Photocurable black composition, cured product of photocurable black composition, and black coated substrate

Abstract

[Problem] To provide a photocurable black composition for forming a black shielding material that reduces the reflection of light irradiating a display from the user side. [Solution] A photocurable black composition comprising: (A) an alkali-soluble resin; (B) a photopolymerization initiator; (C) a photopolymerizable polyfunctional monomer; and (D) carbon black having a nitrogen adsorption specific surface area of 300 m2 / g or more based on JIS K6217-2:2017.. When irradiated with light through a transparent base material, a cured film of a black coated base material obtained from the photocurable black composition suppresses the reflection of the light so as to suppress the occurrence of a white blur on the cured film.

Description

[Technical field]

[0001] The present invention relates to a photocurable black composition, a cured product of the photocurable black composition, and a black-coated substrate having a cured coating of the photocurable black composition, and in particular to a photocurable black composition that allows alkaline development, a cured product of the photocurable black composition, and a black-coated substrate in which a transparent substrate is coated with the cured coating of the photocurable black composition. [Background technology]

[0002] In recent years, there is a need to display analog in-vehicle instruments such as speedometers on the instrument panel of a vehicle instead of placing them on a display. In this case, the periphery of the display area in the display is covered with a coating made of black resist, and a black matrix is ​​formed in the display area.

[0003] A colored photosensitive resin composition used to form a black matrix is ​​disclosed, for example, in Patent Document 1. Specifically, Patent Document 1 discloses a colored photosensitive composition that contains a photopolymerizable compound, a photopolymerization initiator, and a colorant as a light-shielding agent in order to ensure light-shielding properties. This colored photosensitive composition forms a black matrix with high light-shielding properties, and by applying it to a color filter, it is possible to improve the contrast of a liquid crystal display and prevent light leakage. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-168948 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the inventors have found through their research that when light hits a display having a coating or black matrix formed of a black resist based on a composition using a conventional colorant such as carbon black or titanium black as shown in Patent Document 1 from the glass side, i.e., from the user side of the display, the light is dimly reflected not only in the area where the light hits but also in the surrounding area, and the area where the light hits and the surrounding area appear dimly white (hereinafter, this phenomenon is also referred to as white blur in this specification). In particular, when a relatively large coating area formed of a black resist is illuminated by a car light or the like inside a vehicle, the white blur becomes noticeable. The occurrence of white blur leads to a deterioration in visibility of the display area and its surroundings.

[0006] The present invention has been made in consideration of the above-mentioned problems, and an object of the present invention is to provide a photocurable black composition for forming a black shielding material that reduces reflection of light irradiated from the user side to a display. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to achieve the above object, and as a result have found that the above object can be achieved by using carbon black having a predetermined nitrogen adsorption specific surface area as a light-blocking colorant, thereby completing the present invention.

[0008] That is, the above object of the present invention is to (A) an alkali-soluble resin; (B) a photopolymerization initiator; (C) a photopolymerizable multifunctional monomer; (D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 / g or more of carbon black; It has been found that this can be achieved by a photocurable black composition having

[0009] It is preferable that the photocurable black composition of the present invention further contains (E) an ester of cellulose and a short-chain fatty acid.

[0010] Furthermore, it is preferable that the photopolymerizable multifunctional monomer (C) contains an RO-addition photopolymerizable multifunctional monomer (C1) and a lactone-addition photopolymerizable multifunctional monomer (C2), and it is more preferable that the mass ratio (solid content) of the RO-addition photopolymerizable multifunctional monomer (C1) / the lactone-addition photopolymerizable multifunctional monomer (C2) is in the range of 0.5 or more and 10 or less.

[0011] In addition, (D) carbon black is 300m 2 / g or more 400m 2 It is preferable that the nitrogen adsorption specific surface area based on JIS K6217-2:2017 is not more than 1 / g.

[0012] It is also preferable to contain a thermosetting component (F).

