panel, a color filter including the cured product as a black matrix, an image display panel including the color filter, an image display device including the image display panel, and an image display device including the cured product as a light-shielding partition material.

[0024] In another embodiment, the present invention relates to a method for manufacturing a patterned hardened object, comprising:

[0025] a step of applying the photosensitive coloring composition on a substrate to form a coating film;

[0026] A process of performing position selective exposure on the coating film;

[0027] a step of developing the exposed coating film; and

[0028] A step of heating the patterned coating film after development.

[0029] [Effects of the Invention]

[0030] The photosensitive coloring composition of the present invention has excellent storage stability due to the inclusion of silsesquioxane having a specific structure, and despite containing a coloring material, has excellent sensitivity during pattern formation and can suppress the generation of residues and outgassing in the formed cured product. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 A cross-sectional view showing an organic EL panel having a (POL-LESS) structure without a polarizing plate.

[0032] Explanation of Figure Numbers

[0033] 1: Substrate

[0034] 2: TFT drive circuit layer

[0035] 3: Light-shielding isolation wall material (bank)

[0036] 4: Luminous layer

[0037] 5: Touch sensor

[0038] 6: Color filter

[0039] 6a: Black Matrix

[0040] 6b: Color pattern with various colors (RGB)

[0041] 7: Cover glass

[0042] 8: Sealing layer DETAILED DESCRIPTION

[0043] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[0044] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit.

[0045] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The so-called "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that does not contain a cyclic structure on the main chain but is composed only of a chain structure. Among them, the chain hydrocarbon group may be saturated or unsaturated. The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. Among them, the alicyclic hydrocarbon group does not need to be composed only of an alicyclic hydrocarbon structure, and also includes a group having a chain structure in a part thereof. The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. Among them, the aromatic hydrocarbon group does not need to be composed only of an aromatic ring structure, and may also contain a chain structure or an alicyclic hydrocarbon structure in a part thereof. In addition, the ring structure possessed by the alicyclic hydrocarbon group and the aromatic hydrocarbon group may also have a substituent containing a hydrocarbon structure.

[0046] In this specification, "(meth)acryloyl" includes both "acryloyl" and "methacryloyl," "(meth)acrylate" includes both "acrylate" and "methacrylate," and "(meth)acrylate" includes both "acrylate" and "methacrylate."

[0047] Hereinafter, the curable composition of the present invention will be described.

[0048] Curable composition

[0049] The photosensitive coloring composition of the present embodiment (hereinafter also referred to as “the present composition”) contains:

[0050] Silsesquioxane (A) having a structural unit (I) represented by the following formula (1);

[0051] Alkali-soluble resin (B);

[0052] Color material (C);

[0053] a radiation-sensitive linear radical polymerization initiator (D); and

[0054] Organic solvent (G),

[0055] The content of the silanol group relative to the total content of the structural units constituting the silsesquioxane (A) is less than 0.3 in terms of molar ratio.

[0056]

[0057] (In the formula (1), X is a group represented by the following formula (2);

[0058]

[0059] (In the formula (2), R 1 are independently a hydrogen atom or a methyl group; R 2 are each independently an alkanediyl group having 2 to 10 carbon atoms)

[0060] Hereinafter, each component contained in this composition and other components blended as needed will be described.

[0061] <Silsesquioxane (A)>

[0062] Silsesquioxane (A) has a structural unit (I) represented by the following formula (1), and the content of silanol groups relative to the total content of the structural units constituting the silsesquioxane (A) is less than 0.3 in terms of molar ratio.

[0063]

[0064] (In the formula (1), X is a group represented by the following formula (2);

[0065]

[0066] (In the formula (2), R 1 are independently a hydrogen atom or a methyl group; R 2 are each independently an alkanediyl group having 2 to 10 carbon atoms)

[0067] Silsesquioxane is a siloxane compound whose main chain skeleton contains Si-O bonds and is generally obtained by hydrolysis and condensation of trifunctional silane. 1.5 )-(R is a monovalent organic group) are known to be polymers of structural units. Silsesquioxanes are known to have various backbone structures, such as cage structures, ladder structures, and random structures. The silsesquioxane (A) used in the present composition may have any structure, but preferably has a cage structure or a ladder structure.

[0068] The silsesquioxane (A) may have other structural units in addition to the structural unit (I).

[0069] Since the present composition contains the silsesquioxane (A) having a specific structure, it has excellent storage stability, excellent sensitivity during pattern formation, and can suppress the generation of residues and outgassing in the formed cured product.

[0070] [Structural unit (I)]

[0071] The structural unit (I) is represented by the following formula (1).

[0072]

[0073] (In the formula (1), X is a group represented by the following formula (2);

[0074]

[0075] (In the formula (2), R 1 are independently a hydrogen atom or a methyl group; R 2 are each independently an alkanediyl group having 2 to 10 carbon atoms)

[0076] In the above formula (1), there are an average of 1.5 oxygen atoms and one X group per silicon atom. The silsesquioxane (A) includes a structural unit (XSiO 1.5 ).

[0077]

[0078] (In formula (i), * represents a bond to a silicon atom of another structural unit)

[0079] The R 1 is a hydrogen atom or a methyl group.

[0080] The R 2 An alkanediyl group having 2 to 10 carbon atoms. Examples of the alkanediyl group include ethanediyl, propanediyl, butanediyl, hexanediyl, octanediyl, nonanediyl, and decanediyl. Furthermore, some or all of the hydrogen atoms in the alkanediyl group may be substituted with a substituent such as a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxyl group; a carboxyl group; a cyano group; a nitro group; an alkyl group; an alkoxy group; an alkoxycarbonyl group; an alkoxycarbonyloxy group; an acyl group; an acyloxy group; or a group in which the hydrogen atoms of these groups are substituted with a halogen atom.

[0081] Among the alkanediyl groups having 2 to 10 carbon atoms, an alkanediyl group having 2 to 8 carbon atoms is preferred, an alkanediyl group having 2 to 5 carbon atoms is more preferred, and a propanediyl group is further preferred.

[0082] Specific examples of the structural unit (I) are not particularly limited, but include structures represented by the following formulas. In the following formula, R 1 It has the same meaning as the above formula (2).

[0083]

[0084] The silsesquioxane (A) may contain a silanol group (-SiOH), and the content of the silanol group (-SiOH) relative to the total content of the structural units constituting the silsesquioxane (A) is less than 0.3, preferably less than 0.25, and more preferably less than 0.2 in terms of a molar ratio (the molar amount of the silanol group contained / the total molar amount of the structural units constituting the silsesquioxane (A)). When the molar ratio is less than 0.3, the degree of condensation is high, and the tendency of the silsesquioxane to have a cage structure or a ladder structure becomes stronger. As a result, the storage stability of the present composition is excellent, and a cured product (cured film) with excellent resolution, residue, and outgassing can be obtained. In addition, the lower limit of the molar ratio is not particularly limited and may be 0, but may also be 0.01 or 0.05.

[0085] [Structural unit (II)]

[0086] The silsesquioxane (A) preferably has a structural unit (II) represented by the following formula (3) in addition to the structural unit (I) represented by the formula (1).

[0087]

[0088] (In the above formula (3), Y is a monovalent organic group having a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof)

[0089] The monovalent organic group represented by Y may have a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof.

[0090] Examples of the monovalent organic group in Y include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group having a divalent heteroatom-containing group between carbon atoms of the hydrocarbon group or at the end of the carbon chain, a group in which a part or all of the hydrogen atoms of the hydrocarbon group are substituted with a monovalent heteroatom-containing group, or a combination thereof.

[0091] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in Y include a chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0092] Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms in Y include monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, or monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of the monovalent linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl, isopentyl, and neopentyl. Examples of the monovalent linear or branched unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.

[0093] Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms in Y include monocyclic or polycyclic saturated hydrocarbon groups, or monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic saturated hydrocarbon groups include bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecanyl, and tetracyclododecyl. Examples of monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. Examples of polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norbornenyl, tricyclodecanyl, and tetracyclododecenyl. In addition, a bridged alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which two non-adjacent carbon atoms of the carbon atoms constituting the alicyclic ring are bonded via a linking group containing one or more carbon atoms.

[0094] Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in Y include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracenyl; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl.

[0095] Examples of the monovalent heteroatom-containing group include a hydroxyl group, a carboxyl group, a sulfanyl group, a cyano group, a nitro group, and a halogen atom.

[0096] Examples of the divalent heteroatom-containing group include -CO-, -C(=O)O-, -CS-, -NR'-, -O-, -S-, -SO-, -SO2-, or combinations thereof. R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0097] As the Y, a group represented by the following formula (4) is preferred.

