Photosensitive composition for organic el display device and organic el display device

Abstract

Provided are: a photosensitive composition for an organic EL display device, which has excellent storage stability as a photosensitive composition, has excellent curability at low temperatures, and is capable of forming a cured film having good developability and high light-blocking properties; and an organic EL display device comprising a cured film having high light-blocking properties. A photosensitive composition for an organic EL display device includes carbon black, a polymerizable compound, a photopolymerization initiator, and a photosensitive resin, the photopolymerization initiator including a compound having two or more oxime esters in one molecule, the polymerizable compound including a hexa-functional polymerizable compound and a trifunctional polymerizable compound, the trifunctional polymerizable compound including an oxime ester having two or more oxime esters in one molecule, the trifunctional polymerizable compound including an oxime ester having two or more oxime esters in one molecule, and the trifunctional polymerizable compound including an oxime ester having two or more oxime esters in one molecule. The photosensitive composition for an organic EL display device contains the carbon black in an amount of 30-50% by mass of the non-volatile components of the photosensitive composition for an organic EL display device.

Description

Technical Field

[0001] The present invention relates to a photosensitive composition for an organic EL display device and an organic EL display device. Background Art

[0002] In recent years, in electronic devices such as mobile phones and portable information terminals, in order to meet the requirements of thin, lightweight or curved displays, the development and mass production of display devices using organic EL (organic electroluminescence) as a self-luminous component are being promoted. Among them, since the thin and lightweight characteristics are effectively utilized, it is expected to be used in high-definition and small displays of about 0.5 inches (hereinafter referred to as micro displays) such as head-mounted displays and electronic viewfinders.

[0003] There are two main display methods for organic EL displays: a method of forming a film on a white light-emitting layer and using a color filter to display red, green, blue (RGB) and other colors; and a method of vapor-depositing a light-emitting layer that emits light of each color such as RGB and displaying the color. Since microdisplays have fine pixels, it is very difficult to selectively form a film on the RGB light-emitting layer. Therefore, a method of using a color filter in the white light-emitting layer is actively adopted in microdisplays.

[0004] The pixel size of the microdisplay is fine and is 1 μm to 5 μm. Therefore, in the method of making organic EL components and color filters and bonding them to separate substrates that has been used since then, the accuracy may be reduced and color shift may occur. Therefore, a method of forming a color filter on an organic EL component is proposed. In addition, in a microdisplay, a patterned light-shielding film such as a black matrix is ​​usually formed so that the light of the organic EL component passing through the color filter pixel does not mix colors. In addition, a light-shielding portion is sometimes formed on the periphery of the display area of ​​the component in order to suppress the reflected light from the wiring. As one of the methods for forming the light-shielding layer pattern such as the black matrix or the light-shielding portion, a photolithography method using a photosensitive composition is known.

[0005] For example, Patent Document 1 discloses a photosensitive resin composition as a photosensitive composition for a black matrix, which includes a binder resin, a photopolymerizable compound, a photopolymerization initiator, a colorant including a black pigment and other organic pigments, and a thermosetting compound (Patent Document 1).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2019-61216 Summary of the invention

[0009] Problems to be solved by the invention

[0010] The photolithography method generally includes a step of calcining at a high temperature (e.g., 230°C). In order to form a color filter on an organic EL component with low heat resistance, it is required to lower the calcination temperature. In addition, the light-shielding layer on a microdisplay that requires a finer pattern requires further light-shielding properties or a designed pattern shape. The photosensitive resin composition described in Patent Document 1 contains an organic pigment, so there is room for improvement in light-shielding properties. In addition, if the pigment ratio in the coating film is increased in order to improve the light-shielding properties of the coating film, there will be problems with the storage stability of the photosensitive composition or problems such as the generation of residues after development.

[0011] The present disclosure aims to provide a photosensitive composition for an organic EL display device which has excellent storage stability as a photosensitive composition, excellent curability at low temperatures, and can form a cured film having good developability and high light-shielding properties, and an organic EL display device including a cured film having high light-shielding properties.

[0012] Means of solving problems

[0013] The photosensitive composition for an organic EL display device disclosed herein comprises carbon black, a polymerizable compound, a photopolymerization initiator, and a photosensitive resin, wherein:

[0014] The photopolymerization initiator comprises a compound having two or more oxime esters in one molecule,

[0015] The polymerizable compound comprises a hexafunctional polymerizable compound and a trifunctional polymerizable compound,

[0016] The photosensitive composition for an organic electroluminescent display device contains the carbon black in an amount of 30% by mass to 50% by mass of a nonvolatile component of the photosensitive composition for an organic EL display device.

[0017] In one aspect of the photosensitive composition for an organic EL display device, the compound having two or more oxime esters in one molecule includes a compound represented by the following chemical formula (1-1).

[0018] [Chemistry 1]

[0019] Chemical formula (1-1)

[0020]

[0021] In one aspect of the photosensitive composition for an organic EL display device, the average primary particle size of the carbon black is 50 nm or less.

[0022] In one embodiment of the photosensitive composition for an organic EL display device, the specific surface area of ​​the carbon black is 80 m 2 / g~260m 2 / g.

[0023] In one aspect of the photosensitive composition for an organic EL display device, the photopolymerization initiator is contained in an amount of 3% by mass to 16% by mass of a non-volatile component of the photosensitive composition for an organic EL display device.

[0024] In one aspect of the photosensitive composition for an organic EL display device, a ratio of the photosensitive resin in all resin components contained in the photosensitive composition is 80 mass % or more.

[0025] The organic EL display device disclosed herein includes a light shielding layer formed of the photosensitive composition for an organic EL display device.

[0026] Effects of the Invention

[0027] The present disclosure provides a photosensitive composition for an organic EL display device having excellent storage stability, excellent curability at low temperatures, good developability and the ability to form a cured film having high light-shielding properties, and an organic EL display device including a cured film having high light-shielding properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic cross-sectional view of the organic EL display device. DETAILED DESCRIPTION

[0029] Hereinafter, the photosensitive composition for an organic EL display device and the organic EL display device will be described.

[0030] In addition, in this disclosure, "to" which shows a numerical range means that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0031] In the present disclosure, when “(meth)acryloyl”, “(meth)acrylic acid”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” is expressed, it means “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively, unless otherwise specified.

[0032] 1. Photosensitive composition for organic EL display device

[0033] The photosensitive composition for an organic EL display device disclosed herein (hereinafter also referred to as the "photosensitive composition") comprises carbon black, a polymerizable compound, a photopolymerization initiator, and a photosensitive resin, wherein the photopolymerization initiator comprises a compound having two or more oxime esters in one molecule, the polymerizable compound comprises a hexafunctional polymerizable compound and a trifunctional polymerizable compound, and the photosensitive composition comprises the carbon black in an amount of 30% to 50% by mass of the non-volatile components of the photosensitive composition for an organic EL display device.

[0034] The photosensitive composition of the structure contains a compound having two or more oxime esters in one molecule as a photopolymerization initiator, and has excellent curability, especially curability at low temperatures. Therefore, even when a patterned cured film is formed on an organic EL component by photolithography using the photosensitive composition, a light-shielding film can be formed without causing thermal damage to the organic EL component. In addition, since the photosensitive composition has excellent curability, even when the ratio of carbon black is set to 30% to 50% by mass, the developability is also excellent, and a cured film with a designed pattern shape can be formed, and the development residue is also suppressed. In addition, by increasing the ratio of carbon black, a cured film with high light-shielding properties can be formed.

[0035] The present photosensitive composition contains at least carbon black, a polymerizable compound, a photopolymerization initiator, and a photosensitive resin, and may further contain other components within the scope that can solve the problems of the present invention.

[0036] <Carbon black>

[0037] This photosensitive composition uses carbon black as a black component of a colorant. By using carbon black, a cured film having excellent light-shielding properties can be formed.

[0038] In terms of improving dispersibility and light-shielding properties and obtaining a good fine line pattern (linearity), the average primary particle diameter of carbon black is preferably 50 nm or less, more preferably 10 nm to 30 nm, and further preferably 15 nm to 25 nm. By setting the average primary particle diameter to be 10 nm or more, it is also possible to suppress development residue. In addition, in terms of improving dispersibility and light-shielding properties, the specific surface area of ​​carbon black is preferably 80 m 2 / g~260m 2 / g, preferably 100m 2 / g~180m 2 / g, preferably 110m 2 / g~120m 2 / g. By setting the specific surface area to 80m 2 / g or more, the adhesion to the substrate (organic EL element) is also improved.

[0039] Furthermore, the primary particle diameter of carbon black is determined by directly measuring the size of the primary particles based on an electron microscope photograph obtained using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of each primary particle of carbon black are measured, and the average value is set as the particle diameter. Next, for more than 20 carbon black particles, the volume of each particle is approximated as a cube of the particle diameter, and the volume average particle diameter is set as the average primary particle diameter.

[0040] Commercially available carbon black may be used. Examples of commercially available carbon black include #40, #44, #45, #45L, #47, and #52 manufactured by Mitsubishi Chemical Corporation and Printex 55 manufactured by Orion Engineered Carbons. Carbon black may be used alone or in combination of two or more.

[0041] The carbon black may be subjected to a micronization treatment. The micronization method may be appropriately selected from known methods, and examples thereof include wet milling, dry milling, and dissolution separation. Examples of wet milling include salt milling using a kneader method.

[0042] The so-called salt milling treatment is a treatment in which a mixture of carbon black, a water-soluble inorganic salt and a water-soluble organic solvent is mechanically mixed while being heated using a kneading machine such as a kneader, a double-roll mill, a triple-roll mill, a ball mill, a grinder, a sand mill, etc., and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing. The water-soluble inorganic salt (for example, sodium chloride) acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the carbon black during salt milling. By optimizing the conditions for salt milling of carbon black, a carbon black with a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution can be obtained.