[0013] Furthermore, the above-mentioned object of the present invention can also be achieved by a cured product of the photocurable black composition of the present invention, and a black-coated substrate comprising a transparent substrate and a cured coating of the photocurable black composition of the present invention. Effect of the Invention

[0014] According to the present invention, a cured coating formed from a photocurable black composition is applied to a transparent substrate, and when the cured coating is irradiated with light through the transparent substrate, reflection of light is suppressed, and therefore the occurrence of white blur on the cured coating can be suppressed, thereby improving visibility when applied to organic or inorganic EL displays, liquid crystal displays, and the like. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] <Photocurable black composition> The photocurable black composition of the present invention comprises: (A) an alkali-soluble resin; (B) a photopolymerization initiator; (C) a photopolymerizable multifunctional monomer; (D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 / g or more of carbon black; has.

[0016] [(A) Alkali-soluble resin] (A) The alkali-soluble resin is a resin that enables the photocurable black composition to be dissolved in an alkali developer, i.e., enables development with an alkali.

[0017] The (A) alkali-soluble resin may or may not have an ethylenically unsaturated group. The ethylenically unsaturated group is a substituent having an ethylenically unsaturated bond, and examples thereof include a vinyl group and a (meth)acryloyl group. From the viewpoint of reactivity, the (meth)acryloyl group is preferable. Here, the (meth)acryloyl group is a general term for an acryloyl group and a methacryloyl group.

[0018] As the alkali-soluble resin (A), it is preferable to use a carboxyl group-containing resin or a phenol resin, and in particular, it is more preferable to use a carboxyl group-containing resin from the viewpoint of developability.

[0019] As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins that have a carboxyl group in the molecule and further have no ethylenically unsaturated group (non-photosensitive) or have such an ethylenically unsaturated group (photosensitive) can be used.

[0020] Specific examples of the carboxyl group-containing resin having no ethylenically unsaturated group include the following compounds (which may be either oligomers or polymers).

[0021] (1) Carboxyl group-containing urethane resins obtained by the polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with diol compounds containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, and the like, such as dialcohol compounds, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

[0022] (2) Carboxylic acid-containing urethane resin obtained by the polyaddition reaction of diisocyanate and a carboxyl-containing dialcohol compound.

[0023] (3) Carboxyl group-containing resins obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc.

[0024] (4) Carboxyl group-containing polyester resins obtained by reacting a dicarboxylic acid, such as adipic acid, phthalic acid, or hexahydrophthalic acid, with a difunctional epoxy resin or a difunctional oxetane resin, and then adding a dibasic acid anhydride, such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride, to the resulting hydroxyl groups.

[0025] (5) A carboxyl group-containing resin obtained by ring-opening an epoxy resin or an oxetane resin and reacting the resulting hydroxyl group with a polybasic acid anhydride.

[0026] (6) A carboxyl group-containing resin obtained by reacting a reaction product such as a polyalcohol resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule, i.e., a polyphenol compound, with an alkylene oxide such as ethylene oxide or propylene oxide, with a polybasic acid anhydride.

[0027] Specific examples of the carboxyl group-containing resin having an ethylenically unsaturated group include the following compounds (which may be either oligomers or polymers): The ethylenically unsaturated bond in the carboxyl group-containing resin is preferably derived from acrylic acid, methacrylic acid, or a derivative thereof.

[0028] (7) Carboxyl group-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with diol compounds containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, and the like, such as dialcohol compounds, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

[0029] (8) Carboxylic group-containing photosensitive urethane resin obtained by a polyaddition reaction of a diisocyanate, a (meth)acrylate of a bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, or biphenol type epoxy resin, or a partially acid anhydride-modified product thereof, and a carboxyl group-containing dialcohol compound.

[0030] (9) A photosensitive urethane resin containing a carboxyl group, which is terminated with (meth)acrylation by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, during the synthesis of the resin (7) or (8) described above.

[0031] (10) A carboxyl group-containing photosensitive urethane resin having a terminal (meth)acryloyl group obtained by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (8) or (9) described above.