[0098]

[0099] (In the formula (4), R 1 are independently a hydrogen atom or a methyl group; R 2 are each independently an alkanediyl group having 2 to 10 carbon atoms; R 3 is a divalent organic group; Y1 is a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof)

[0100] As the R 2 The alkanediyl group having 2 to 10 carbon atoms represented by the above-mentioned group has the same meaning as that of the above-mentioned formula (1).

[0101] As the R 3 The divalent organic group represented by α is preferably a group obtained by removing one hydrogen atom from the monovalent organic group described above for Y.

[0102] The above-mentioned formula (4) is preferably a group selected from the group consisting of groups represented by the following formula (4a), the following formula (4b), and the following formula (4c).

[0103]

[0104] (In the above formula (4a), formula (4b) and formula (4c), R 4 is a single bond or a divalent organic group; X is a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, or an alkoxy group; n is an integer from 0 to 4; when n is 2 or more, multiple Xs are the same or different; R 1 、R 2 、R 3 It has the same meaning as the formula (4); * represents the bonding site)

[0105] As the R 4 The divalent organic group represented by α is preferably a group obtained by removing one hydrogen atom from the monovalent organic group described above for Y.

[0106] Examples of the alkyl group represented by X include the chain hydrocarbon group having 1 to 20 carbon atoms in Y.

[0107] Examples of the alkyl portion of the alkoxy group represented by X include the above-mentioned alkyl groups.

[0108] n is an integer of 0 to 4, and preferably 0 or 1.

[0109] Specific examples of the structural unit (II) are not particularly limited, but include structures represented by the following formula. In the following formula, R 1 It has the same meaning as in the above formula (4), and m is an integer of 2 to 4.

[0110]

[0111] The lower limit of the content of the structural unit (I) relative to the total content of the structural unit (I) and the structural unit (II) in the silsesquioxane (A) is preferably 10 mol%, more preferably 30 mol%, further preferably 50 mol%, and particularly preferably 60 mol%. The upper limit of the content is preferably 100 mol%, more preferably 95 mol%, and further preferably 90 mol%. By setting the content of the structural unit (I) within this range, lithography performance can be improved, which is preferred.

[0112] The silsesquioxane (A) may also have other structural units in addition to the structural units (I) and (II). Examples of other structural units include structural units having a silanol group (-SiOH) or -(R a SiO 1.5 )-(R a is a monovalent hydrocarbon group) (except for the structural unit corresponding to the structural unit (I) or the structural unit (II)).

[0113] The lower limit of the total content of structural units (I) and structural units (II) relative to all structural units in the silsesquioxane (A) is preferably 60 mol%, more preferably 70 mol%, and even more preferably 80 mol%. The upper limit of the total content is not particularly limited and may be 100 mol%.

[0114] The lower limit of the weight average molecular weight (Mw) of the silsesquioxane (A) is preferably 1,000, more preferably 2,000, and still more preferably 3,000. The upper limit of the weight average molecular weight is preferably 20,000, more preferably 10,000, and still more preferably 6,000.

[0115] As the lower limit of the content of silsesquioxane (A) in the present composition, relative to the total solid content (100% by mass) of the present composition, it is preferably 10% by mass, more preferably 15% by mass, and further preferably 20% by mass. On the other hand, as the upper limit of the content, it is preferably 90% by mass, more preferably 80% by mass, further preferably 70% by mass, and particularly preferably 60% by mass. In addition, the so-called total solid content refers to all components other than solvents such as organic solvents (G). By setting the content of silsesquioxane (A) to the range, the storage stability can be further improved, and the generation of residues and outgassing can be suppressed, so it is preferred.

[0116] The method for producing the silsesquioxane (A) is not particularly limited, and the silsesquioxane (A) can be synthesized, for example, by the following synthesis method.

[0117] (Synthesis method)

[0118] The synthesis scheme (M-1) is shown below.

[0119]

[0120] In the process (M-1), R 11 is an alkyl group having 1 to 6 carbon atoms. k, m, and n are natural numbers satisfying k=m+n. X and Y have the same meanings as X and Y in formula (1) and formula (3).

[0121] The silsesquioxane represented by formula (1) can be obtained by hydrolyzing and condensing the trialkoxysilane represented by formula (1A) as a starting material in the presence of a base. Silsesquioxane (A) can then be obtained by reacting an SH compound with the silsesquioxane.

[0122] Examples of the trialkoxysilane represented by formula (1A) include acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, acryloxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, acryloxyoctyltriethoxysilane, and methacryloxyoctyltriethoxysilane. Among these, acryloxypropyltrimethoxysilane and methacryloxypropyltrimethoxysilane are more preferred.

[0123] In addition, trialkoxysilanes other than the trialkoxysilane represented by formula (1A) may be used together. Examples of other trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, 4-vinylphenyltrimethoxysilane, and 4-vinylphenyltriethoxysilane.

[0124] Examples of the base used in the hydrolysis condensation reaction include trimethylamine, triethylamine, tripropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, sodium hydroxide, potassium hydroxide, etc. Among these, triethylamine is preferred.

[0125] Examples of the SH compound in the process (M-1) include monovalent thiol compounds having a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a combination thereof. Examples of the addition reaction method of the SH compound include Michael addition reaction, ene-thiol reaction, etc., preferably Michael addition reaction. Specifically, examples of the SH compound include compounds represented by the following formula (SH-1) to (SH-20), among which compounds represented by the following formula (SH-1) to (SH-12) are preferred, compounds represented by the following formula (SH-1) to (SH-9) are more preferred, and compounds represented by the following formula (SH-1) and (SH-5) are further preferred.

[0126]

[0127] Examples of the base used in the Michael addition reaction include trimethylamine, triethylamine, tripropylamine, imidazole, diazabicycloundecene, pyridine, morpholine, piperazine, piperidine, sodium hydroxide, potassium hydroxide, etc. Among these, triethylamine is preferred.

[0128] An example of the synthesis method is shown in the following scheme (M-1-1).

[0129]

[0130] <Alkali-soluble resin (B)>

[0131] The alkali-soluble resin (B) is a component that exhibits good developability with an alkaline developer. The alkali-soluble resin (B) is generally a resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group (excluding the resin corresponding to the silsesquioxane (A)), and preferably a resin having a carboxyl group.

[0132] Examples of the alkali-soluble resin (B) include acrylic resins, silicone resins, and novolac resins. From the viewpoint of storage stability, acrylic resins are preferred.

[0133] The alkali-soluble resin (B) preferably has a group containing an unsaturated double bond, such as a (meth)acryloyl group or a vinyl group, from the viewpoint of further improving developability and the physical properties of the cured product. Examples of such alkali-soluble resins (B) include acid-modified epoxy (meth)acrylate resins, such as acid-modified cresol novolac-type epoxy (meth)acrylate resins, phenol novolac-type epoxy (meth)acrylate resins, bisphenol A-type epoxy (meth)acrylate resins, bisphenol F-type epoxy (meth)acrylate resins, biphenyl-type epoxy (meth)acrylate resins, and trisphenol methane-type epoxy (meth)acrylate resins. Examples of the alkali-soluble resin (B) also include acid-modified cardo-based resins having a (meth)acryloyl group and a carboxyl group.

[0134] (Acrylic resin)

[0135] Examples of the acrylic resin include copolymers of a monomer having an alkali-soluble functional group and other copolymerizable monomers.

[0136] Examples of the monomer having an alkali-soluble functional group include:

[0137] Carboxyl-containing monomers such as (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid, mono(2-(meth)acryloyloxyethyl) succinate, and ω-carboxy-polycaprolactone mono(meth)acrylate;

[0138] Hydroxyl-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate;

[0139] Monomers containing phenolic hydroxyl groups such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.

[0140] Examples of the other copolymerizable monomers include:

[0141] (Meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, and dicyclopentadienyl (meth)acrylate;

[0142] Aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene;

[0143] Conjugated dienes such as butadiene and isoprene;

[0144] Unsaturated maleimides such as phenylmaleimide and cyclohexylmaleimide;

[0145] Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and other vinyl cyanide compounds;

[0146] Macromonomers having a polymerizable unsaturated group such as a (meth)acryloyl group at one end of the polymer chain, such as polystyrene, polymethyl (meth)acrylate, polyethyl (meth)acrylate, and polybenzyl (meth)acrylate, etc. These can be used alone or in combination of two or more.

[0147] The lower limit of the content of the monomer having an alkali-soluble functional group in all monomers (100% by mass) constituting the acrylic resin is preferably 5% by mass, more preferably 8% by mass. The upper limit of the content is not particularly limited, but is preferably 40% by mass, more preferably 30% by mass.