[0043] When the carbon black is subjected to salt milling treatment, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified from natural resins, etc. may be used. The resin used is preferably solid at room temperature and water-insoluble, and further preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass relative to 100 parts by mass of the carbon black.

[0044] The average primary particle size of carbon black can be adjusted to the above range by performing the salt milling treatment.

[0045] The content of carbon black in the photosensitive composition is 30% to 50% by mass of the nonvolatile components of the photosensitive composition. By setting the content to 30% to 50% by mass, both the storage stability of the photosensitive composition and the light shielding property of the cured product can be achieved.

[0046] (Other colorants)

[0047] The photosensitive composition may also include other colorants other than carbon black within the scope of the effect of the present invention. As other colorants, known black pigments or organic pigments of various colors can be cited. In terms of storage stability or light-shielding properties of the composition, the content ratio of other colorants in the photosensitive composition is preferably less than 5 parts by mass, more preferably less than 1 part by mass, and further preferably less than 0.1 parts by mass, relative to 100 parts by mass of carbon black.

[0048] <Polymerizable compounds>

[0049] The polymerizable compound is suitably selected from the compound that can be polymerized by the action of the photopolymerization initiator described later. As the polymerizable compound, it is preferably a compound having one or more ethylenically unsaturated bonds in one molecule, and it is preferably a polyfunctional compound having two or more ethylenically unsaturated bonds. In addition, as ethylenically unsaturated bonds, vinyl, (meth) acryloyl, etc. can be listed, preferably (meth) acryloyl, preferably acryloyl. Furthermore, the polymerizable compound also includes a polymerizable oligomer having a molecular weight of about 1000 or less.

[0050] Examples of polymerizable compounds include di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; di(meth)acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; poly(meth)acrylates of trivalent or higher polyols such as glycerol, trimethylolpropane, pentaerythritol, and dipentaerythritol; and oligo(meth)acrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, and spirane resins.

[0051] The present photosensitive composition preferably contains a hexafunctional polymerizable compound from the viewpoint of improving curability. Examples of the hexafunctional polymerizable compound include dipentaerythritol hexa(meth)acrylate and the like.

[0052] Furthermore, the present photosensitive composition is preferably a combination of a hexafunctional polymerizable compound and a trifunctional polymerizable compound. By using a trifunctional polymerizable compound in combination, the linearity of the patterned cured film is improved. The weight ratio of the hexafunctional polymerizable compound to the trifunctional polymerizable compound is preferably 99 / 1 to 1 / 99, and more preferably 90 / 10 to 50 / 50.

[0053] Specific examples of trifunctional polymerizable compounds include trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide (EO) modified tri(meth)acrylate, trimethylolpropane propylene oxide (PO) modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. Among these, trimethylolpropane EO modified tri(meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, etc. are preferred in terms of improving developability. Two or more of these can be used in combination.

[0054] The polymerizable compound may further use other (meth)acrylate monomers. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate. Various acrylates and methacrylates such as (meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecyl (meth)acrylate, (meth)acrylate of hydroxymethylated melamine, epoxy (meth)acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc., but are not limited to these.

[0055] The content of the polymerizable compound in the photosensitive composition is preferably 5% to 40% by mass of the nonvolatile components of the photosensitive composition, and more preferably 20% to 30% by mass. By setting it within the above range, peeling when forming a fine pattern can be eliminated, and the tapered portion of the pattern can be suppressed from being elongated, thereby forming a high-definition fine pixel pattern.

[0056] <Photopolymerization initiator>

[0057] The photopolymerization initiator can be appropriately selected from initiators that accelerate the polymerization reaction of a polymerizable compound by the action of light and can be used.

[0058] In the present photosensitive composition, in terms of ultraviolet curability, color characteristics, chemical resistance, and excellent developability, the photopolymerization initiator is preferably a compound containing two or more oxime esters (>C=N-OC(=O)-) in one molecule (hereinafter also referred to as oxime ester-based photopolymerization initiator).

[0059] Oxime ester photopolymerization initiators cause the cleavage of the NO bond of oxime by absorbing ultraviolet rays, generating imino radicals and alkoxy radicals. These free radicals generate highly active free radicals by further decomposition, so patterns can be formed with less exposure. In addition, oxime ester photopolymerization initiators have high quantum efficiency, so they have excellent curability even when the colorant (carbon black) in the composition is at a high concentration. According to this photosensitive product, a cured film with excellent developability and good pattern formability can be formed by photolithography. In addition, by using oxime ester photopolymerization initiators, the light-shielding property and chemical resistance of the cured film are also excellent.

[0060] Among them, as a compound having two or more oxime esters (>C═N—OC(═O)—) in one molecule, an oxime ester-based photopolymerization initiator represented by the following general formula (1) is preferred.

[0061] (Oxime ester photopolymerization initiator represented by general formula (1))

[0062] [Chemistry 2]

[0063] General formula (1)

[0064]

[0065] (In the general formula (1), W1 and W2 each independently represent a carbonyl bond (-CO-) or a single bond, and at least one of W1 and W2 is a carbonyl bond (-CO-);

[0066] R a is an alkyl group having 2 to 6 carbon atoms, R b is an alkyl group having 4 to 10 carbon atoms, R c is a group containing at least a hydrocarbon ring or a heterocyclic ring, and may further contain at least one divalent linking group selected from an alkylene chain having 1 to 4 carbon atoms, a sulfide bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-), R b With R c are different substituents; R d and R e are each independently an alkyl group having 1 to 6 carbon atoms)

[0067] R a Examples of the alkyl group include straight-chain alkyl groups such as ethyl, propyl, butyl, and hexyl.

[0068] As Rb The alkyl group in includes linear alkyl groups such as butyl, hexyl, octyl, and dodecyl.

[0069] As R c Examples of the hydrocarbon ring in R include aliphatic hydrocarbon rings such as cyclohexyl, and aromatic hydrocarbon rings such as phenyl, naphthyl, and anthracenyl. c The heterocyclic ring in the above-mentioned hydrocarbon ring may be a ring formed by replacing one or more carbon atoms of the hydrocarbon ring with a nitrogen atom, an oxygen atom or a sulfur atom.

[0070] In addition, R d and R e Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl.

[0071] Among them, the oxime ester-based photopolymerization initiator represented by the general formula (1) is preferably a compound represented by the following chemical formula (1-1).

[0072] [Chemistry 3]

[0073] Chemical formula (1-1)

[0074]

[0075] The photopolymerization initiator may also use other photopolymerization initiators while using the compound having two or more oxime esters in one molecule. As other photopolymerization initiators, there can be listed: a compound having one oxime ester in one molecule or a photopolymerization initiator other than an oxime ester-based polymerization initiator. Among them, the oxime ester-based photopolymerization initiator having one oxime ester in one molecule is preferably an oxime ester-based photopolymerization initiator represented by the following general formula (2) or general formula (3).

[0076] (Oxime ester photopolymerization initiator represented by general formula (2))

[0077] [Chemistry 4]

[0078] General formula (2)

[0079]

[0080] (In the general formula (2), Z represents a direct bond or a -C(=O)- group, and R 1 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, R 2 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, R 3 ~R 10 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or R 11 -C(=O)-; 11represents an aryl group which may have a substituent)

[0081] R 1 ~R 10 Examples of the alkyl group having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and dodecyl.

[0082] As R 2 ~R 11 The aryl group in includes phenyl, naphthyl, anthracenyl and the like.

[0083] Furthermore, the phrase "Z is directly bonded" means that Z has no atom and the two atoms connected to Z in the general formula (2) are directly bonded.

[0084] The substituents that the alkyl and aryl groups may have refer to the substituents that may replace the hydrogen atoms that the alkyl or aryl groups have. Examples of the substituents include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; alkoxy groups such as methoxy groups, ethoxy groups, and tert-butoxy groups; aryloxy groups such as phenoxy groups and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups, butoxycarbonyl groups, and phenoxycarbonyl groups; acyloxy groups such as acetyloxy groups, propionyloxy groups, and benzoyloxy groups; acyl groups such as acetyl groups, benzoyl groups, isobutyryl groups, acyl groups, methacryloyl groups, and methoxyoxalyl groups; alkylthio groups such as methylthio groups and tert-butylthio groups; arylthio groups such as phenylthio groups and p-tolylthio groups; alkylamino groups such as methylamino groups and cyclohexylamino groups; dimethylamino groups, diethylamino groups, morpholino groups, and piperidinyl groups. dialkylamino groups; arylamino groups such as phenylamino and p-tolylamino groups; alkyl groups such as methyl, ethyl, t-butyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclooctadecyl groups; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, and phenanthryl groups; heterocyclic groups such as furanyl and thienyl groups; and hydroxyl, carboxyl, formyl, mercapto, sulfonyl, methanesulfonyl, p-toluenesulfonyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinicogroup, phosphono, trimethylammonium, dimethylsulfonium, and triphenylphenacylphosphonium groups.

[0085] In addition, these substituents may exist in more than one or more than one type, and the hydrogen atoms of these substituents may be further substituted by other substituents.

[0086] Among them, the oxime ester photopolymerization initiator represented by the general formula (2) is preferably: Z is a direct bond or a -C(=O)- group, R 1 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, R 2 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, R 3~R 10 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or R 11 -CO- group. Among them, more preferably: R 4 ~R 6 and R 8 ~R 10 is a hydrogen atom, R 7 is a hydrogen atom, or R 11 -CO- group, R 11 It is an aryl group which may have a substituent.

[0087] Among them, the oxime ester photopolymerization initiator represented by the general formula (2) is preferably a compound represented by the following chemical formula (2-1) or chemical formula (2-2).

[0088] [Chemistry 5]

[0089]

[0090] (Oxime ester photopolymerization initiator represented by general formula (3))

[0091] [Chemistry 6]

[0092] General formula (3)

[0093]

[0094] (In general formula (3), R 21 and R 22 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R 23 and R 24 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R 25 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or R 26 -CO- group, R 26 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group)

[0095] R 21 ~R 26 The alkyl group having 1 to 20 carbon atoms in the R 1 ~R 10 The alkyl group having 1 to 20 carbon atoms is the same as the alkyl group.