[0032] (11) A carboxyl group-containing photosensitive resin obtained by reacting a difunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.

[0033] (12) A carboxyl group-containing photosensitive resin obtained by reacting a multifunctional epoxy resin with the hydroxyl groups of a bifunctional (solid) epoxy resin further epoxidized with epichlorohydrin, reacting the resin with (meth)acrylic acid, and adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0034] (13) Carboxyl group-containing polyester photosensitive resins obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.

[0035] (14) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule, i.e., a polyphenol compound, with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product such as a polyalcohol resin, with an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid, and further reacting the resulting reaction product with a polybasic acid anhydride.

[0036] (15) A carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride.

[0037] (16) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the above-mentioned (3) carboxyl group-containing resin.

[0038] The photosensitive carboxyl group-containing resin may be any other than those described in (7) to (16), and may be used alone or in combination. In particular, it is preferable to use the carboxyl group-containing photosensitive resin described in (16).

[0039] In (16), the unsaturated carboxylic acid is a compound having one unsaturated group and at least one carboxyl group in one molecule, and examples thereof include acrylic acid, methacrylic acid, modified unsaturated monocarboxylic acids in which the unsaturated group and the carboxylic acid are chain-extended, such as β-carboxyethyl (meth)acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acids having an ester bond due to lactone modification or the like, modified unsaturated monocarboxylic acids having an ether bond, and further compounds having two or more carboxyl groups in the molecule, such as maleic acid. These may be used alone or in combination of two or more.

[0040] In addition, in (16), the unsaturated group-containing compound is preferably a (meth)acrylic acid ester, and examples thereof include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and hexyl (meth)acrylate, hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and caprolactone-modified 2-hydroxyethyl (meth)acrylate, and glycol-modified (meth)acrylates such as methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, isooctyloxydiethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate. These may be used alone or in combination of two or more. In this specification, (meth)acrylate is a general term for acrylate and methacrylate.

[0041] Furthermore, in (16), the compound having one epoxy group and one or more (meth)acryloyl groups in one molecule may be a compound having an ethylenically unsaturated group and an oxirane ring in one molecule, and examples thereof include glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylbutyl (meth)acrylate, and 3,4-epoxycyclohexylmethylaminoacrylate. Among these, 3,4-epoxycyclohexylmethyl (meth)acrylate is preferred. These (b) compounds having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in combination of two or more.

[0042] The above-mentioned carboxyl group-containing resins, whether photosensitive or non-photosensitive, have the following characteristics: Since they have many carboxyl groups on the side chains of the backbone polymer, they can be developed with a dilute alkaline aqueous solution.

[0043] The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film is good, and the alkaline development is good. On the other hand, when the acid value is 200 mgKOH / g or less, dissolution of the exposed part by the developer can be suppressed, so that the line is prevented from becoming thinner than necessary, and in some cases, the exposed part and the unexposed part are prevented from being dissolved and peeled off by the developer without distinction, and the resist pattern can be drawn well.

[0044] The weight-average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, and more preferably 5,000 to 100,000. When the weight-average molecular weight is 2,000 or more, the tack-free performance is good, the development resistance of the coating film after exposure is good, the film loss during development is suppressed, and the resolution is also good. On the other hand, when the weight-average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

[0045] The amount of such a carboxyl group-containing resin is suitably in the range of 10 to 95% by mass, preferably 10 to 80% by mass, based on the total mass (solid content) of the photocurable black composition. When the amount of the carboxyl group-containing resin is in the range of 10% to 95% by mass based on the total mass (solid content) of the photocurable black composition, the coating strength is good, and the viscosity of the photocurable black composition is appropriate, improving the coatability, etc.

[0046] In the present invention, as the alkali-soluble resin (A), either a photosensitive carboxyl group-containing resin or a carboxyl group-containing resin having no photosensitivity can be used, or a mixture of these can be used.

[0047] The mixing ratio may be any ratio as long as it is adjusted so that the alkali-soluble resin (A) has an ethylenically unsaturated bond equivalent of 1,200 or more.