[0148] The acrylic resin may be produced by any method, but not limited to, suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, or other known methods. Conventionally known conditions may also be employed for the production of the acrylic resin.

[0149] (Polysilicone resin)

[0150] As the polysiloxane resin, a hydrolysis condensate of a hydrolyzable silane compound can be cited. Here, the so-called "hydrolyzable silane compound" refers to a compound containing a group that can be hydrolyzed to generate a silanol group or a group that can form a siloxane condensate, and a "hydrolysis condensate" refers to a condensate formed by condensing the silanol groups of the hydrolyzed silane compound with each other. As such a polysiloxane resin, for example, the polysiloxane resin described in Japanese Patent Laid-Open No. 2017-048355 can be cited. In addition, a silsesquioxane (that is, a silsesquioxane that is not equivalent to the silsesquioxane (A)) having a silanol group content of 0.3 or more in terms of a molar ratio relative to the total content of the structural units constituting the silsesquioxane can also be included.

[0151] (phenolic novolac resin)

[0152] The novolac resin can be obtained by polycondensing phenols with aldehydes such as formaldehyde using a known method.

[0153] Examples of the phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene Bisphenol, methylenebis(p-cresol), resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc. These may be used alone or in combination of two or more.

[0154] In addition, examples of the aldehydes include, in addition to formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. These may be used alone or in combination of two or more.

[0155] The novolac resin preferably has a group containing an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and more preferably has a side chain represented by the following formula (5). In this case, it is preferred that the main chain further has an aromatic ring. Among them, the side chain represented by the following formula (5) and the phenolic novolac main chain are more preferably

[0156] Chain of resin.

[0157] Examples of the resin having a side chain represented by the following formula (5) and a phenolic novolac main chain include acid-modified cresol novolac epoxy (meth)acrylate resins and acid-modified phenol novolac epoxy (meth)acrylate resins.

[0158]

[0159] In the formula (5), R 5 is a hydrogen atom or a methyl group. 6 and R 7 Each is independently a divalent organic group. * indicates the bonding site to the main chain.

[0160] As the R 5 , preferably a hydrogen atom.

[0161] As the R 6 and R 7 The divalent organic group represented by can preferably be a group obtained by removing one hydrogen atom from the monovalent organic group in Y of the above formula (3).

[0162] As the R6 and R 7 The carbon number of the divalent organic group is not particularly limited, but the lower limit thereof may be 1. On the other hand, the upper limit thereof may be 20 or 10, for example.

[0163] As the R 6 , preferably a divalent hydrocarbon group, more preferably a divalent chain hydrocarbon group and a divalent alicyclic hydrocarbon group. 7 , preferably a group in which an oxygen atom (—O—) is bonded to the terminal of the main chain side of the divalent hydrocarbon group, such as —CH 2 —O—*.

[0164] Examples of acid-modified cresol novolac-type epoxy (meth)acrylate resins include polymers represented by the following formula (6). Acid-modified cresol novolac-type epoxy (meth)acrylate resins can be obtained, for example, by reacting an acid anhydride such as phthalic anhydride or 1,2,3,6-tetrahydrophthalic anhydride with an epoxy (meth)acrylate resin obtained by reacting (meth)acrylic acid with a cresol novolac-type epoxy resin.

[0165]

[0166] In the above formula (6), p and q are each independently an integer of 1 to 30.

[0167] Alternatively, as the alkali-soluble resin (B), a cardo-based resin having a side chain represented by the formula (5) and having undergone a predetermined acid modification may be used. Commercially available products of such resins include "WR-301" (ADEKA Co.), an acid-modified cardo-based resin.

[0168] The lower limit of the acid value of the alkali-soluble resin (B) is preferably 10 mgKOH / g, more preferably 20 mgKOH / g, and even more preferably 40 mgKOH / g. The upper limit of the acid value is preferably 300 mgKOH / g, more preferably 270 mgKOH / g, and even more preferably 250 mgKOH / g. The acid value represents the number of mg of KOH required to neutralize 1 g of the solid content of the alkali-soluble resin (B).

[0169] The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 1,000 or more and 20,000 or less.

[0170] The alkali-soluble resin (B) may be used alone or in combination of two or more.

[0171] The lower limit of the content of the alkali-soluble resin (B) (the total amount in the case of multiple amounts) is preferably 5% by mass, more preferably 10% by mass, further preferably 20% by mass, and particularly preferably 30% by mass, relative to the total solids content (100% by mass) of the present composition. Furthermore, the upper limit is preferably 90% by mass, more preferably 80% by mass, further preferably 70% by mass, and particularly preferably 60% by mass, relative to the total solids content (100% by mass) of the present composition. When the content of the alkali-soluble resin (B) is within this range, more sufficient lithographic performance can be achieved.

[0172] <Radiation-sensitive linear radical polymerization initiator (D)>

[0173] The radiation-sensitive radical polymerization initiator (D) is a compound that can generate radicals in response to radiation and initiate polymerization. Specific examples of the radiation-sensitive radical polymerization initiator (D) include O-acyl oxime compounds, α-amino ketone compounds, α-hydroxy ketone compounds, and acylphosphine oxide compounds. Among these, oxime-based photopolymerization initiators such as O-acyl oxime compounds are preferred.

[0174] The use of the oxime ester-based photoinitiator is preferred from the viewpoint of increasing sensitivity, suppressing in-plane line width variations, and improving the residual film rate when forming a fine line pattern.

[0175] As the oxime ester-based photoinitiator, from the perspective of reducing contamination of the composition or the equipment by decomposition products, those having an aromatic ring are preferred, those having a condensed ring containing an aromatic ring are more preferred, and those having a condensed ring containing a benzene ring and a heterocyclic ring are even more preferred.

[0176] Examples of the oxime ester photoinitiator include 1,2-octanedione-1-[4-(phenylthio)phenyl-2-(O-benzoyloxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and oxime ester photoinitiators described in Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2010-527338, Japanese Patent Application Publication No. 2013-041153, and Japanese Patent Application Publication No. 2021-076846. Commercially available products include Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03 (all manufactured by BASF), ADEKA Arkls NCI-930 having a diphenyl sulfide skeleton (manufactured by ADEKA), TR-PBG-345, TR-PBG-304 having a carbazole skeleton, TR-PBG-365 having a fluorene skeleton, and TR-PBG-3057 having a diphenyl sulfide skeleton (all manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.).

[0177] The radiation-sensitive linear radical polymerization initiator (D) may be used alone or in combination of two or more.

[0178] The lower limit of the content of the radiation-sensitive linear radical polymerization initiator (D) (the total amount in the case of multiple types) is preferably 1 mass %, more preferably 3 mass %, relative to the total solid content (100 mass %) of the present composition. On the other hand, the upper limit of the content is preferably 40 mass %, more preferably 30 mass %. When the content ratio of the (D) component is within the above range, the present composition can form a cured product with good resolution and development adhesion even at a low exposure dose, and is therefore preferred.

[0179] Color material (C)

[0180] This composition contains a coloring material (C). By having a coloring material (C), a desired color can be imparted according to the application of the photosensitive composition.

[0181] The coloring material (C) is not particularly limited and may be any of an organic pigment, an inorganic pigment, and a dye.

[0182] Examples of the organic pigments include compounds classified as pigments in the Colour Index (CI; published by The Society of Dyers and Colourists). Specifically, the following compounds have the following Colour Index (CI) numbers.

[0183] Yellow pigments such as CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, and CI Pigment Yellow 211;

[0184] Orange pigments such as CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, and CI Pigment Orange 74;

[0185] CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179 , CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272 and other red pigments;

[0186] CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38 and other purple pigments;

[0187] Blue pigments such as CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, and CI Pigment Blue 80;

[0188] Green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, and CI Pigment Green 59;

[0189] Brown pigments such as CI Pigment Brown 23 and CI Pigment Brown 25;

[0190] Black pigments such as CI Pigment Black 1, CI Pigment Black 7, CI Pigment Black 31, CI Pigment Black 32, lactam-based black pigments, and perylene-based black pigments.

[0191] In the present invention, the organic pigment may be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

[0192] Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc yellow, lead sulfate, chrome yellow, zinc yellow, Bengala (red iron (III) oxide), cadmium red, ultramarine, dark blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, and carbon black.

[0193] These color materials can also be used by modifying the particle surface of the pigment using a polymer as needed. Examples of polymers for modifying the pigment particle surface include polymers described in Japanese Patent Laid-Open No. 8-259876 or commercially available polymers or oligomers for dispersing various pigments. Methods for coating the surface of carbon black with a polymer are disclosed in Japanese Patent Laid-Open No. 9-71733, Japanese Patent Laid-Open No. 9-95625, and Japanese Patent Laid-Open No. 9-124969.