[0096] R 21 ~R 26 The aryl group in can be set to be the same as the R 2 ~R 11The same group as the aromatic group in .

[0097] As R 26 Examples of the heterocyclic ring in the heterocyclic group include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thiandene, indole, carbazole, coumarin, quinoline, phthalazine, and quinoxaline.

[0098] The substituents that the alkyl group and the aryl group may have may be the same substituents as those in the general formula (2).

[0099] The oxime ester photopolymerization initiator represented by the general formula (3) is preferably: R 21 is an aryl group which may have a substituent, R 22 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, R 23 and R 24 is a hydrogen atom, R 25 is a hydrogen atom, or R 26 -CO- group.

[0100] Among them, the oxime ester-based photopolymerization initiator represented by the general formula (3) is preferably a compound represented by the following chemical formula (3-1).

[0101] [Chemistry 7]

[0102] Chemical formula (3-1)

[0103]

[0104] In addition, examples of photopolymerization initiators other than the oxime ester-based photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone, 2-benzyl-2-dimethylamino -1-(4-morpholinylphenyl)-butane-1-one and other acetophenone compounds; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzil dimethyl ketal and other benzoin compounds; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl Thioxanthone compounds such as 2,4-diisopropylthioxanthone and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)- Triazine compounds such as s-triazine, 2-(4-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxyphenylvinyl)-6-triazine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; titanocene compounds, etc.

[0105] These photopolymerization initiators may be used alone or in combination of two or more at any ratio as needed.

[0106] As commercially available products of photopolymerization initiators, acetophenone compounds include "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one), "IRGACURE 369" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone), and "IRGACURE 379" (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one), all of which are manufactured by BASF Japan. Phosphine compounds include "IRGACURE 369" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone), all of which are manufactured by BASF Japan. Japan) "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) and "IRGACURE TPO" (2,4,6-trimethylbenzoyldiphenylphosphine oxide).

[0107] The content ratio of the photopolymerization initiator in the photosensitive composition is preferably 3% to 16% by mass of the non-volatile components of the photosensitive composition, and is more preferably 10% to 16% by mass from the viewpoint of photocurability and developability. If the photopolymerization initiator is 3 parts by mass or more, the adhesion to the substrate is excellent. In addition, if the photopolymerization initiator is 16 parts by mass or less, the resolution is excellent.

[0108] The proportion of the compound having two or more oxime esters in one molecule in the photopolymerization initiator is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the photopolymerization initiator.

[0109] <Sensitizer>

[0110] The present photosensitive composition may further contain a sensitizer.

[0111] Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone; 1,2-diketone derivatives such as benzyl or camphorquinone; benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine pigments; acridine derivatives, azine derivatives, derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives phthalocyanine derivatives, pyrylium derivatives, thiopyranium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organic ruthenium complexes, or michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methyl phenyl glyoxylate, benzil, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethyl isophthalophenone, 3,3'-tetra(tert-butylperoxycarbonyl)benzophenone or 4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

[0112] Among the sensitizers, thioxanthone derivatives, michler's ketone derivatives, and carbazole derivatives are particularly suitable for sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are mentioned.

[0113] In addition, commercial products of the sensitizer include "KAYACURE DETX-S" (2,3-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "EAB-F" (4,4'-bis(diethylamino)benzophenone, manufactured by Hodogaya Chemical Industry Co., Ltd.).

[0114] Furthermore, a sensitizer that absorbs light in the ultraviolet to near-infrared region may be contained.

[0115] The sensitizer may be used alone or in combination of two or more at any ratio as needed.

[0116] When the sensitizer is used, the content is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator contained in the photosensitive composition, from the viewpoint of photocurability and developability.

[0117] <Resin>

[0118] The photosensitive composition contains a resin, which at least includes a photosensitive resin. The resin is preferably a transparent resin having a transmittance of 80% or more in the total wavelength region of 400nm to 700nm when forming a film with a thickness of 2μm, and the transmittance is preferably 95% or more. Examples of the resin include: binder resins and resin-type dispersants. Examples of binder resins include: thermoplastic resins, alkali-soluble resins, alkali-soluble photosensitive resins, etc. In terms of pattern forming properties based on photolithography, the resin preferably includes a resin with alkali solubility. The photosensitive resin is a resin having a polymerizable unsaturated group such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group as a photosensitive group. The photosensitive resin is a resin having a photosensitive group in a binder resin and a resin-type dispersant. Furthermore, in the present photosensitive composition, the resin refers to a resin having a molecular weight or a weight average molecular weight of 1000 or more, including resins with various functionalities described later. First, the binder resin is described.

[0119] (Alkali soluble resin)

[0120] Examples of alkali-soluble resins include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of alkali-soluble thermoplastic resins include acrylic resins having acidic groups, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0121] (Thermoplastic resin)

[0122] Thermoplastic resins may also include resins that are not alkali soluble. Examples of thermoplastic resins that are not alkali soluble include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, cellulose, polyethylene (high-density polyethylene (HDPE), low-density polyethylene (LDPE)), polybutadiene, and polyimide resins.

[0123] (Alkali soluble photosensitive resin)

[0124] The alkali-soluble photosensitive resin has photosensitivity due to the presence of a polymerizable unsaturated group. The alkali-soluble photosensitive resin may be any resin as long as it is alkali-soluble and photosensitive, and a known resin may be used, but a resin synthesized by the following method (i) or method (ii) is preferred. When an alkali-soluble photosensitive resin is used, three-dimensional crosslinking is performed by light irradiation, and the crosslinking density is increased, thereby improving the chemical resistance of the film.

[0125] [Method (i)]

[0126] Method (i) includes, for example, the following method: first, synthesizing an epoxy-containing monomer and a polymer of other monomers; then, adding a monocarboxyl-containing monomer to the epoxy group of the polymer, and reacting the generated hydroxyl group with a polyacid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl-containing monomer is a monomer having one carboxyl group.

[0127] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0128] Examples of the monomer containing a monocarboxyl group include (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and monocarboxylic acids such as (meth)acrylic acid substituted with halogenated alkyl, alkoxy, halogen, nitro, or cyano groups at the α-position.

[0129] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group which does not form an acid anhydride.

[0130] Other monomers include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;

[0131] (Meth)acrylamide such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine; (meth)acrylamide such as styrene or α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; fatty acid vinyl esters such as vinyl acetate or vinyl propionate; and the like.

[0132] Other examples include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4- Maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3 -Dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine and other N-substituted maleimides, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenol ethylene oxide (EO) modified (meth) acrylate, p-cumylphenol EO or propylene oxide (PO) modified (meth) acrylate, nonylphenol EO modified (meth) acrylate, nonylphenol PO modified (meth) acrylate, etc.

[0133] [Method (ii)]

[0134] Method (ii) includes, for example, the following method: synthesizing hydroxyl-containing monomers, carboxyl-containing monomers, and other monomers to produce a polymer; and then reacting the isocyanate group of the isocyanate-containing monomer with the hydroxyl group of the polymer to synthesize an alkali-soluble photosensitive resin.

[0135] Examples of hydroxyl-containing monomers include methacrylate hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, or polyester mono(meth)acrylates obtained by addition polymerization of polyγ-valerolactone, polyε-caprolactone, and / or poly-12-hydroxystearic acid, etc., can also be cited. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0136] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis(methacryloyloxy)ethyl isocyanate.

[0137] Usable monomers other than the above monomers include the other monomers exemplified in the above method (i) and monomers containing a phosphoric acid ester group.

[0138] The phosphoric acid ester group-containing monomer is, for example, a compound obtained by reacting a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid with a hydroxyl group of a hydroxyl group-containing monomer.

[0139] (Resin type dispersant)

[0140] The resin-type dispersant has a colorant affinity site that is adsorbed to carbon black and a relaxation site that has a high affinity for components other than carbon black and causes steric repulsion between dispersed particles.

[0141] Regarding the resin-type dispersant, as a resin-type dispersant having an acidic group, for example, there can be listed: carbamate-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylates, ammonium salts of polycarboxylates, alkylamine salts of polycarboxylates, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, or modified products thereof; amides or salts thereof formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphate series, etc.

[0142] Examples of the polymer dispersant having a basic group include nitrogen-containing graft copolymers, nitrogen-containing acrylic block copolymers having a functional group including a tertiary amine group, a quaternary ammonium salt group, a nitrogen-containing heterocycle, etc. in a side chain, and urethane polymer dispersants.

[0143] The resin type dispersant is preferably photosensitivity. In addition, the resin type dispersant preferably has an acidic group, and the acid value is preferably 5 mgKOH / g to 150 mgKOH / g, more preferably 10 mgKOH / g to 120 mgKOH / g, and further preferably 20 mgKOH / g to 120 mgKOH / g. In addition, the resin type dispersant preferably does not have an amine, and the amine value is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and further preferably 1 mgKOH / g or less.

[0144] Examples of commercially available resin dispersants include BYK Chemie Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Latimu Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. manufactured by Japan BASF Japan) company's EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Precision Technology (Ajinomoto Ajisper - PA111, PB711, PB821, PB822, PB824, etc. manufactured by Fine-Techno.

[0145] (Resin with thermosetting group)

[0146] In addition, each of the above resins may have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

[0147] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000. The value of Mw / Mn is preferably 10 or less. In addition, Mn is a number average molecular weight.

[0148] The acid value of the resin is preferably 50 mgKOH / g to 200 mgKOH / g, more preferably 70 mgKOH / g to 180 mgKOH / g, and still more preferably 90 mgKOH / g to 170 mgKOH / g. A moderate acid value can achieve a high balance among alkali solubility, adhesion, and residue suppression.