[0048] The photosensitive carboxyl group-containing resin and the non-photosensitive carboxyl group-containing resin may be other than those described above, and each may be used alone or in combination. Among the carboxyl group-containing resins, resins without aromatic rings are particularly preferred because they have excellent light resistance.

[0049] The phenolic resin may be a compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton or a phenylene skeleton, or both skeletons, or a phenolic hydroxyl group-containing compound, for example, a phenolic resin having various skeletons synthesized using phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, or the like.

[0050] For example, known and commonly used phenolic resins such as phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenolic resin, Xylok type phenolic resin, terpene modified phenolic resin, polyvinylphenols, bisphenol F, bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes can be used.

[0051] These may be used alone or in combination of two or more.

[0052] Examples of commercially available phenolic resins include HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Besumoru CZ-256-A (manufactured by DIC Corporation), Shounol BRG-555, Shounol BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), and polyvinylphenols CST70, CST90, S-1P, and S-2P (manufactured by Maruzen Oil Co., Ltd.). These phenolic resins can be used alone or in appropriate combination of two or more kinds.

[0053] In the present invention, as the alkali-soluble resin (A), either a carboxyl group-containing resin or a phenolic resin, or a mixture of these, may be used as long as it satisfies the conditions that it has an ethylenically unsaturated bond equivalent of 1200 or more or does not have an ethylenically unsaturated group.

[0054] The photocurable black composition used in the present invention further contains the following photopolymerization initiator.

[0055] [(B) Photopolymerization initiator] (B) Photopolymerization initiator polymerizes (meth)acrylate by irradiation with energy rays. (B) Photopolymerization initiator includes known and commonly used compounds such as benzophenone-based, acetophenone-based, aminoacetophenone-based, benzoin ether-based, benzil ketal-based, acylphosphine oxide-based, oxime ether-based, oxime ester-based, and titanocene-based compounds.

[0056] As the (B) photopolymerization initiator, an oxime ester-based photopolymerization initiator containing a structural portion represented by the following general formula (I) is preferred. The oxime ester-based photopolymerization initiator is more preferably a dimeric oxime ester-based photopolymerization initiator. The oxime ester-based photopolymerization initiator preferably has a carbazole structure, and is more preferably a dimeric oxime ester-based photopolymerization initiator having a carbazole structure. As the aminoacetophenone-based photopolymerization initiator, an α-aminoacetophenone-based photopolymerization initiator containing a structural portion represented by the following general formula (II) is exemplified. As the acylphosphine oxide-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator containing a structural portion represented by the following general formula (III) is exemplified. As the titanocene-based photopolymerization initiator, a titanocene-based photopolymerization initiator represented by the following general formula (IV) is exemplified.

[0057] [ka] TIFF0007638878000002.tif49165

[0058] In general formula (I), R 1 R represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group. 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group.

[0059] R 1 and R 2 The phenyl group represented by the following formula may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

[0060] R 1 and R 2 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 20 carbon atoms, which may contain one or more oxygen atoms in the alkyl chain, and may be substituted with one or more hydroxyl groups.

[0061] R 1 and R 2 The cycloalkyl group represented by the following formula is preferably a cycloalkyl group having 5 to 8 carbon atoms.

[0062] R 1 and R 2 The alkanoyl group represented by the following formula is preferably an alkanoyl group having 2 to 20 carbon atoms.

[0063] R 1 and R 2 The benzoyl group represented by the following formula may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like.

[0064] In general formula (II), R 3 and R 4 each independently represents an alkyl group or an arylalkyl group having 1 to 12 carbon atoms; R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or two of them may be bonded to form a cyclic alkyl ether group.

[0065] In general formula (III), R 7 and R 8 each independently represents an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group, or a carbonyl group having 1 to 20 carbon atoms (excluding the case where both are carbonyl groups having 1 to 20 carbon atoms).

[0066] In general formula (IV), R 9 and R 10 each independently represents a halogen atom, an aryl group, a halogenated aryl group, or a heterocycle-containing halogenated aryl group.