[0194] As the black colorant, a single black colorant or a mixture of red, green, blue, etc. can be used. These black colorants can be appropriately selected from inorganic pigments, organic pigments, and dyes, and can be used alone or in combination.

[0195] Examples of the single black colorant include organic pigments and inorganic pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, perylene black, lactam black, cyanine black, and titanium black.

[0196] As the dye, a dye that emits a desired color can be used, and examples of the specific structural portion (chromophore) that serves as the basis for color development include triarylmethane-based cationic chromophores, methine-based cationic chromophores, azo-based cationic chromophores, diarylmethane-based cationic chromophores, quinoneimine-based cationic chromophores, anthraquinone-based cationic chromophores, cyanine-based cationic chromophores, squarylium-based cationic chromophores, and xanthene-based cationic chromophores.

[0197] When the present composition is used for forming a light-shielding partition wall material, a black organic pigment, titanium black, or carbon black is preferably used as the colorant (C) from the viewpoint of preventing light leakage from the adjacent light-emitting layer.

[0198] When a pigment is used as the color material (C), dispersion treatment using a pigment dispersant is preferred because a uniformly dispersed pigment can be obtained in the present composition. In such cases, a pigment and a pigment dispersant may be used when preparing the present composition. Preferably, a pigment dispersion prepared by mixing the pigment, pigment dispersant, and dispersion medium is prepared before preparing the present composition, and the prepared pigment dispersion is used to prepare the present composition.

[0199] Examples of the pigment dispersant include cationic pigment dispersants, anionic pigment dispersants, nonionic pigment dispersants, and amphoteric pigment dispersants. Specifically, polyester pigment dispersants, polyamine pigment dispersants, and acrylic pigment dispersants are examples. These pigment dispersants may be used alone or in combination of two or more.

[0200] When the pigment dispersant is used, the amount of the pigment dispersant used is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the pigment, from the viewpoint of easily obtaining a pigment dispersion in which the pigment is uniformly dispersed.

[0201] The color materials (C) can be used alone or in combination of two or more.

[0202] The lower limit of the content of the color material (C) (the total amount in the case of multiple types) is preferably 1 mass %, more preferably 5 mass %, and further preferably 10 mass % relative to the total solid content (100 mass %) of the present composition. On the other hand, the upper limit of the content is preferably 50 mass %, more preferably 40 mass %, further preferably 30 mass %, and particularly preferably 20 mass %. By setting the content of the color material (C) within the above range, it is possible to achieve both developability and a preferred degree of coloration, which is therefore preferred.

[0203] <Polymerizable compound (E)>

[0204] The present composition may also contain a polymerizable compound (E). The polymerizable compound (E) is preferably a compound having two or more polymerizable groups and functions as a crosslinking agent. The polymerizable group is preferably a group capable of free radical polymerization, for example, an ethylenically unsaturated group, an oxirane group, an oxetanyl group, an N-alkoxymethylamino group, etc. Among these, the polymerizable compound (E) is preferably a compound having two or more (meth)acryloyl groups.

[0205] Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylates obtained by reacting a trivalent or higher-valent aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride.

[0206] Among these, the polymerizable compound (E) is preferably a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, a caprolactone-modified polyfunctional (meth)acrylate, a polyfunctional urethane (meth)acrylate, or a polyfunctional (meth)acrylate having a carboxyl group. More preferred are a polyfunctional (meth)acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, a polyfunctional urethane (meth)acrylate, or a polyfunctional (meth)acrylate having a carboxyl group. Among the polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred.

[0207] Examples of commercially available products include Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, and Aronix M-520 (manufactured by Toagosei Co., Ltd.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, and KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), and Viscoat #230, Viscoat #300, Viscoat #802, and Viscoat #1420.

[0208] #2500, Viscoat #1000, Viscoat #1080 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-BPE-10, NK Ester A-GLY-9E, NK Ester A-9550, NK Ester A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0209] The polymerizable compound (E) can be used alone or in combination of two or more.

[0210] The lower limit of the content of the polymerizable compound (E) (the total amount in the case of multiple types) is preferably 3% by mass, more preferably 5% by mass, relative to the total solid content (100% by mass) of the present composition. Furthermore, the upper limit of the content is preferably 70% by mass, more preferably 60% by mass, relative to the total solid content of the present composition. A content of the polymerizable compound (E) within this range is preferred because sufficient curability as a coating film and sufficient alkali developability as a photosensitive coloring composition can be ensured, and the generation of outgassing, etc. can be sufficiently suppressed.

[0211] <Organic solvent (G)>

[0212] The present composition contains an organic solvent (G). The organic solvent (G) is not particularly limited, and examples thereof include alcohol solvents, ether solvents, ester solvents, ketone solvents, and amide solvents. The organic solvent (G) may be used alone or in combination of two or more.

[0213] Examples of the alcoholic solvent include alkyl alcohols such as methanol, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, and diacetone alcohol; and aromatic alcohols such as benzyl alcohol.

[0214] Examples of the ether solvent include: ethylene glycol monoalkyl ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

[0215] Examples of the ester solvent include carboxylic acid esters such as ethyl acetate, isopropyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; polyol carboxylic acid ester solvents such as propylene glycol diacetate; and polyol partial ether carboxylic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.

[0216] Examples of the ketone-based solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0217] Among these, ether solvents and ester solvents are preferred, ester solvents are more preferred, and polyol partial ether carboxylate solvents are further preferred. Among ether solvents and ester solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate are preferred.

[0218] The content of the organic solvent (G) in this composition is not particularly limited, and is preferably adjusted in the following range with the solid component (composition other than the solvents such as the organic solvent (G)) concentration of this composition. As the lower limit of the solid component concentration in this composition, it is preferably 5 mass %, more preferably 10 mass %, and then preferably 15 mass %. On the other hand, as the upper limit of solid component concentration, it is preferably 60 mass %, more preferably 50 mass %, and then preferably 40 mass %.

[0219] <Other ingredients>

[0220] In addition to the aforementioned components, the present composition may also contain other components. Examples of these other components include hardeners, hardening accelerators, antioxidants, and surfactants such as fluorine-based surfactants and silicone-based surfactants. The content of these other components in the curable composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0221] <Method for preparing photosensitive coloring composition>

[0222] The photosensitive coloring composition of the present invention can be prepared by mixing the components at a predetermined ratio and dissolving them in an organic solvent (G). The prepared composition is preferably filtered using a filter having a pore size of about 0.2 μm.

[0223] Hardened Matter

[0224] The cured product of the present invention (hereinafter also referred to as the "cured product") can be formed by curing the photosensitive coloring composition prepared as described above. The photosensitive coloring composition has high storage stability and high radiation sensitivity. The cured product obtained from the photosensitive coloring composition is a cured product in which the generation of residue and outgassing is suppressed. Therefore, the cured product can be preferably used as, for example, a color filter (color pattern or black matrix) or a light-shielding partition wall material (bank). In addition to the above, it can also be preferably used as an interlayer insulating film, a planarizing film, etc.

[0225] When a cured product formed by curing the curable composition of the present invention is used as a light-shielding partition wall material, the optical density (DO value) of the cured product is preferably 0.5 to 4.0, more preferably 0.7 to 3.5. When the optical density is within this range, sufficient light-shielding properties can be achieved as a light-shielding partition wall material, which is preferred.

[0226] The cured product of the present invention may be a patterned film.

[0227] 《Method for producing hardened products》

[0228] The method for manufacturing a patterned cured product in this embodiment includes:

[0229] a step of applying the photosensitive coloring composition on a substrate to form a coating film (coating film forming step);

[0230] a step of performing position-selective exposure on the coating film (exposure step);

[0231] a step of developing the exposed coating film (development step); and

[0232] A step of heating the developed pattern (heating step).

[0233] According to the method for producing a cured product, since the photosensitive coloring composition is used, a patterned cured product can be formed in which the generation of residues and outgassing is suppressed.

[0234] [Step 1: Coating Film Formation Step]

[0235] In this step, the photosensitive coloring composition is applied to the surface on which the film is to be formed (hereinafter also referred to as the "film-forming surface") and preferably subjected to a heat treatment (pre-baking) to remove the solvent and form a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, the photosensitive coloring composition is applied to a substrate on which a switching element such as a thin film transistor (TFT) is provided to form a coating film. Examples of substrates that can be used include glass substrates, silicon substrates, and resin substrates. The surface of the substrate on which the coating film is to be formed can be formed with a metal thin film depending on the intended use, or can be subjected to various surface treatments such as hexamethyldisilazane (HMDS) treatment.