[0149] The resin can be used alone or in combination of two or more. The content of the resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, relative to 100 parts by mass of carbon black. If an appropriate amount is contained, a film can be easily formed, and good light-shielding properties can be easily obtained. In terms of good film-forming properties and various resistances, it is preferably more than 20 parts by mass, and in terms of relatively high carbon black concentration and good light-shielding properties, it is preferably less than 400 parts by mass.

[0150] In addition, among all the resin components contained in the photosensitive composition, the proportion of the photosensitive resin is preferably 80% by mass or more, more preferably 90% by mass or more. By including a large amount of photosensitive resin, the developability or curability is further improved. Among them, it is preferred that the resin-type dispersant described later has photosensitivity. Among all the resin components, it is the mass ratio of the photosensitive resin in the total mass of the binder resin and the resin-type dispersant.

[0151] <Optional ingredients>

[0152] The present photosensitive composition may further contain other components within a range in which the effects of the present invention are exhibited. Hereinafter, each component that may be contained in the present photosensitive composition will be described.

[0153] (Thermosetting compounds)

[0154] The photosensitive composition may also contain a thermosetting compound. In this way, when manufacturing a color filter, in the heating step after patterning the coating film by photolithography, the crosslinking density is increased, thereby improving the heat resistance. In addition, carbon black is difficult to aggregate in the heating step, so the light shielding property is further improved.

[0155] Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0156] ((Epoxide))

[0157] Examples of epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. ), polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), condensation products of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), condensation products of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.), condensation products of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins obtained by glycidylating alcohols, etc.

[0158] Examples of commercially available epoxy compounds include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, and Epicoat 191P (these are trade names; manufactured by Shell Oil Epoxy Co., Ltd.), Epicoat 1004 and Epicoat 1256 (these are trade names; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H and 502H (trade names; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade names; manufactured by Nippon Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (the above are trade names; manufactured by Nippon Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (the above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE-3150 (the above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Product name: Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (the above are trade names; manufactured by Nagase ChemteX), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), etc.

[0159] The content of the epoxy compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, relative to 100 parts by mass of carbon black. If the epoxy compound is appropriately added, the heat resistance and pattern shape of the film are further improved.

[0160] ((Oxetane Compounds))

[0161] The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0162] Examples of the monofunctional oxetane compound include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloyloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0163] Examples of commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

[0164] Examples of the difunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl- 3-Hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3 -oxetanyl methyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanyl methyl) ether, triethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, 1,4-bis(3-ethyl-3-oxetanyl methoxy) butane, 1,6-bis(3-ethyl-3-oxetanyl methoxy) hexane, polyethylene glycol bis(3-ethyl-3-oxetanyl methoxy) bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether modified with ethylene oxide (EO), bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether modified with propylene oxide (PO), EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl methyl) ether, and the like.

[0165] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd. and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0166] Examples of the compound having an oxetane group having three or more functional groups include pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetra(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetra(3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, The invention also includes a polymer obtained by free radical polymerization of (meth)acrylic acid monomers such as OXE-30, dipentaerythritol penta(3-ethyl-3-oxetanyl methyl) ether, caprolactone-modified dipentaerythritol penta(3-ethyl-3-oxetanyl methyl) ether, di-trimethylolpropane tetra(3-ethyl-3-oxetanyl methyl) ether, and a resin containing an oxetanyl group (for example, an oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462, etc.) or the like.

[0167] The content of the oxetane compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, relative to 100 parts by mass of carbon black. When an appropriate amount is contained, the solvent resistance of the film is further improved.

[0168] ((Melamine Compounds))

[0169] The melamine compound is a compound having a melamine ring structure. The melamine compound includes a low molecular weight compound or a high molecular weight compound. The melamine compound is preferably a compound having a methylol group or an ether group bonded to the melamine ring. Preferably, the number of bonds of the methylol group and / or ether group per melamine ring is 5.0 or more on average. If the number of bonds is appropriate, the solvent resistance of the film is further improved and the contrast ratio is difficult to decrease.

[0170] Examples of commercially available products of the melamine compound include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 (manufactured by Sanwa Chemical Co., Ltd.); and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 (manufactured by Japan Cytec Industries, Ltd.).

[0171] Among these, in terms of further improving the cross-linking density of the film, preferred are Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Japan Cytec Industries) having an average number of methylol and / or ether groups per melamine ring of 5.0 or more.

[0172] When a thermosetting compound is used, the total content of the thermosetting compound is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, relative to 100 parts by mass of carbon black. In terms of good film-forming properties and various resistances, it is preferably 20 parts by mass or more, and in terms of obtaining good light-shielding properties, it is preferably 400 parts by mass or less.

[0173] (Antioxidant)

[0174] The photosensitive composition may also contain an antioxidant. The antioxidant can improve storage stability and prevent the photopolymerization initiator or the thermosetting compound from oxidizing and yellowing due to the heat step during thermal curing or annealing of indium tin oxide (ITO).

[0175] The so-called "antioxidant" is any compound that has a function of absorbing ultraviolet rays, capturing free radicals, or decomposing peroxides. Specifically, antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds. As the antioxidant, known ultraviolet absorbers, antioxidants, etc. can be used.

[0176] Among these antioxidants, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants or sulfur antioxidants are preferred from the viewpoint of achieving a balance between transmittance and sensitivity of the coating film, and hindered phenol antioxidants, hindered amine antioxidants or phosphorus antioxidants are more preferred.

[0177] Examples of the hindered phenol antioxidant include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylene-bis-(4,6-dimethyl-phenol), 4,4'-butylene 2,2'-dimethyl-bis-(2-tert-butyl-5-methylphenol), 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'-thiodiethylbis-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid). In addition, oligomer-type and polymer-type compounds having a hindered phenol structure may also be used.

[0178] Examples of the hindered amine antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 [(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], poly[(6-morpholinyl-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetra[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, etc. In addition, oligomer-type and polymer-type compounds having a hindered amine structure may also be used.

[0179] Examples of the phosphorus antioxidant include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyl isooctylphosphite, phenyl isodecylphosphite, phenyl di(tridecyl)phosphite, diphenyl isooctylphosphite, diphenyl isodecylphosphite, diphenyl tridecylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, 4,4'-isopropylidene diphenol alkylphosphite, trisnonylphenylphosphite, tris-dinonylphenylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, and di(2,4-di-t-butylphenyl)pentaerythritol diphosphite. Phosphites, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetra-tridecyl 4,4'-butylenebis(3-methyl-6-tert-butylphenol) diphosphite, hexa-tridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-tert-butylphenyl)phosphite, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphite, 1,3-bis(diphenoxyphosphinooxy)-benzene, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, etc. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.

[0180] Examples of the sulfur-based antioxidant include 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol. In addition, oligomer-type and polymer-type compounds having a thioether structure may also be used.

[0181] Examples of the benzotriazole antioxidant include oligomer-type and polymer-type compounds having a benzotriazole structure.

[0182] Examples of benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 2-hydroxy-4-chlorobenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure may also be used.

[0183] Examples of the triazine antioxidant include 2,4-bis(allyl)-6-(2-hydroxyphenyl)-1,3,5-triazine, etc. In addition, oligomer-type and polymer-type compounds having a triazine structure may also be used.

[0184] Examples of salicylate antioxidants include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer-type and polymer-type compounds having a salicylate structure may also be used.

[0185] These antioxidants may be used alone or in combination of two or more at any ratio as needed.

[0186] In view of brightness and sensitivity, the content of the antioxidant is preferably 0.5% by mass to 5.0% by mass in all nonvolatile components of the photosensitive composition.

[0187] (Adhesion enhancer)

[0188] The photosensitive composition may contain an adhesion enhancer such as a silane coupling agent in order to improve adhesion to the substrate. By improving adhesion with the adhesion enhancer, the reproducibility of thin lines becomes good and the resolution is improved.

[0189] Examples of the adhesion enhancer include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, (meth) acrylic silanes such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, and 3-glycidyloxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl Silane coupling agents such as methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, mercapto-based silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryl-based silanes such as p-phenylenetrimethoxysilane, urea-based silanes such as 3-ureidopropyltriethoxysilane, sulfide-based silanes such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanate-based silanes such as 3-isocyanatepropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the coloring agent in the coloring composition. Within this range, the effect is greater and the balance of adhesion, resolution and sensitivity is good, which is more preferred.

[0190] (Leveling agent)

[0191] In order to improve the leveling property of the composition, the photosensitive composition may also include a leveling agent. As a leveling agent, a dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferred. As a specific example of a dimethylsiloxane having a polyether structure in the main chain, there are: FZ-2122 manufactured by Toray-Dow corning, BYK-333 manufactured by BYK Chemie, etc. As a specific example of a dimethylsiloxane having a polyester structure, there are BYK-310 and BYK-370 manufactured by BYK Chemie, etc. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used together. Regarding the content ratio of the leveling agent, it is preferably used at 0.003% by mass to 0.5% by mass in all solid components of the coloring composition.

[0192] As for the leveling agent, the following substances are particularly useful: a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and having a hydrophilic group but low solubility in water, and having a low surface tension reducing ability when added to the coloring composition, and having a good wettability to the glass plate despite the low surface tension reducing ability, and preferably using a substance that can sufficiently suppress the charging property without causing coating film defects caused by bubbling. As a leveling agent having such preferred characteristics, dimethyl polysiloxane having a polyalkylene oxide unit can be preferably used. As the polyalkylene oxide unit, there are polyethylene oxide units and polypropylene oxide units, and dimethyl polysiloxane may also have polyethylene oxide units and polypropylene oxide units.

[0193] Anionic, cationic, nonionic, or amphoteric surfactants may be added to the leveling agent. Two or more surfactants may be mixed and used.

[0194] Examples of the anionic surfactant to be auxiliary added to the leveling agent include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalene sulfonates, sodium alkyldiphenyl ether disulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0195] Examples of cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts or ethylene oxide adducts thereof. Examples of nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylaminoacetic acid betaine, alkyl imidazoline, etc.; and fluorine-based or silicone-based surfactants.