[0067] Examples of the oxime ester photopolymerization initiator containing a structural portion represented by general formula (I) include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], a compound represented by the following formula (I-1), 2-(acetyloxyiminomethyl)thioxanthen-9-one, and oxime ester compounds having a carbazole skeleton, such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and a compound represented by the following general formula (I-2).

[0068] [ka] TIFF0007638878000004.tif48160

[0069] In general formula (I-2), R 11 is R in general formula (I). 1 is synonymous with R 12 and R 14 each independently represents R in general formula (I) 2 Synonymous with R. 13 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbonyl group.

[0070] Such an oxime ester-based photopolymerization initiator is preferable because it can increase the sensitivity of the photocurable black composition of the present invention to exposure to light for direct imaging, and has excellent resolution. In addition, it is particularly preferable that the oxime ester-based photopolymerization initiator is a dimer.

[0071] The dimeric oxime ester photopolymerization initiator is more preferably a compound represented by the following general formula (I-3).

[0072] [ka]

[0073] In general formula (I-3), R 23 R represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, or a naphthyl group. 21 , R 22 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a benzofuryl group, or a benzothienyl group.

[0074] Ar represents a single bond, an alkylene group having 1 to 10 carbon atoms, a vinylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furylene group, a 2,5-pyrrole-diyl group, a 4,4'-stilbene-diyl group, or a 4,2'-styrene-diyl group.

[0075] n represents an integer of 0 to 1.

[0076] R 23 The alkyl group represented by the following formula is preferably an alkyl group having 1 to 17 carbon atoms.

[0077] R 23 The alkoxy group represented by the following formula is preferably an alkoxy group having 1 to 8 carbon atoms.

[0078] R 23 The phenyl group represented by the following formula (1) may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having an alkyl group with 1 to 8 carbon atoms), or a dialkylamino group (preferably having an alkyl group with 1 to 8 carbon atoms).

[0079] R23 The naphthyl group represented by the formula (I) may have a substituent, and the substituent may be R 23 The substituents which the phenyl group represented by the following formula may have are the same as those mentioned above.

[0080] R 21 and R 22 The alkyl group represented by the following formula is preferably an alkyl group having 1 to 17 carbon atoms.

[0081] R 21 and R 22 The alkoxy group represented by the following formula is preferably an alkoxy group having 1 to 8 carbon atoms.

[0082] R 21 and R 22 The phenyl group represented by the following formula (1) may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, an alkylamino group (preferably having an alkyl group with 1 to 8 carbon atoms), or a dialkylamino group (preferably having an alkyl group with 1 to 8 carbon atoms).

[0083] R 21 and R 22 The naphthyl group represented by the formula (I) may have a substituent, and the substituent may be R 21 and R 22 The substituents which the phenyl group represented by the following formula may have are the same as those mentioned above.

[0084] Furthermore, in the general formula (I-3), R 21 , R 23 are each independently a methyl group or an ethyl group, R 22 It is preferred that n is 0; R is methyl or phenyl; Ar is a single bond, a phenylene group, a naphthylene group or a thienylene group; and n is 0.

[0085] As the compound represented by the general formula (I-3), the following compound is more preferable.

[0086] [ka]

[0087] When such an oxime ester-based photopolymerization initiator is used, it is preferable to use it in combination with an acylphosphine oxide-based photopolymerization initiator containing a structural moiety represented by general formula (III), since this improves the sensitivity to light exposure and also improves the cross-sectional shape of the cured coating of the photocurable black composition.

[0088] Examples of the α-aminoacetophenone-based photopolymerization initiator containing the structural portion represented by general formula (II) include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone. Commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins BV.

[0089] Examples of the acylphosphine oxide photopolymerization initiator containing a structural portion represented by general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Omnirad TPO and Omnirad 819 manufactured by IGM Resins BV.

[0090] The titanocene photopolymerization initiator represented by the general formula (IV) includes bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.