[0236] Examples of the method for applying the photosensitive coloring composition include spraying, roller coating, spin coating, slot die coating, rod coating, and inkjet coating. Of these, spin coating, slot die coating, or rod coating is preferred. Pre-baking conditions vary depending on the type and content ratio of each component in the photosensitive coloring composition, but are, for example, performed at 60°C to 130°C for 0.5 to 10 minutes. The thickness of the formed coating (i.e., the thickness after pre-baking) is preferably 0.1 μm to 12 μm. The photosensitive coloring composition applied to the film-forming surface may be dried under reduced pressure (vacuum drying (VCD)) before pre-baking.

[0237] [Process 2: Exposure process]

[0238] In this process, at least a portion of the coating formed in the process 1 is selectively irradiated with radiation. The "position selectivity" is to partially irradiate the coating with radiation through a mask having a predetermined pattern. By position selective exposure, a hardened material having a pattern can be formed. Examples of radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams. Among these, ultraviolet rays are preferred, and examples include g-rays (wavelength 436nm), h-rays (wavelength 405nm), and i-rays (wavelength 365nm). The exposure amount of radiation is preferably 0.1J / m 2 ~20,000J / m 2 .

[0239] [Process 3: Development process]

[0240] In this process, the coating film irradiated with radiation in the process 2 is developed. Specifically, for the coating film irradiated with radiation in the process 2, positive development is performed to remove the irradiated part of the radiation or negative development is performed to remove the non-irradiated part of the radiation using a developer. As a developer, for example, an aqueous solution of an alkali (alkaline compound) can be cited. As an alkali, for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and the alkali exemplified in paragraph

[0127] of Japanese Patent Laid-Open No. 2016-145913 can be cited. As the alkali concentration in the alkaline aqueous solution, from the perspective of obtaining appropriate developability, it is preferably 0.01% by mass to 5% by mass. As a developing method, for example, a suitable method such as a coating method, an immersion method, a shaking immersion method, and a spray method can be cited. The developing time also varies according to the composition of the composition, for example, it is 30 seconds to 120 seconds. In addition, it is preferred that after the developing process, the patterned coating film is rinsed with running water.

[0241] [Step 4: Heating step]

[0242] In this process, the coating film developed in the process 3 is heated (post-baking). Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding the post-baking conditions, the heating temperature is, for example, 120°C to 250°C. For example, when the heating treatment is performed on a hot plate, the heating time is 5 minutes to 40 minutes, and when the heating treatment is performed in an oven, the heating time is 10 minutes to 80 minutes. By proceeding in the manner described above, a cured product having a target pattern can be formed on the substrate. The shape of the pattern of the cured product is not particularly limited, and examples thereof include: line and space pattern, dot pattern, hole pattern, and grid pattern.

[0243] The cured product formed using the photosensitive coloring composition can be preferably used as, for example, a color filter (color pattern or black matrix) or a light-shielding partition material. In addition to the above, it can also be preferably used as an interlayer insulating film, a planarizing film, etc.

[0244] Color Filters

[0245] The color filter of the present invention may include the cured product as a color pattern having each color (RGB), or may include the cured product as a black matrix.

[0246] Image Display Panel

[0247] The image display panel of the present invention only needs to include the color filter, and other structures are not particularly limited. Figure 1 As shown, an organic EL panel without a polarizer (POL-LESS) structure is constructed by stacking a TFT driving circuit layer 2, a light-shielding barrier material (bank) 3, a light-emitting layer 4 having three primary colors, a sealing layer 8, a touch sensor 5, a color filter 6 including a black matrix 6a and color patterns 6b having respective colors (RGB), and a cover glass 7 on a substrate 1. This cured product can be used as a color filter or light-shielding barrier material for such a POL-LESS structured organic EL panel.

[0248] Image Display Device

[0249] The image display device of the present invention comprises the present cured product and the image display panel. The present cured product may be used as a light-shielding partition wall material. Examples of the display device include liquid crystal display devices, organic EL display devices, micro-light emitting diode (LED) display devices, quantum dot luminescent display devices, and the like. In addition, preferably, a display device having Figure 1 The organic EL display device shown does not have an organic EL panel with a polarizing plate (POL-LESS) structure.

[0250] [Example]

[0251] Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples.

[0252] [Weight average molecular weight (Mw)]

[0253] Mw was measured by gel permeation chromatography (GPC) using the following conditions.

[0254] Equipment: Showa Denko Co., Ltd.'s "GPC-101"

[0255] Tube: A tube string made by connecting "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" manufactured by Showa Denko Co., Ltd.

[0256] Mobile phase: tetrahydrofuran

[0257] Column temperature: 40°C

[0258] Flow rate: 1.0 mL / min

[0259] Sample concentration: 1.0 mass%

[0260] Sample injection volume: 100 μL

[0261] Detector: Differential refractometer

[0262] Standard material: monodisperse polystyrene

[0263] <Compounds used in synthesis>

[0264] The compounds used in the synthesis are shown below.

[0265] Silsesquioxane (AC-SQ):

[0266] AC-SQ TA-100 manufactured by Toagosei Co., Ltd.: Silsesquioxane with the following structural units

[0267]

[0268] SH compounds: the following compounds (SH-1) to (SH-9)

[0269]

[0270] Silane compound: the following compounds (TAS-1) to (TAS-8)

[0271]

[0272] [Synthesis Example 1] Synthesis of Silsesquioxane (A-1)

[0273] After adding 50.0g (210mmol) of compound (TAS-1), 50mL of ethyl acetate and 0.2g (0.1mmol) of 4-methoxyphenol to a 300mL three-necked flask including a thermometer, the temperature was raised to 30°C while stirring. After that, 4.8g (47.4mmol) of triethylamine and 12.7g of ultrapure water were slowly added, the temperature was raised to 60°C and stirred for 3 hours. After that, the mixture was cooled to 30°C while stirring, 2.3g (21.7mmol) of compound (SH-1) was added, and the mixture was reacted at 50°C for 2 hours. At this time, GPC was confirmed, and the weight average molecular weight (Mw) was 4400, and the residual amount of compound (SH-1) was less than 0.1%, so it was confirmed that Michael addition was carried out quantitatively. After the reaction was completed, it was transferred to a separatory funnel, 100mL of ethyl acetate was added, and the mixture was washed once with 100mL of 1M hydrochloric acid water and three times with 50mL of water. Next, 80 g of propylene glycol monomethyl ether acetate (PGMEA) was added and the mixture was concentrated to 100 g. 80 g of PGMEA was then added again and concentrated. The solids concentration was then adjusted to 50% with PGMEA to obtain a solution of silsesquioxane (A-1). The weight-average molecular weight (Mw) of the obtained silsesquioxane (A-1) was 4400.

[0274] The obtained silsesquioxane (A-1) was reprecipitated with hexane and then dried, and the obtained substance was dissolved in dimethyl sulfoxide-d 6 Determination of 1H-nuclear magnetic resonance (NMR) showed δ12.2ppm (broad), 6.3ppm (s, 0.75H), 6.1ppm (s, 0.75H), 5.9ppm (s, 0.75H), 4.0ppm (d, 2H), 2.5ppm to 2.7ppm (m, 2H), 1.6ppm (m, 2H), and 0.6ppm (m, 2H). This indicates that compound (SH-1) undergoes quantitative Michael addition. Furthermore, Si-NMR analysis of silsesquioxane (A-1) revealed that multiple peaks were observed for component T2 (a component having a silanol group) at -55ppm to -58ppm, and multiple peaks were observed for component T3 (a component not having a silanol group) at -65ppm to -70ppm. In this Synthesis Example 1, the component not having a silanol group corresponds to either the structural unit (I) or the structural unit (II) in the aforementioned embodiment. The silanol group content (SiOH content ratio) relative to the total content (100 mol%) of structural units (I) and structural units (II) in silsesquioxane (A-1), calculated based on the strength of components T2 and T3, was 0.2 in terms of molar ratio. Based on this, it was inferred that the obtained silsesquioxane (A-1) had a highly condensed cage structure as its main structure. In addition, based on the amount of raw materials used, etc., the molar ratio of structural units (I) of the unadded compound (SH-1) to structural units (II) of the added compound (SH-1) in the obtained silsesquioxane (A-1) was calculated to be 90:10.