[0196] (hardener, hardening accelerator)

[0197] In order to assist the hardening of the thermosetting component, the photosensitive composition may also contain a hardener and a hardening accelerator as needed. As the hardener, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these. As long as they can react with the thermosetting resin, any hardener can be used. In addition, among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine hardeners can be preferably cited. As the hardening accelerator, for example, amine compounds (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), s-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2,4-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s-triazine-isocyanuric acid adduct, etc.), etc. These can be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting component.

[0198] (Storage Stabilizer)

[0199] The photosensitive composition may also contain a storage stabilizer in order to stabilize the viscosity over time.

[0200] Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, tert-butylcatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the colorant.

[0201] (Solvent)

[0202] The photosensitive composition may also contain a solvent. This makes it easier to adjust the viscosity of the photosensitive composition, so that a film with a smooth surface can be easily formed. The solvent can be appropriately selected according to the purpose of use and contained in an appropriate amount.

[0203] Examples of the solvent include ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0204] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0205] As the ether solvent, there can be mentioned an ether solvent without a hydroxyl group and an ether alcohol solvent (a solvent containing -OH and -O- in the molecule). Examples of the ether alcohol solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, etc.

[0206] Examples of the ether solvent having no hydroxyl group include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenethyl ether, and methyl anisole.

[0207] Among these, from the viewpoint of compatibility and coating properties of the photosensitive composition, it is preferred that the photosensitive composition contains an ether alcohol solvent.

[0208] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and dipropylene glycol diacetate.

[0209] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0210] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butanediol, and glycerin.

[0211] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0212] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0213] Among these, a solvent having a boiling point of 120° C. or higher and 245° C. or lower at 1 atm is preferred in terms of coating properties and drying properties. For example, more preferred are propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, cyclohexanone, tripropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like; further preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, cyclohexanone, tripropylene glycol monomethyl ether, 3-methoxy-1-butanol, and the like.

[0214] In addition, in order to adjust the photosensitive composition to an appropriate viscosity and form a coating film with a uniform film thickness as the target, the solvent is preferably used in an amount of 200 to 900 parts by mass, more preferably 300 to 570 parts by mass, relative to 100 parts by mass of the non-volatile component of the photosensitive composition. The viscosity of the photosensitive composition is preferably 2.4 to 7.2 mPa·s, more preferably 3.4 to 6.4 mPa·s.

[0215] (Dispersing aid)

[0216] When dispersing carbon black, etc., a dispersing aid such as a pigment derivative or a surfactant may be used instead of or in combination with the resin-type dispersant. The dispersing aid has a great effect of preventing the reagglomeration of the dispersed carbon black, so the viscosity stability of the photosensitive composition using the dispersing aid becomes good, and the obtained cured film has excellent light-shielding properties.

[0217] ((Pigment derivatives))

[0218] Examples of the pigment derivative include compounds obtained by introducing a basic substituent, an acidic substituent or a phthalimide methyl group which may have a substituent into an organic pigment, anthraquinone, acridone or triazine, for example, Japanese Patent Laid-Open No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, Japanese Patent Publication No. 2001-335717, Japanese Patent Publication No. 2003-13661, Japanese Patent Publication No. 2004-13764, Japanese Patent Publication No. 2005-13866 The compounds described in Japanese Patent Laid-Open No. 2003-128669, Japanese Patent Laid-Open No. 2004-091497, Japanese Patent Laid-Open No. 2007-156395, Japanese Patent Laid-Open No. 2008-094873, Japanese Patent Laid-Open No. 2008-094986, Japanese Patent Laid-Open No. 2008-095007, Japanese Patent Laid-Open No. 2008-195916, Japanese Patent No. 4585781, etc., can be used alone or in combination of two or more.

[0219] With regard to the viewpoint that dispersibility improves, relative to 100 mass parts of carbon black, the content of pigment derivative is preferably more than 0.5 mass parts, and then preferably more than 1 mass parts, and most preferably more than 3 mass parts. In addition, with regard to the viewpoint of heat resistance and light resistance, it is preferably below 40 mass parts, and then preferably below 35 mass parts.

[0220] (Surfactant)

[0221] Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts or ethylene oxide adducts thereof; and amphoteric surfactants such as alkyl betaines such as alkyl dimethylaminoacetic acid betaine and alkyl imidazolines. These surfactants may be used alone or in combination of two or more thereof, and are not necessarily limited to these.

[0222] When a resin type dispersant or surfactant is used, the content ratio is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of carbon black. When the content is less than 0.1 parts by mass, it is difficult to obtain the effect of addition, and when the content is more than 55 parts by mass, the dispersion is sometimes affected by the excess dispersant.

[0223] (Mercaptan Chain Transfer Agent)

[0224] The photosensitive composition may also contain a thiol-based chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, the thiol acts as a chain transfer agent in the free radical polymerization process after light irradiation, generating thiyl radicals that are less susceptible to polymerization inhibition by oxygen, thereby improving the sensitivity of the photosensitive composition.

[0225] The thiol chain transfer agent is preferably a multifunctional thiol having two or more thiol groups (SH groups), and more preferably having three or more SH groups. As the number of functional groups increases, photocuring from the surface of the film to the deepest part is facilitated.

[0226] Examples of the polyfunctional thiol include hexane dithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol dithiopropionate, trimethylolpropane trithiopropionate, and pentaerythritol tetrathiopropionate.

[0227] The thiol chain transfer agents may be used alone or in combination of two or more.

[0228] The content of the thiol chain transfer agent is preferably 0.5% to 10%, more preferably 1% to 8% of all non-volatile components of the photosensitive composition. If an appropriate amount is contained, the taper shape, wrinkles, film shrinkage, photosensitivity and pattern shape are further improved.

[0229] <Method for producing photosensitive composition>

[0230] The method for producing the photosensitive composition may be, for example, a method in which a carbon black dispersion is first prepared, and then a polymerizable compound, a photopolymerization initiator, a photocurable resin, and other components as needed are added.

[0231] Carbon black dispersion can be prepared, for example, by using various dispersing devices such as a kneader, a double-roll mill, a triple-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or a grinder to finely disperse the colorant, preferably together with a dispersing aid, in a colorant carrier such as a binder resin and / or an organic solvent. In the case of using a colorant different from carbon black, the colorant and the carbon black can be dispersed simultaneously, or they can be mixed after preparing the dispersion liquid separately. In addition, in the case of a colorant with high solubility, it is sufficient to dissolve it by stirring, and the dispersing step may not be performed.

[0232] In addition, the obtained composition is preferably separated by centrifugation, filtration using a sintered filter or a membrane filter, etc., to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, further preferably coarse particles of 0.5 μm or more, and particularly preferably coarse particles of 0.3 μm or more, and mixed dust.

[0233] 2. Organic EL display device

[0234] Reference Figure 1, the structure of the organic EL display device disclosed in the present invention (hereinafter also referred to as the present organic EL display device) is described. Figure 1 The organic EL display device 100 shown in the example includes: a substrate 10, a pixel electrode 20, an organic EL layer 30, and a color filter layer 40. The color filter layer 40 has red pixels 4R, green pixels 4G, and blue pixels 4B in a pattern, and further a black matrix 5 is arranged between the color pixels. Figure 1 In the example of FIG. 1 , a sealing layer 32 and a close contact layer 34 are provided between the organic EL layer 30 and the color filter layer 40, and an overcoat layer 42, a close contact layer 44, and a protective layer 46 are provided on the display surface side of the color filter layer 40. In addition, a partition wall 3 corresponding to each pixel is arranged on the organic EL layer 30. In addition, although not shown, a wiring pattern is formed on the substrate 10 at the periphery of the display area. A light shielding portion may also be provided on the wiring pattern.

[0235] The organic EL display device has excellent light shielding properties and can suppress reflected light from a wiring pattern because the light shielding layer including the black matrix 5 and the light shielding portion is a cured film formed from the photosensitive composition.

[0236] The substrate 10 is a substrate formed with pixel electrodes 20, preferably a silicon substrate. The pixel electrodes 20 are electrodes for driving the organic EL layer, and as an example, are thin film transistor (TFT) arrays. In addition, the protective layer 46 can be a cover glass or a known hard coating layer.

[0237] The organic EL layer 30 is an organic light-emitting single layer or multiple layers containing a light-emitting substance. In the case of multiple layers, for example, it can be a three-layer structure in which a hole transport layer, an electron transport organic light-emitting layer, and an electron transport layer are sequentially stacked. A hole (electron) injection layer, a hole (electron) transport layer, and a layer that separates the injection function and the transport function can also be provided, or a layer that blocks hole (electron) transport can be provided.

[0238] As an example of the organic EL layer, there can be mentioned a structure in which an anode, an organic layer, and a cathode are stacked in this order from the silicon substrate side and airtightly covered with a sealing layer.

[0239] The anode is disposed on a silicon substrate and is composed of a conductive material with a large work function. Examples of conductive materials with a large work function include nickel, silver, gold, platinum, palladium, selenium, rhodium, ruthenium, iridium, rhenium, tungsten, molybdenum, chromium, tantalum, niobium, or alloys thereof, or tin oxide (SnO2), indium tin oxide (ITO: Indium tin oxide), zinc oxide, titanium oxide, and the like.

[0240] The cathode is formed of a conductive material with a small work function. As such a conductive material, for example, an alloy of active metals such as Li, Mg, and Ca and metals such as Ag, Al, and In, or a structure formed by stacking these metals, can be used. In addition, a structure formed by thinly inserting a compound layer of active metals such as Li, Mg, and Ca and halogens such as fluorine and bromine or oxygen between the organic layer and the cathode can also be used.

[0241] The anode and cathode are patterned into suitable shapes according to the driving method of the display device. For example, when the driving method of the organic EL display device is a simple matrix type, the anode and cathode are formed into intersecting stripes, and the intersecting parts become organic EL elements.