[0091] Commercially available oxime ester photopolymerization initiators include IRGACURE OXE01 (1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)]) and IRGACURE OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)) manufactured by BASF Japan, N-1919 and NCI-831 manufactured by ADEKA, TR-PBG-304 manufactured by Changzhou Strong Electronic New Materials Co., Ltd., and TOE-04-A3 manufactured by Nippon Chemical Industry Co., Ltd.

[0092] The amount of the (B) photopolymerization initiator is from 1 to 30 parts by mass, preferably from 3 to 25 parts by mass, and more preferably from 4 to 20 parts by mass, per 100 parts by mass (solid content) of the (A) alkali-soluble resin.

[0093] When the blending amount of the photopolymerization initiator (B) is 1 part by mass or more and 30 parts by mass or less per 100 parts by mass (solid content) of the alkali-soluble resin (A), good resolution is obtained.

[0094] [(C) Photopolymerizable polyfunctional monomer] The photocurable black composition of the present invention contains a known and commonly used photopolymerizable multifunctional monomer. The photopolymerizable multifunctional monomer is a compound having two or more ethylenically unsaturated groups in one molecule. The photopolymerizable multifunctional monomer is photocured by irradiation with active energy rays, thereby curing the photocurable black composition.

[0095] Examples of compounds used as the photopolymerizable polyfunctional monomer include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, etc. Specific examples include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as ethylene oxide adducts, propylene oxide adducts, and ε-caprolactone adducts thereof; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols. polyhydric acrylates such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and other glycidyl ether polyacrylates; and, without being limited to the above, examples thereof include acrylates and melamine acrylates obtained by directly acrilating polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols, or by urethane acrilation via diisocyanates, and at least one of the methacrylates corresponding to the above acrylates.

[0096] In particular, it is preferable that the photopolymerizable multifunctional monomer (C) contains an RO-addition photopolymerizable multifunctional monomer (C1) and a lactone-addition photopolymerizable multifunctional monomer (C2). In the present invention, RO refers to alkylene oxide, and alkylene oxide includes ethylene oxide (EO) and propylene oxide (PO). In the present invention, lactone includes γ-butyrolactone, δ-valerolactone, ε-caprolactone, and methylated ε-caprolactone.

[0097] (C1) Examples of the RO-addition photopolymerizable polyfunctional monomer include ethylene oxide adducts and propylene oxide adducts of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; and ethylene oxide adducts and propylene oxide adducts of polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate.

[0098] Furthermore, examples of the (C2) lactone-addition photopolymerizable polyfunctional monomer include ε-caprolactone adducts of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; and ε-caprolactone adducts of polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate.

[0099] When the photopolymerizable multifunctional monomer (C) contains an RO addition photopolymerizable multifunctional monomer (C1) and a lactone addition photopolymerizable multifunctional monomer (C2), the mass ratio (solid content) of the RO addition photopolymerizable multifunctional monomer (C1) / lactone addition photopolymerizable multifunctional monomer (C2) in the photocurable black composition of the present invention is in the range of 0.5 to 10, preferably in the range of 0.5 to 7, and particularly preferably in the range of 1 to 5. When the mass ratio (solid content) of the RO addition photopolymerizable multifunctional monomer (C1) / lactone addition photopolymerizable multifunctional monomer (C2) is in the range of 0.5 to 10, the resolution becomes good.

[0100] Moreover, the (C) photopolymerizable polyfunctional monomer preferably has three or more ethylenically unsaturated groups in one molecule, and more preferably has 3 to 6 ethylenically unsaturated groups in one molecule.

[0101] The amount of the photopolymerizable polyfunctional monomer (C) to be blended is in the range of 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass (solid content) of the alkali-soluble resin (A), and preferably in the range of 5 parts by mass or more and 40 parts by mass or less.

[0102] When the blending amount is 5 parts by mass or more and 50 parts by mass or less, the resolution becomes good.

[0103] In addition to the (C) photopolymerizable polyfunctional monomer, a photopolymerizable monofunctional monomer may be contained. Examples of the photopolymerizable monofunctional monomer include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate.