[0275] [Synthesis Example 2 to Synthesis Example 16]

[0276] Silsesquioxanes (A-2) to (A-16) were synthesized using the same method as in Synthesis Example 1 according to the combinations shown in Table 1. The weight average molecular weight and silanol group content of each silsesquioxane obtained were measured in the same manner as in Synthesis Example 1, and the molar ratio of structural unit (I) to structural unit (II) was calculated. The measurement results are shown in Table 1.

[0277] [Table 1]

[0278]

[0279] [Comparative Synthesis Example 1] Synthesis of Linear Polysiloxane Having Acryloyl Groups

[0280] In a 500 mL separable flask equipped with a stirrer, thermometer, nitrogen inlet, and reflux line, 23.4 g (99.8 mmol) of compound (TAS-1), 211 g of 1-methoxy-2-propanol, 1.8 g of water, and 0.12 g of phosphoric acid were added and stirred at 60°C for 4 hours. After the reaction, 211 g of 1-methoxy-2-propanol was added and the mixture was concentrated to 160 g. 211 g of 1-methoxy-2-propanol was added again and the mixture was concentrated to 75 g. 1-methoxy-2-propanol was then added to obtain a solution of polysiloxane (RS-1) having an acryloyl group with a solids concentration of 20%. Si-NMR analysis of polysiloxane (RS-1) revealed multiple peaks observed for the T2 component at -55 ppm to -58 ppm, and multiple peaks for the T3 component at -65 ppm to -70 ppm. The molar ratio of the silanol group content (SiOH content ratio) relative to the total content of structural units (I) and (II) in polysiloxane (RS-1), calculated from the strengths of components T2 and T3, was 1.1. This indicates that polysiloxane (RS-1) contains a large number of linear structures.

[0281] [Comparative Synthesis Example 2] Michael Addition to Polysiloxane

[0282] Add polysiloxane (RS-1) into a 500 mL three-necked flask equipped with a thermometer and a nitrogen inlet tube.

[0283] After 117 g (99.8 mol of polycondensate of TAS-1), 1.1 g (10.4 mmol) of compound (SH-1) and 174 g of tetrahydrofuran were added, 2.3 g (22.7 mmol) of triethylamine was gradually added and the temperature was raised to 50° C., resulting in gelation.

[0284] [Synthesis Example 17] Polymerization of Alkali-Soluble Straight-Chain Polysiloxane (B-1)

[0285] Add the compound to a 500 mL separable flask equipped with a stirrer, thermometer, and reflux tube.

[0286] 6.1 g (26.0 mmol) of (TAS-1), 13.9 g (70.0 mmol) of compound (TAS-7), 1.0 g (4.0 mmol) of compound (TAS-8), 211 g of 1-methoxy-2-propanol, 1.8 g of water, and 0.12 g of phosphoric acid were stirred at 60°C for 4 hours. After the reaction was completed, 211 g of 1-methoxy-2-propanol was added and the mixture was concentrated to 160 g. 211 g of 1-methoxy-2-propanol was added again and the mixture was concentrated to 75 g. 1-methoxy-2-propanol was then added to obtain a solution of polysiloxane (B-1) having an acryloyl group with a solid content concentration of 20%. Si-NMR measurement of polysiloxane (B-1) revealed multiple peaks observed at -55 ppm to -58 ppm for the T2 component and at -65 ppm to -70 ppm for the T3 component. The molar ratio of the silanol group content (SiOH content ratio) relative to the total content of the structural units constituting polysiloxane (B-1), calculated from the strengths of components T2 and T3, was 1.1. This suggests that polysiloxane (B-1) contains a large number of linear structures. The weight-average molecular weight (Mw) of polysiloxane (B-1) was 1,200.

[0287] [Synthesis Example 18] Polymerization of Alkali-Soluble Straight-Chain Polysiloxane (B-2)

[0288] In a 500 mL separable flask equipped with a stirrer, a thermometer, and a reflux tube, 11.7 g (59.0 mmol) of a silane compound (TAS-7), 10.7 g (41.0 mmol) of a silane compound (TAS-8), 211 g of 1-methoxy-2-propanol, 1.8 g of water, and 0.12 g of phosphoric acid were added and stirred at 60°C for 4 hours. After the reaction was completed, 211 g of 1-methoxy-2-propanol was added and the mixture was concentrated to 160 g. 211 g of 1-methoxy-2-propanol was added again and the mixture was concentrated to 75 g. 1-methoxy-2-propanol was then added to obtain a solution of polysiloxane (B-2) having an acryloyl group with a solids concentration of 20%. Si-NMR analysis of polysiloxane (B-2) revealed multiple peaks observed at -55 ppm to -58 ppm for the T2 component and at -65 ppm to -70 ppm for the T3 component. The molar ratio of silanol groups (SiOH content ratio) to the total content of structural units constituting polysiloxane (B-2), calculated from the strengths of components T2 and T3, was 1.1. This suggests that polysiloxane (B-2) contains a large number of linear structures. The weight-average molecular weight (Mw) of polysiloxane (B-2) was 1,400.

[0289] [Synthesis Example 19] Polymerization of Alkali-Soluble Poly(Meth)Acrylic Resin (B-3)

[0290] A 200 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a reflux line was charged with 3.8 g of acrylic acid, 9.6 g of Cyclomer M100 (manufactured by Daicel), 3.2 g of phenylmaleimide, 2.6 g of styrene, a solution of 12.8 g of methyl methacrylate dissolved in 68 g of PGMEA, 4.2 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.8 g of n-dodecylmercaptan. The mixture was heated to 70°C while stirring and stirred for 5 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a poly(meth)acrylic acid resin (B-3) solution having a solids concentration of 32%. The weight average molecular weight (Mw) of the poly(meth)acrylic acid resin (B-3) was 4,000.

[0291] [Synthesis Example 20] Polymerization of Alkali-Soluble Poly(Meth)Acrylic Resin (B-4)

[0292] A 200 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a reflux line was charged with 3.8 g of acrylic acid, 9.6 g of n-butyl methacrylate, 3.2 g of phenylmaleimide, 2.6 g of styrene, a solution of 12.8 g of methyl methacrylate dissolved in 68 g of PGMEA, 4.2 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.8 g of n-dodecylmercaptan. The mixture was heated to 70°C while stirring and stirred for 5 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a poly(meth)acrylic acid resin (B-4) solution having a solids concentration of 32%. The weight average molecular weight (Mw) of the poly(meth)acrylic acid resin (B-4) was 4,200.

[0293] [Synthesis Example 21] Polymerization of a resin (B-5) having acrylate and carboxylic acid groups obtained by modifying a cresol novolac type epoxy (meth)acrylate resin into an acid anhydride

[0294] A cresol novolac-type epoxy resin (manufactured by DIC Corporation, trade name: Epiclon N-695, epoxy equivalent: 220) was placed in a four-necked flask equipped with a stirrer and a reflux cooler.

[0295] 220 parts of propylene glycol were added, 214 parts of carbitol acetate were added, and heated to dissolve. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95°C to 105°C, 72 parts of acrylic acid were slowly added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80°C to 90°C, 106 parts of tetrahydrophthalic anhydride were added, and the mixture was reacted for 8 hours. After cooling, the mixture was taken out to obtain a resin (B-5) having acrylate and carboxylic acid groups obtained by modifying a cresol novolac type epoxy (meth)acrylate resin into anhydride (solid content concentration: 50%). The acid value of the solid content of the resin (B-5) obtained in the above manner was 85 mgKOH / g, and the weight average molecular weight (Mw) was about 3,500.

[0296] [Synthesis Example 22] Alkali-soluble silsesquioxane resin (B-7)

[0297] With reference to paragraphs

[0050] to

[0051] of Japanese Patent No. 4734832, polymerization of silsesquioxane having a glycidyloxypropyl group in the side chain was carried out. In addition, when isopropyl alcohol was distilled off, an appropriate amount of PGMEA was added to thereby prepare a solid content concentration of 50% by mass. 50g of the resin solution, 25g of isopropyl alcohol, and 1.5g (11.9mmol) of compound (SH-3) were added to a 300mL three-necked flask including a thermometer and heated to 30°C while stirring. 0.2g (0.6mmol) of tetrabutylammonium bromide was added thereto, the mixture was heated to 50°C and stirred for 3 hours. After the reaction was completed, isopropyl alcohol was distilled off, transferred to a separating funnel, 100mL of ethyl acetate was added, and washed 3 times with 100mL of water. Next, 50g of PGMEA was added and concentrated to a liquid volume of 50g, and then 50g of PGMEA was added again and concentrated. Thereafter, the solid content concentration was adjusted to 50% by mass with PGMEA to obtain a solution of silsesquioxane (B-7). The weight average molecular weight (Mw) of the obtained silsesquioxane (B-7) was 4400.