[0242] The organic layer has at least a white light-emitting layer, but is usually composed of multiple organic layers, and can be set to have a charge injection layer such as a hole injection layer or an electron injection layer, or a hole transport layer that transports holes to the white light-emitting layer, or a charge transport layer such as an electron transport layer that transports electrons to the white light-emitting layer. The organic layer can be set to any of all known structures having a white light-emitting layer.

[0243] The light-emitting layer can use a known one that can obtain white light. Regarding the white light-emitting characteristics, it is sufficient as long as there is light emission in at least three regions, namely the red region (600nm to 780nm), the green region (475nm to 600nm), and the blue region (380nm to 475nm). The number of light emission peaks does not necessarily need to be three or more, for example, even if there are two light emission peaks, it is sufficient as long as there is light emission in the said region. However, in order to obtain a wide color reproducibility, it is preferred to use a white light-emitting layer with more than three light emission peaks, preferably with a light emission peak in more than one of the three color regions.

[0244] As the material constituting such a white light-emitting layer, if it is a material that emits fluorescence or phosphorescence, it is not particularly limited. In addition, the light-emitting material may also have hole transport properties or electron transport properties. As the light-emitting material, pigment-based materials, metal complex-based materials, and polymer-based materials, etc. can be listed.

[0245] Examples of the pigment materials include cyclopentylamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silylene derivatives, thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, triphenylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

[0246] Examples of the metal complex material include aluminum hydroxyquinoline complexes, benzohydroxyquinoline beryllium complexes, benzoxazole zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, and europium complexes, or metal complexes having a rare earth metal such as Al, Zn, Be, or Tb, Eu, Dy on the central metal and an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, and quinoline structure on the ligand.

[0247] Examples of the polymer material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and polymerized products of the pigment material and metal complex material.

[0248] As a method for forming the white light-emitting layer, for example, there can be cited: evaporation method, printing method, inkjet method, or spin coating method, casting method, dipping method, rod coating method, blade coating method, roller coating method, gravure coating method, flexographic printing method, spray coating method, and self-organization method (alternating adsorption method, self-organized monomolecular film method), etc. It is particularly preferred to use evaporation method, spin coating method, and inkjet method. The film thickness of the white light-emitting layer is usually about 5nm to 5μm.

[0249] In addition, the organic EL layer may also include a hole injection layer between the white light-emitting layer and the anode. By providing the hole injection layer, the injection of holes into the white light-emitting layer is stabilized, and the luminous efficiency can be improved. As the forming material of the hole injection layer, the material commonly used in the hole injection layer of the organic EL component can be used. In addition, the forming material of the hole injection layer only needs to have either the hole injection property or the electron barrier property.

[0250] Specifically, as the forming material of the hole injection layer, there can be listed: triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyaryl alkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, distilbene derivatives, silazane derivatives, polysilane-based, aniline-based copolymers, and conductive polymer oligomers such as thiophene oligomers.

[0251] Furthermore, examples of materials for forming the hole injection layer include porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds. The film thickness of the hole injection layer is usually about 5 nm to 1 μm.

[0252] In addition, the organic EL layer may include an electron injection layer between the white light-emitting layer and the cathode. By providing the electron injection layer, the injection of electrons into the white light-emitting layer is stabilized, and the light emission efficiency can be improved.

[0253] Examples of materials for forming the electron injection layer include nitro-substituted fluorene derivatives, anthraquinone dimethane derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthylenediol, carbodiimides, fluorenylidene methane derivatives, anthraquinone dimethane and anthrone derivatives, oxadiazole derivatives, thiazole derivatives in which the oxygen atom of the oxadiazole ring of the oxadiazole derivative is replaced by a sulfur atom, quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group, metal complexes of 8-hydroxyquinoline derivatives such as tris(8-hydroxyquinoline)aluminum, phthalocyanine, metal phthalocyanine, and distyrylpyrazine derivatives.

[0254] The color filter layer 40 is a layer disposed on the organic EL layer 30 directly or via other layers such as the adhesion layer 34, and has a black matrix 5 between the red pixel 4R, the green pixel 4G, the blue pixel 4B, and each color pixel. Furthermore, the color filter layer may further have a magenta pixel, a cyan pixel, a yellow pixel, or other pixels.

[0255] In terms of high definition, the area of ​​each pixel is preferably 1 μm 2 ~50μm 2 , preferably 1 μm 2 ~30μm 2 In terms of color reproducibility and the like, the thickness of each color pixel is preferably 0.1 μm to 5 μm, and more preferably 0.2 μm to 4 μm.

[0256] <Method for manufacturing organic EL display device>

[0257] When manufacturing an organic EL display device, first prepare a laminate including a substrate 10, a pixel electrode 20, and an organic EL layer 30. The manufacturing method of each layer can be appropriately selected from known methods. The color filter layer 40 can be directly formed on the organic EL layer 30, or a sealing layer 32 and / or a close-contact layer 34 can be formed on the organic EL layer 30, and formed on the sealing layer 32 or the close-contact layer 34. The sealing layer 32 can use a known curable resin, preferably an ultraviolet curable resin, and a thermosetting resin can also be used in combination. The ultraviolet curable resin is not particularly limited, and is preferably an acrylic resin that shows sensitivity to i-rays (wavelength 365nm). By forming a sealing layer, the surface on which the color filter layer is formed can be flattened.

[0258] The color filter layer 40 is preferably formed by photolithography. In the case of photolithography, in addition to the present photosensitive composition, photosensitive compositions for red, green, blue, etc. are also prepared.

[0259] The color filter layer 40 is usually first formed as a light shielding layer including a black matrix 5. The black matrix 5 is formed by coating the photosensitive composition on the organic EL layer 30, the sealing layer 32 or the adhesion layer 34 to form a coating film, and then exposing, developing and heating to harden.

[0260] The coating method can be appropriately selected from known methods such as spray coating, dip coating, bar coating, roll coating, and spin coating.

[0261] The exposure method may include a method of using ultraviolet light, electron beam, etc., such as a low-pressure mercury lamp, a high-pressure mercury lamp, or a metal halide lamp as a light source, and performing exposure through a shield of a predetermined pattern. A developer such as an alkaline developer is used to remove the uncured photosensitive composition, thereby obtaining a patterned light-shielding layer.

[0262] From the viewpoint of protecting the organic EL layer, the temperature of the heat curing is preferably 120° C. or lower, and more preferably 100° C. or lower. By using the photosensitive composition, sufficient curing can be achieved even at a low temperature of 120° C. or lower.

[0263] The thickness of the black matrix (light shielding layer) is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 2.0 μm, and further preferably 1.0 μm to 2.0 μm. The thickness of the black matrix may be the same as or different from the thickness of the light shielding portion provided at the periphery of the device.

[0264] Next, a red, green, and blue photosensitive composition is used to form a coating film, which is then exposed, developed, and heated to form pixels of each color. Furthermore, an overcoat layer 42, a bonding layer 44, a protective layer 46, etc. may be formed on the display surface side of the color filter layer 40 by a known method.

[0265] As described above, an organic EL display device including a light-shielding layer having excellent light-shielding properties can be obtained.

[0266] Example

[0267] Hereinafter, the present invention will be described by way of Examples. In addition, "parts" and "%" in the Examples represent "parts by weight" and "% by weight", respectively. The present invention is not limited to the Examples.

[0268] <Manufacturing of resin type dispersant solution>

[0269] (Resin type dispersant solution 1): Photosensitive resin

[0270] 8 parts of 3-mercapto-1,2-propanediol, 12 parts of pyromellitic anhydride, 80 parts of propylene glycol monomethyl etheracetate (PGMAc), and 0.2 parts of monobutyltin oxide as a catalyst were placed in a reaction container including a gas introduction tube, a thermometer, a condenser, and a stirrer, and after replacing with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). The acid value was measured to confirm that more than 95% of the anhydride was half-esterified. Next, 15 parts of methyl methacrylate (MMA), 10 parts of t-butylacrylate (tBA), 10 parts of ethyl acrylate (EA), 5 parts of methacrylic acid (MAA), 10 parts of benzyl methacrylate (BzMA), and 50 parts of 2-hydroxyethyl methacrylate (HEMA) were added, and the reaction container was heated to 80°C, and 1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed by solid content measurement that 95% of the reaction was carried out. Then, the air in the flask was replaced, 54.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 parts of hydroquinone were added, and the reaction was carried out at 70°C for 4 hours (third step). After confirming the disappearance of the peak at 2270 cm-1 due to the isocyanate group by infrared spectroscopy (IR), the reaction solution was cooled and the solid content was adjusted with PGMAc to obtain a resin-type dispersant solution 1 as a photosensitive resin with a solid content of 40%. The obtained resin-type dispersant had an acid value of 36 and a weight average molecular weight of 12,000.

[0271] (Resin type dispersant solution 2): Non-photosensitive

[0272] Into a reaction vessel including a gas introduction tube, a thermometer, a condenser, and a stirrer, 30 parts of ethyl acrylate, 20 parts of tert-butyl acrylate, and 40 parts of 2-methyl methacrylate were placed, and replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution obtained by dissolving 0.1 parts of 2,2'-azobisisobutyronitrile in 45.7 parts of cyclohexanone was added to 6 parts of 3-mercapto-1,2-propanediol, and reacted for 10 hours. It was confirmed by solid content measurement that 95% reacted. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride, 70 parts of PGMAc, and 0.20 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120°C for 7 hours. It was confirmed by acid value measurement that more than 98% of the anhydride was half-esterified, and the reaction was terminated. After the reaction, the nonvolatile content was adjusted to 40% by weight to obtain a PGMAc solution (resin dispersant solution 2) of a resin type dispersant having a weight average molecular weight of 8,100, an acid value of 50 mgKOH / g, and a glass transition temperature of a vinyl polymerization site of 22.5°C.