[0104] Furthermore, the photocurable black composition of the present invention has a nitrogen adsorption specific surface area of ​​300 m based on (D) JIS K6217-2:2017. 2 It is preferable that the carbon black contains carbon black having a molecular weight of 1 / g or more.

[0105] [(D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 / g or more of carbon black] (D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 Carbon black having a surface area of ​​at least 100 nm provides the black shielding material (black coated substrate) obtained from the photocurable black composition with the necessary light shielding properties and the effect of suppressing so-called white blur.

[0106] (D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 Commercially available carbon black products having a molecular weight of at least 1 / g include #2300, #2350, #2600, and #2650 (all manufactured by Mitsubishi Chemical Corporation).

[0107] In addition, the nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 / g or more 400m 2 It is preferable that the molecular weight is not more than 1 / g.

[0108] (D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 The amount of carbon black, which is at least 8 parts by mass / g, is in the range of 8 parts by mass or more and 40 parts by mass or less, preferably 10 parts by mass or more and 30 parts by mass or less, and particularly preferably 10 parts by mass or more and 20 parts by mass or less, relative to the total mass (solid content) of the photocurable black composition.

[0109] (D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300m 2 By setting the blending amount of carbon black having a molecular weight of 1000 to 15000 / g in the range of 8 parts by mass or more and 40 parts by mass or less relative to the total mass (solids content) of the photocurable black composition, it is possible to provide a photocurable black composition that can be photocured while maintaining the shielding properties required for a black shielding material (black coated substrate).

[0110] [(E) Ester of cellulose and short-chain fatty acid] The photocurable black composition of the present invention preferably contains (E) an ester of cellulose and a short-chain fatty acid. In the present invention, the short-chain fatty acid refers to one having 4 or less carbon atoms, and the ester of cellulose and a short-chain fatty acid includes not only one in which the hydrogen of the hydroxyl group of the cellulose molecule is completely replaced by an acyl group, but also one in which the hydroxyl group remains in the cellulose molecule.

[0111] By including (E) an ester of cellulose and a short-chain fatty acid in the photocurable black composition of the present invention, the development resistance is improved and the tackiness (dryness to the touch) of the cured product is also improved.

[0112] (E) Examples of esters of cellulose and short-chain fatty acids include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP). Commercially available cellulose acetate butyrate (CAB) products include CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-381-0.1, and CAB-381-0.5 (all manufactured by Eastman Co.), and commercially available cellulose acetate propionate (CAP) products include CAP-504-0.2 and CAP-482-0.5 (all manufactured by Eastman Co.).

[0113] When (E) an ester of cellulose and a short-chain fatty acid is added, the amount added is preferably in the range of 2 parts by mass or more and 15 parts by mass or less relative to the total mass (solid content) of the photocurable black composition.

[0114] (E) When the blending amount of the ester of cellulose and a short-chain fatty acid is in the range of 2 parts by mass or more and 15 parts by mass or less relative to the total mass (solid content) of the photocurable black composition, the development resistance is improved and the tackiness (dryness to the touch) of the cured product is improved.

[0115] [(F) Thermosetting component] From the viewpoint of improving the heat resistance and shape stability of the cured product, the photocurable black composition of the present invention is preferably heat-cured in addition to photocuring, and therefore, the photocurable black composition of the present invention preferably contains an (F) thermosetting component.

[0116] As the (F) thermosetting component, known and commonly used thermosetting resins such as isocyanate compounds (including blocked isocyanate compounds), amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds, and episulfide resins can be used.

[0117] In the present invention, epoxy resins are particularly preferably used.

[0118] As the epoxy resin, a known and commonly used multifunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be liquid, solid, or semi-solid. Here, liquid, solid, and semi-solid refer to the state of the epoxy resin at 30°C, respectively.