[0298] [Synthesis Example 23] Alkali-soluble silsesquioxane resin (B-8)

[0299] In a 300mL three-necked flask including a thermometer, 52.5g (210mmol) of KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.), 50mL of ethyl acetate and 0.2g (0.1mmol) of 4-methoxyphenol were added and the mixture was heated to 30°C while stirring. After that, 4.8g (47.4mmol) of triethylamine and 12.7g of ultrapure water were slowly added, the temperature was raised to 60°C and stirred for 3 hours. After the reaction was completed, the mixture was transferred to a separatory funnel, 100mL of ethyl acetate was added, and the mixture was washed once with 100mL of 1M hydrochloric acid water and 3 times with 50mL of water. Next, 80g of propylene glycol monomethyl ether acetate (PGMEA) was added and concentrated to a liquid volume of 100g, and then 80g of PGMEA was added again and concentrated. After that, a silsesquioxane resin solution was obtained by adjusting the solid content concentration to 50% by mass using PGMEA. 50 g of the resin solution, 25 g of isopropyl alcohol, and compound (SH-3) were mixed.

[0300] After 1.5g (11.9mmol) was added to a 300mL three-necked flask including a thermometer, the temperature was raised to 30°C while stirring. 0.2g (0.6mmol) of tetrabutylammonium bromide was added thereto, the temperature was raised to 50°C and stirred for 3 hours. After the reaction was completed, the isopropanol was distilled off, moved to a separatory funnel, 100mL of ethyl acetate was added, and washed 3 times with 100mL of water. Next, 50g of PGMEA was added, and after concentrating to a liquid volume of 50g, 50g of PGMEA was added again and concentrated. After that, a solution of silsesquioxane (B-8) was obtained by adjusting the solid content concentration to 50% by mass using PGMEA. The weight average molecular weight (Mw) of the obtained silsesquioxane (B-8) was 3600.

[0301] [Preparation Example 1] Preparation of Pigment Dispersion (C-1)

[0302] 12.0 parts by mass of a lactam pigment [Irgaphor Black S0100CF (manufactured by BASF Japan)] as a colorant, 11.8 parts by mass of BYK-LPN21116 (manufactured by BYK Chemie Japan Co., Ltd., solid content concentration 40.0% by mass) as a dispersant based on the solution, 13.0 parts by mass of an alkali-soluble poly(meth)acrylic resin (B-4) as a binder based on a polymer solution (solid content concentration 32% by mass), and a mixed solution containing 55.0 parts by mass of propylene glycol methyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a dispersion medium were mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion (C-1) as a color material.

[0303] [Preparation Example 2] Preparation of Pigment Dispersion (C-2)

[0304] A pigment dispersion (C-2) was prepared in the same manner as in Preparation Example 1 except that the type of colorant was changed to carbon black (TPX1227R, manufactured by Cabot Corporation).

[0305] [Preparation Example 3] Preparation of Pigment Dispersion (C-3)

[0306] In addition to changing the type of colorant to perylene pigment (Irgaphor Black

[0307] A pigment dispersion (C-3) was prepared in the same manner as in Preparation Example 1 except that FK4280, manufactured by BASF Corporation was used.

[0308] [Preparation Example 4] Preparation of Pigment Dispersion (C-4)

[0309] A pigment dispersion (C-4) was prepared in the same manner as in Preparation Example 1 except that the type of colorant was changed to titanium black (titanium nitride, manufactured by Jemco).

[0310] [Preparation Example 5] Preparation of Pigment Dispersion (C-5)

[0311] A pigment dispersion (C-5) was prepared in the same manner as in Preparation Example 1 except that the type of the colorant was changed to CI Pigment Green 58.

[0312] [Preparation Example 6] Preparation of Pigment Dispersion (C-6)

[0313] A pigment dispersion (C-6) was prepared in the same manner as in Preparation Example 1 except that the type of the colorant was changed to CI Pigment Yellow 138.

[0314] [Preparation Example 7] Preparation of Pigment Dispersion (C-7)

[0315] A pigment dispersion (C-7) was prepared in the same manner as in Preparation Example 1 except that the type of colorant was changed to CI Pigment Blue 15:6.

[0316] [Preparation Example 8] Preparation of Pigment Dispersion (C-8)

[0317] A pigment dispersion (C-8) was prepared in the same manner as in Preparation Example 1 except that the type of the colorant was changed to CI Pigment Red 177.

[0318] [Preparation Example 9] Preparation of Pigment Dispersion (C-9)

[0319] A pigment dispersion (C-9) was prepared in the same manner as in Preparation Example 1 except that the colorant was changed to 6 parts by mass of CI Pigment Blue 60 and 6 parts by mass of CI Pigment Violet 29.

[0320] [Preparation Example 10] Preparation of Pigment Dispersion (C-10)

[0321] A pigment dispersion (C-10) was prepared in the same manner as in Preparation Example 1 except that the type of the colorant was changed to CI Pigment Orange 38.

[0322] <Preparation of Photosensitive Composition>

[0323] Each component used for preparation of the photosensitive composition of an Example and a comparative example is shown.

[0324] (Silsesquioxane (A), etc.)

[0325] (A-1) to (A-16): Silsesquioxane (A-1) to Silsesquioxane (A-16) synthesized in Synthesis Examples 1 to 16

[0326] (RS-1): polysiloxane (RS-1) synthesized in Comparative Synthesis Example 1

[0327] (AC-SQ): AC-SQ TA-100 manufactured by Toagosei Co., Ltd.

[0328] (Alkali-soluble resin (B))

[0329] (B-1) to (B-2): linear polysiloxane synthesized in Synthesis Examples 17 and 18

[0330] (B-3) to (B-4): poly(meth)acrylic acid resin synthesized in Synthesis Examples 19 to 20

[0331] (B-5): a resin having acrylate and carboxylic acid groups obtained by modifying the cresol novolac type epoxy (meth)acrylate resin synthesized in Synthesis Example 21 into an acid anhydride

[0332] (B-6): "WR-301" manufactured by ADEKA (44% solid content PGMEA solution), resin obtained by modifying cardol resin into anhydride, and resin having acrylate and carboxylic acid groups

[0333] (B-7) to (B-8): silsesquioxane resins synthesized in Synthesis Examples 22 to 23

[0334] (Color material (C))

[0335] (C-1) to (C-10): Pigment dispersions (C-1) to (C-10) obtained in Preparation Examples 1 to 10

[0336] (Radiosensitive linear radical polymerization initiator (D))

[0337] (D-1): Irgacure OXE02 (manufactured by BASF Japan)

[0338] (D-2): Irgacure OXE01 (manufactured by BASF Japan)

[0339] (D-3): Oxime initiator represented by the following formula (D-3)

[0340]

[0341] (Polymerizable compound (E))

[0342] (E-1): Dipentaerythritol hexaacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0343] (E-2): Aronix M-520 (manufactured by Toagosei Co., Ltd.)

[0344] (E-3): UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.)

[0345] (Surfactant (F))

[0346] (F-1): Megafac F-554 (manufactured by DIC Corporation)

[0347] (Solvent (G))

[0348] (G-1): Propylene glycol monomethyl ether acetate (PGMEA)

[0349] (G-2): Propylene glycol monomethyl ether (PGME)

[0350] [Example 1]

[0351] 24.2 parts by mass of the pigment dispersion (C-1), 8.5 parts by mass of (A-1) as (A) silsesquioxane, 21.3 parts by mass of (B-3) as (B) alkali-soluble resin, 0.8 parts by mass of an oxime-based initiator (D-1) as (D) a radiation-sensitive radical polymerization initiator, and 0.4 parts by mass of a fluorine-based surfactant (F-1) as a surfactant (F) were added to 44.8 parts by mass of (G-1) as a solvent (G) so that the final solid content became 17.0% to prepare a coloring composition.

[0352] [Example 2 to Example 21, Comparative Examples 1 to 4]

[0353] Except having changed into the composition shown in Table 2, it carried out similarly to Example 1, and prepared the coloring composition of Example 2 - Example 21 and Comparative Example 1 - Comparative Example 4.

[0354] [Table 2]

[0355]

[0356] [evaluate]

[0357] The following items were evaluated by the methods described below for the colored compositions prepared in Examples 1 to 21 and Comparative Examples 1 to 4. The evaluation results are shown in Table 3.