[0273] <Manufacturing of adhesive resin>

[0274] (Acrylic resin solution (D-1)): Photosensitive resin

[0275] In a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device on a separable four-necked flask, 100 parts of propylene glycol monomethyl ether acetate were placed, and the vessel was heated to 120° C. while nitrogen gas was injected into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours at the same temperature to carry out polymerization reaction. Next, the air in the flask was replaced, and 0.3 parts of tris-dimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120° C. for 5 hours. The reaction was terminated when the solid content acid value = 0.8, and a resin solution with a weight average molecular weight of about 12,000 (measured by gel permeation chromatography (GPC)) was obtained.

[0276] Furthermore, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added, and the mixture was reacted at 120°C for 4 hours. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 20%, thereby preparing an acrylic resin solution (D-1).

[0277] (Acrylic resin solution (D-2)): Photosensitive resin

[0278] 182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube. After the atmosphere in the flask was changed from air to nitrogen, the temperature was raised to 100° C., and then the following solution was added dropwise from the dropping funnel to the flask over 2 hours. The solution was prepared by adding 3.6 g of azobisisobutyronitrile to a mixture of 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 136 g of propylene glycol monomethyl ether acetate, and stirring was continued at 100° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 35.5 g of glycidyl methacrylate [0.25 mol (50 mol% relative to the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of tris-dimethylaminomethylphenol and 0.145 g of hydroquinone were added to the flask, and the reaction was continued at 110° C. for 6 hours, and propylene glycol monomethyl ether acetate was added so that the non-volatile component became 20%, to obtain an acrylic resin solution (D-2) having a solid acid value of 79 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[0279] (Acrylic resin solution (D-3)): Non-photosensitive

[0280] 196 parts of cyclohexanone were placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device on a separable four-necked flask, and the temperature was raised to 80°C. After nitrogen substitution in the reaction vessel, a mixture of 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of p-cumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution.

[0281] After cooling to room temperature, about 2 parts of the resin solution were sampled, dried by heating at 180°C for 20 minutes, and the non-volatile content was measured. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to prepare an acrylic resin solution (D-3). The weight average molecular weight (Mw) was 26,000.

[0282] <Manufacturing of Carbon Black Dispersion>

[0283] (Dispersion (PK-1))

[0284] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-1) with a non-volatile component of 20% by weight.

[0285] Carbon black (Mitsubishi Chemical Co., Ltd. #40): 15.0 parts

[0286] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0287] Propylene glycol monomethyl ether acetate: 70.0 parts

[0288] (Dispersion (PK-2))

[0289] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-2) with a non-volatile component of 20% by weight.

[0290] Carbon black (Mitsubishi Chemical Co., Ltd. #45): 15.0 parts

[0291] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0292] Propylene glycol monomethyl ether acetate: 70.0 parts

[0293] (Dispersion (PK-3))

[0294] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-3) with a non-volatile component of 20% by weight.

[0295] Carbon black (Mitsubishi Chemical #45L): 15.0 parts

[0296] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0297] Propylene glycol monomethyl ether acetate: 70.0 parts

[0298] (Dispersion (PK-4))

[0299] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-4) with a non-volatile component of 20% by weight.

[0300] Carbon black (Orion Engineered Carbons, Printex 55): 15.0 parts

[0302] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0303] Propylene glycol monomethyl ether acetate: 70.0 parts

[0304] (Dispersion (PK-5))

[0305] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-5) with a non-volatile component of 20% by weight.

[0306] Carbon black (Mitsubishi Chemical Co., Ltd. #47): 15.0 parts

[0307] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0308] Propylene glycol monomethyl ether acetate: 70.0 parts

[0309] (Dispersion (PK-6))

[0310] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-6) with a non-volatile component of 20% by weight.

[0311] Carbon black (Mitsubishi Chemical Co., Ltd. #52): 15.0 parts

[0312] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0313] Propylene glycol monomethyl ether acetate: 70.0 parts

[0314] (Dispersion (PK-7))

[0315] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-7) with a non-volatile component of 20% by weight.

[0316] Carbon black (Mitsubishi Chemical Co., Ltd._#44): 15.0 parts

[0317] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0318] Propylene glycol monomethyl ether acetate: 70.0 parts

[0319] (Dispersion (PK-8))

[0320] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-8) with a non-volatile component of 20% by weight.

[0321] Carbon black (Mitsubishi Chemical Co., Ltd._#33): 15.0 parts

[0322] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0323] Propylene glycol monomethyl ether acetate: 70.0 parts

[0324] (Dispersion (PK-9))

[0325] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-9) with a non-volatile component of 20% by weight.

[0326] Carbon black (Mitsubishi Chemical Co., Ltd. #5): 15.0 parts

[0327] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0328] Propylene glycol monomethyl ether acetate: 70.0 parts

[0329] (Dispersion (PK-10))

[0330] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-10) with a non-volatile component of 20% by weight.

[0331] Carbon black (Mitsubishi Chemical #1000): 15.0 parts

[0332] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0333] Propylene glycol monomethyl ether acetate: 70.0 parts

[0334] (Dispersion (PK-11))

[0335] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-11) with a non-volatile component of 20% by weight.

[0336] Carbon black (Mitsubishi Chemical Co., Ltd. #40): 15.0 parts

[0337] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0338] Propylene glycol monomethyl ether acetate: 70.0 parts

[0339] (Dispersion (PK-12))

[0340] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-12) with a non-volatile component of 20% by weight.

[0341] Carbon black (Mitsubishi Chemical Co., Ltd. #40): 15.0 parts

[0342] Resin type dispersant solution 1 (photosensitive resin): 6.25 parts

[0343] Resin type dispersant solution 2 (non-photosensitive resin): 6.25 parts

[0344] Propylene glycol monomethyl ether acetate: 70.0 parts

[0345] (Dispersion (PK-13))

[0346] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-13) with a non-volatile component of 20% by weight.

[0347] Carbon black (Mitsubishi Chemical Co., Ltd. #40): 15.0 parts

[0348] Resin type dispersant solution 1 (photosensitive resin): 9.4 parts

[0349] Resin type dispersant solution 2 (non-photosensitive resin): 3.1 parts

[0350] Propylene glycol monomethyl ether acetate: 70.0 parts

[0351] (Dispersion (PK-14))

[0352] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-14) with a non-volatile component of 20% by weight.

[0353] CI Pigment Yellow 139 (Paliotol Yellow D1819 manufactured by BASF Japan): 3.75 parts

[0354] CI Pigment Red 254 ("Irgajin Red L3630" manufactured by BASF Japan): 2.85 parts

[0356] CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Color): 0.90 parts

[0357] CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Color): 7.50 parts

[0358] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0359] Propylene glycol monomethyl ether acetate: 70.0 parts

[0360] (Dispersion (PK-15))

[0361] The following mixture was stirred and mixed in a uniform manner, and then dispersed for 3 hours using zirconium oxide beads with a diameter of 0.5 mm using an Eigermill ("Mini model M-250MKII" manufactured by Eiger Japan), and then filtered using a 5.0 μm filter to prepare a pigment dispersion (PK-15) with a non-volatile component of 20% by weight.

[0362] Perylene black pigment (Lumogen Black FK4280 manufactured by BASF Japan): 15.0 parts

[0364] Resin type dispersant solution 1 (photosensitive resin): 12.5 parts

[0365] Propylene glycol monomethyl ether acetate: 70.0 parts

[0366] <Production of photosensitive composition>

[0367] [Example 1]

[0368] (Black photosensitive composition (R-4))

[0369] The following mixture was stirred and mixed so as to become uniform, and then filtered through a 0.5 μm filter to obtain a photosensitive composition (R-4).

[0370] Dispersion (PK-1): 56.0 parts

[0371] Polymerizable compound (B-1): 3.0 parts

[0372] Polymerizable compound (B-2): 3.0 parts

[0373] Photopolymerization initiator (C-1): 2.8 parts

[0374] Leveling agent (non-volatile matter 1%): 1.00 part

[0375] Solvent (S-1): 34.2 parts

[0376] [Examples 2 to 28, Comparative Examples 1 to 6]

[0377] (Preparation of photosensitive compositions (R-1 to R-3, R-5 to R-34))

[0378] A photosensitive composition was obtained in the same manner as in the photosensitive composition (R-4) except that the types and blending amounts of the pigment dispersion, the polymerizable compound, the photopolymerization initiator, and the resin solution were changed to those shown in Tables 1 to 4.

[0379] [Table 1]

[0380]

[0381] [Table 2]

[0382]

[0383] [Table 3]

[0384]

[0385] [Table 4]

[0386]

[0387] The abbreviations in the table are shown below.

[0388] <Polymerizable compounds>

[0389] Polymerizable compound B-1: dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)

[0390] Polymerizable compound B-2: Trimethylolpropane EO-modified triacrylate ("Aronix M-350" manufactured by Toagosei Co., Ltd.)

[0391] Polymerizable compound B-3: trimethylolpropane triacrylate ("Aronix M-309" manufactured by Toagosei Co., Ltd.)

[0392] <Photopolymerization initiator>

[0393] [Chemistry 8]

[0394] Photopolymerization initiator (C-1)

[0395]

[0396] [Chemistry 9]

[0397] Photopolymerization initiator (C-2)

[0398]

[0399] <Leveling agent>

[0400] Leveling agent: A solution prepared by dissolving 1 part of "FZ-2122" manufactured by Toray-Dow Corning in 99 parts of propylene glycol monomethyl ether acetate (PGMAc)

[0401] <Chain transfer agent>

[0402] TPMB: Trimethylolpropane tris(3-mercaptobutyrate) ("TPMB" manufactured by Showa Denko K.K.)

[0403] PEMP: Pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.)