[0358] <Resolution Evaluation>

[0359] Each prepared photosensitive coloring composition was applied to a soda glass substrate having an indium tin oxide (ITO) film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 1.5 μm. Subsequently, a photomask capable of forming a line pattern with a line width varying in the range of 1 μm to 50 μm with a line width of 1 μm was used, and a 35 mJ / cm 2 The coating film was exposed to radiation with wavelengths of 365 nm, 405 nm, and 436 nm. The exposed glass substrate with the coating was then placed on a horizontal rotating stage of a rotary spray developer (AD-2000, manufactured by Tatsuzawa Industry Co., Ltd.) and developed using a 0.04% by mass potassium hydroxide aqueous solution at 23°C for 60 seconds. The developed substrate was then rinsed with ultrapure water, air-dried, and post-baked in a clean oven at 230°C for 30 minutes to form a line pattern.

[0360] The resulting substrate with a line pattern was observed under an optical microscope to determine the appearance of the formed line pattern, the presence of residue, and the minimum line width that can be formed without defects in a shape corresponding to the photomask. A smaller minimum line width indicates that even narrow lines can be fully exposed to the substrate side, resulting in a pattern with excellent adhesion to the substrate. This indicates higher sensitivity during exposure (higher transmittance of the photosensitive coloring composition used for radiation (particularly g-rays, h-rays, and i-rays)).

[0361] (Evaluation Criteria)

[0362] ○: No appearance abnormalities (cracks, etc.), minimum line width less than 6μm

[0363] ×: There are abnormal appearances (cracks, etc.), or the minimum line width is 6μm or more

[0364] <Evaluation of residue>

[0365] Each of the prepared photosensitive coloring compositions was applied to a soda glass substrate having an ITO film formed on its surface using a spin coater, and then dried under reduced pressure at room temperature to form a coating film having a thickness of 1.5 μm. Subsequently, a photosensitive coloring composition was applied to the substrate at 35 mJ / cm2 using an MPA-600FA manufactured by Canon Co., Ltd. through a photomask. 2 The coating film is exposed to radiation of wavelengths of 365 nm, 405 nm and 436 nm. Afterwards, the exposed glass substrate with the coating film is placed on a horizontal rotating platform of a rotary spray developer (AD-2000, manufactured by Longze Industry (Co., Ltd.)), and a 0.04 mass% potassium hydroxide aqueous solution is used for liquid development at 23 ° C for 60 seconds. Afterwards, the developed substrate is cleaned with ultrapure water, air-dried, and then baked in a clean oven at 100 ° C for 5 minutes, thereby forming a quadrilateral hole pattern with rounded corners of 5 μm in length and width on the substrate. For the obtained pattern substrate, after platinum is sputtered using JEC-3000FC (manufactured by Japan Electronics (Co., Ltd.)), a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd. (Co., Ltd.) is used to observe the inside of the hole pattern (the part removed by development) and the number of foreign matter (point-shaped foreign matter) present therein is measured. The evaluation criteria are as follows. Fewer foreign materials inside the pattern mean less residue during development, ie, better developability.

[0366] (Evaluation Criteria)

[0367] ○: The number of foreign matter inside the hole pattern is less than 5

[0368] ×: The number of foreign matter inside the hole pattern is 5 or more

[0369] <Easy to comment>

[0370] As shown below, the outgassing generated when the cured products of the photosensitive coloring compositions obtained in Examples and Comparative Examples were heated was measured using a gas chromatograph based on the headspace method. First, the composition was applied to a silicon wafer substrate using a spin coater and then dried under reduced pressure at room temperature to form a coating film with a thickness of 1.5 μm. Subsequently, the composition was heated at 35 mJ / cm using an MPA-600FA manufactured by Canon. 2 The coating film was exposed to radiation with wavelengths of 365 nm, 405 nm, and 436 nm. The film was then post-baked in a clean oven at 230°C for 30 minutes to produce a cured film. The resulting cured film was cut into 1 cm squares, sealed in a headspace vial, and heated at 230°C for 15 minutes. The generated gas was measured using the headspace method. The amount of generated gas was determined based on the following criteria.

[0371] (Evaluation Criteria)

[0372] ○: The generated gas is less than 600 ppm

[0373] △: The generated gas is 600 ppm or more and less than 1000 ppm

[0374] ×: The generated gas is 1000 ppm or more

[0375] <Evaluation of storage stability>

[0376] The viscosity of each prepared photosensitive coloring composition at 25°C was evaluated using RE85L manufactured by Toki Sangyo Co., Ltd. The samples were stored at 5°C for one week, and then the viscosity at 25°C was re-evaluated. The increase in viscosity after storage relative to the initial viscosity was calculated and evaluated based on the following criteria.

[0377] (Evaluation Criteria)

[0378] ○: Thickening rate is -5% or more and less than 5%

[0379] ×: Thickening rate is 5% or more

[0380] <Measurement of optical density (OD value)>

[0381] Each prepared photosensitive coloring composition was applied using a spin coater onto a soda glass substrate having a SiO2 film formed on its surface for preventing sodium ion elution, and then dried under reduced pressure at room temperature to form a coating film having a film thickness of 3.0 μm.

[0382] Then, using MPA-600FA manufactured by Canon, a photomask was used to conduct the irradiation at 35 mJ / cm 2The obtained coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of .

[0383] The exposed, coated glass substrate was then placed on a horizontal rotating platform of a rotary spray developer (AD-2000, manufactured by Tatsuzawa Industry Co., Ltd.) and subjected to flood development using a 0.04% by mass potassium hydroxide aqueous solution at 23°C for 60 seconds. The developed substrate was then rinsed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes, forming a 2 cm × 4 cm strip pattern on the substrate.

[0384] The optical density (OD value) of the obtained stripe pattern was measured using a white-black transmission densitometer 361T manufactured by X-Rite Co., Ltd. A higher OD value indicates a higher light-shielding property.

[0385] [Table 3]

[0386]

[0387] As shown in Table 3, the photosensitive coloring compositions of Examples 1 to 21 were excellent in storage stability and formed cured products with excellent resolution, residue, and outgassing. On the other hand, the comparative examples did not yield compositions that fully satisfied the storage stability, resolution, residue, and outgassing requirements.

Claims

1. A photosensitive coloring composition comprising: a silsesquioxane having a structural unit (I) represented by the following formula (1); Alkali soluble resin; color materials; Radiation-sensitive linear free radical polymerization initiator; and organic solvents, The content of the silanol group relative to the total content of the structural units constituting the silsesquioxane is less than 0.3 in terms of molar ratio; In the formula (1), X is a group represented by the following formula (2); In the formula (2), R 1 are independently a hydrogen atom or a methyl group; R 2 Each independently represents an alkanediyl group having 2 to 10 carbon atoms.

2. The photosensitive coloring composition according to claim 1, comprising a silsesquioxane having a structural unit (II) represented by the following formula (3) in addition to the structural unit (I) represented by the formula (1); In the formula (3), Y is represented by the following formula (4a), formula (4b) or formula (4c); In the formula (4a), formula (4b) and formula (4c), R 1 are independently a hydrogen atom or a methyl group; R 2 are each independently an alkanediyl group having 2 to 10 carbon atoms; R 3 is a divalent organic group; R 4 is a single bond or a divalent organic group; X is a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group or an alkoxy group; n is an integer from 0 to 4; when n is 2 or more, multiple Xs are the same or different; * represents a bonding site.

3. The photosensitive coloring composition according to claim 2, wherein The content of the structural unit (I) relative to the total content of the structural unit (I) and the structural unit (II) in the silsesquioxane is 10 mol% or more and 100 mol% or less. The photosensitive coloring composition according to claim 1 , further comprising a polymerizable compound having two or more polymerizable groups. 5 . A cured product obtained by curing the photosensitive coloring composition according to claim 1 .

6. The cured product according to claim 5, wherein The optical density is in the range of 0.5 to 4.

0. 7 . The cured product according to claim 5 , which is a color filter, a black matrix, or a light-shielding partition material.

8. An image display panel comprising the cured product according to claim 5 as a color pattern of a color filter. 9 . An image display device comprising the image display panel according to claim 8 .

10. A color filter comprising the hardened material according to claim 5 as a black matrix.

11. An image display panel comprising the color filter according to claim 10. 12 . An image display device comprising the image display panel according to claim 11 .

13. An image display device comprising the cured product according to claim 5 as a light-shielding partition wall material.

14. A method for manufacturing a patterned hardened object, comprising: A step of applying the photosensitive coloring composition according to any one of claims 1 to 4 on a substrate to form a coating film; A process of performing position selective exposure on the coating film; a step of developing the exposed coating film; and A step of heating the patterned coating film after development.

15. The manufacturing method according to claim 14, wherein: The patterned hardened object is a color filter, a black matrix or a light-shielding isolation wall material.

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