[0404] <Solvent>

[0405] Solvent S-1: Propylene glycol monomethyl ether acetate

[0406] Solvent S-2: Cyclohexanone

[0407] Solvent S-3: Tripropylene glycol monomethyl ether

[0408] Solvent S-4: 3-methoxy-1-butanol

[0409] <Optical density>

[0410] After applying the black photosensitive composition on a 100 mm×100 mm glass substrate by spin coating, a coating film with a dry film thickness of 1.2 μm was prepared, and heated at 100° C. for 5 minutes. The optical density (optical density (OD)) of the black photosensitive composition-coated substrate obtained in this way was measured using a Macbeth densitometer (GRETAGD200-II) to obtain the optical density (OD) when the film thickness was 1.2 μm.

[0411] In addition, OD was evaluated in three stages according to the following criteria.

[0412] A: 2.7 or above

[0413] B: 2.5 or more and less than 2.7

[0414] C: less than 2.5

[0415] <Pixel shape (linearity)>

[0416] Each photosensitive composition used in the examples was applied onto a silicon wafer substrate having a diameter of 200 mm using a spin coater so that the thickness after drying was 1.00 μm, and dried at 70° C. for 1 minute to obtain a substrate. Next, an i-ray stepper exposure apparatus FPA-3000i4 (manufactured by Canon) was used to perform 8000 J / m at a wavelength of 365 nm. 2 Exposure. The exposure is performed through a photomask having a square opening of 400 μm square. The exposed film is subjected to liquid development for 1 minute using TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industry). After the liquid development, it is rinsed with pure water for 20 seconds by rotary spraying and then spin dried. The linearity of the pixels formed by the opening is observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech Corporation) and evaluated according to the following criteria.

[0417] A: The linearity of the pixels is generally good (a good level for practical use)

[0418] B: The linearity of the pixel is locally good (a practical level)

[0419] C: The linearity of pixels is generally poor (not suitable for practical use)

[0420] <Pixel shape (cross section)>

[0421] Each photosensitive composition used in the examples was applied onto a silicon wafer substrate having a diameter of 200 mm using a spin coater so that the thickness after drying was 1.00 μm, and dried at 70° C. for 1 minute to obtain a substrate. Next, an i-ray stepper exposure apparatus FPA-3000i4 (manufactured by Canon) was used to perform 8000 J / m at a wavelength of 365 nm. 2 Exposure. The exposure is performed through a photomask having a square opening of 5 mm square. The exposed film is subjected to liquid development for 1 minute using TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industry). After the liquid development, it is rinsed with pure water for 20 seconds by rotary spraying and then spin dried. The pixels formed by the opening are cut out, and the cross-section is observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech Corporation), and evaluated according to the following criteria.

[0422] A: The pixel end is in close contact with the substrate (a practically preferable level)

[0423] B: The floating of the pixel edge is less than 3μm (a practical level)

[0424] C: The floating of the pixel edge is 3 μm or more (a level not suitable for practical use)

[0425] <Developability (residue)>

[0426] Each photosensitive composition was applied to a silicon wafer substrate having a diameter of 200 mm using a spin coater so that the thickness after drying was 1.2 μm, and dried at 70° C. for 1 minute to obtain a substrate. Next, an i-ray stepper exposure apparatus FPA-3000i4 (manufactured by Canon) was used to perform 8000 J / m at a wavelength of 365 nm. 2 Exposure. The exposure is performed through a photomask having a square opening of 400 μm square. The exposed film is subjected to liquid development for 1 minute using TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industry). After the liquid development, it is rinsed with pure water for 20 seconds by rotary spraying and then rotary dried. The development residue of the non-exposed part is observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech Corporation) and evaluated according to the following criteria.

[0427] A: No development residue in the non-exposed area (a practically better level)

[0428] B: Development residue exists in part of the non-exposed area (practical level)

[0429] C: Development residues are present in the entire non-exposed area (level not suitable for practical use)

[0430] <Solvent resistance>

[0431] Each photosensitive composition was applied to a silicon wafer substrate having a diameter of 200 mm using a spin coater so that the thickness after drying was 1.2 μm, and dried at 70° C. for 1 minute to obtain a substrate. Next, an i-ray stepper exposure apparatus FPA-3000i4 (manufactured by Canon) was used to perform 8000 J / m at a wavelength of 365 nm. 2 Exposure. The exposure is performed through a photomask with a square opening of 400 μm square. The exposed film is subjected to liquid development for 1 minute using TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industry). After the liquid development, it is rinsed with pure water for 20 seconds by rotary spraying and then rotary dried. After rotary drying, it is baked at 100°C for 5 minutes using a hot plate to obtain a black pattern substrate. The film thickness of the obtained pattern is measured using a contact film thickness meter ("Dektak 150" manufactured by Bruker Japan). After the film thickness measurement, the substrate is immersed in methoxypropyl acetate at 23°C for 5 minutes, and the film thickness is measured again and evaluated according to the following criteria.

[0432] A: The film thickness change before and after immersion is less than 5%

[0433] B: The film thickness change before and after immersion is 5% or more and less than 10%

[0434] C: The film thickness change before and after immersion is 10% or more

[0435] <Storage stability>

[0436] The initial viscosity on the second day after the curable resin composition was prepared and the viscosity after one week of aging at 40° C. The viscosity change rate over time was calculated from the obtained initial viscosity and viscosity over time using the following formula, and the storage stability was evaluated according to the following criteria.

[0437] [Change rate of viscosity over time] = |([initial viscosity] - [viscosity over time]) / [initial viscosity]| × 100

[0438] The measurement conditions were as follows: an E-type viscometer ("TV-25 Viscometer" manufactured by Toki Sangyo Co., Ltd.) was used, and the measurement was performed at 25° C., rotor No. 1, measurement time of 3 minutes, and rotation speed of 20 rpm.

[0439] A: The change rate is less than 5%

[0440] B: The change rate is 5% or more and less than 10%

[0441] C: Change rate is more than 10%

[0442] <Development Adhesion>

[0443] Each photosensitive composition was applied to a silicon wafer substrate having a diameter of 200 mm using a spin coater so that the thickness after drying was 1.2 μm, and dried at 70° C. for 1 minute to obtain a substrate. Next, an i-ray stepper exposure apparatus FPA-3000i4 (manufactured by Canon) was used to perform 8000 J / m at a wavelength of 365 nm. 2 The exposure was performed 10 times at different positions on the silicon wafer substrate through a photomask having a square opening of 400 μm square. The film after exposure was subjected to liquid development for 1 minute using TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industry). After liquid development, the film was rinsed with pure water for 20 seconds by rotary spraying, and then rotary dried. The pixel residual rate of the exposed part was observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech Corporation), and evaluated according to the following criteria.

[0444] A: The number of remaining pixels is 10 (a practically optimal level)

[0445] B: The number of remaining pixels is 8 or more and 9 or less (a practical level)

[0446] C: The number of remaining pixels is less than 8 (not suitable for practical use)

[0447] The above-mentioned evaluation results are shown in Tables 5 to 8.

[0448] [Table 5]

[0449]

[0450] [Table 6]

[0451]

[0452] [Table 7]

[0453]

[0454] [Table 8]

[0455]

[0456] It is shown that the photosensitive compositions for organic EL display devices of Examples 1 to 28 have excellent storage stability, excellent curability at low temperatures, and can form cured films with good developability and high light-shielding properties. The photosensitive compositions contain carbon black, a polymerizable compound, a photopolymerization initiator containing a compound having two or more oxime esters in one molecule, and a photosensitive resin, wherein the polymerizable compound contains a hexafunctional polymerizable compound and a trifunctional polymerizable compound, and the carbon black accounts for 30% to 50% by mass in the non-volatile components.

[0457] Industrial Applicability

[0458] The present invention can be used as a black photosensitive composition for an organic EL display device used in electronic devices such as smart glass, head-mounted displays, and electronic image finders.

[0459] This application claims the benefit of priority based on Japanese patent application No. 2022-101262, filed on June 23, 2022, the disclosure of which is hereby incorporated by reference in its entirety.

[0460] Explanation of symbols

[0461] 10: substrate, 20: pixel electrode, 30: organic EL layer, 40: color filter layer, 100: organic EL display device, 4R: red pixel, 4G: green pixel, 4B: blue pixel, 3: partition wall, 5: black matrix (light shielding layer), 32: sealing layer, 34: adhesion layer, 42: outer coating layer, 44: adhesion layer, 46: protective layer

Claims

1. A photosensitive composition for an organic electroluminescent display device, characterized in that: It includes carbon black, a polymerizable compound, a photopolymerization initiator, and a photosensitive resin, wherein: The photopolymerization initiator comprises a compound having two or more oxime esters in one molecule, The polymerizable compound comprises a hexafunctional polymerizable compound and a trifunctional polymerizable compound, The photosensitive composition for an organic electroluminescent display device contains the carbon black in an amount of 30% by mass to 50% by mass of a nonvolatile component of the photosensitive composition for an organic electroluminescent display device.

2. The photosensitive composition for an organic electroluminescent display device according to claim 1, characterized in that: The compound having two or more oxime esters in one molecule includes a compound represented by the following chemical formula (1-1): [Chemistry 1] Chemical formula (1-1) 3. The photosensitive composition for an organic electroluminescent display device according to claim 1, characterized in that: The average primary particle size of the carbon black is 50 nm or less.

4. The photosensitive composition for an organic electroluminescent display device according to claim 1, characterized in that: The specific surface area of ​​the carbon black is 80 m 2 / g~260m 2 / g.

5. The photosensitive composition for an organic electroluminescent display device according to claim 1, characterized in that: The photopolymerization initiator is contained in an amount of 3% by mass to 16% by mass in a nonvolatile component of the photosensitive composition for an organic electroluminescent display device.

6. The photosensitive composition for an organic electroluminescent display device according to claim 1, characterized in that: The photosensitive resin accounts for 80% by mass or more of all the resin components contained in the photosensitive composition.

7. An organic electroluminescent display device, characterized in that: A light shielding layer comprising the photosensitive composition for an organic electroluminescent display device according to any one of claims 1 to 6.

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