[0119] Examples of epoxy resins include bisphenol A type epoxy resins such as jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation; EPICLON 840, EPICLON 850, EPICLON 850-S, EPICLON 1050, and EPICLON 2055 manufactured by DIC Corporation; Epotohto YD-011, YD-013, YD-127, and YD-128 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; DER317, DER331, DER661, and DER664 manufactured by Dow Chemical Co., Ltd.; and Sumiepoxy ESA-011, ESA-014, ELA-115, and ELA-128 manufactured by Sumitomo Chemical Co., Ltd. (all trade names). 165, brominated epoxy resins such as Epotohto YDB-400 and YDB-500 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., DER542 manufactured by Dow Chemical Co., Ltd., Sumiepoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. (all trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Co., Ltd., DEN431 and DEN438, EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC, Epotohto YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Nippon Kayaku Co., Ltd., Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Co., Ltd., YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., EPICLON N-680, EPICLON N-690, EPICLON Novolac type epoxy resins such as N-695 (both trade names); EPICLON manufactured by DIC Corporation 830, bisphenol F type epoxy resins such as jER807 manufactured by Mitsubishi Chemical Corporation, Epototo YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (all trade names); hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., YX8034 manufactured by Mitsubishi Chemical Corporation; glycidyl amine type epoxy resins such as jER604 manufactured by Mitsubishi Chemical Corporation, Epototo YH-434 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names); hydantoin type epoxy resins; alicyclic epoxy resins such as Celloxide 2021 manufactured by Daicel Chemical Industries, Ltd. (all trade names); YL-933 manufactured by Mitsubishi Chemical Corporation, TEN manufactured by Nippon Kayaku Co., Ltd.trihydroxyphenylmethane type epoxy resins such as EPPN-501, EPPN-502 (all trade names); bixylenol type or biphenol type epoxy resins or mixtures thereof such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Corporation, and EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac type epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resins such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; heterocyclic epoxy resins such as TEPIC (all trade names) manufactured by Nissan Chemical Industries, Ltd.; Bressene type epoxy resins manufactured by NOF Corporation; Examples of epoxy resins include, but are not limited to, diglycidyl phthalate resins such as NMA DGT; tetraglycidyl xylenoyl ethane resins such as ZX-1063 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; and CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.).

[0120] These epoxy resins are various in the form of liquid, solid, or semi-solid at 30° C., and may be used alone or in combination of two or more. Also, an epoxy resin may be used in combination with other known and commonly used thermosetting components as described above.

[0121] When the (F) thermosetting component is blended, the blending amount thereof is preferably in the range of 30 parts by mass or more and 120 parts by mass or less, and more preferably in the range of 40 parts by mass or more and 80 parts by mass or less, per 100 parts by mass (solid content) of the (A) alkali-soluble resin.

[0122] [Leveling agent] The photocurable black composition of the present invention preferably contains a leveling agent. The leveling agent adjusts the flowability of the photocurable black composition and flattens the coating film of the photocurable black composition. Examples of the leveling agent include surfactants, and among them, it is preferable to use a leveling agent containing a polyacrylate compound as a main component.

[0123] Commercially available leveling agents containing polyacrylate compounds as their main components include BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-381, BYK-392, BYK-394, and BYK-3441 (all manufactured by BYK Japan; BYK is a registered trademark).

[0124] When the photocurable black composition of the present invention contains a leveling agent, the amount of the leveling agent is preferably in the range of 0.05 parts by mass or more and 5 parts by mass or less, and more preferably in the range of 0.1 parts by mass or more and 3 parts by mass or less, relative to the total mass (solid content) of the photocurable black composition.

[0125] [Other ingredients] The photocurable black composition of the present invention may further contain, as necessary, known and commonly used additives such as known and commonly used polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine; known and commonly used inorganic fillers, such as barium sulfate, barium titanate, silicon oxide powder, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder; known and commonly used thickeners, such as finely powdered silica, organic bentonite, and montmorillonite; silicone-based and fluorine-based defoamers, antioxidants, photopolymerization sensitizers, light stabilizers, dispersants, curing accelerators, flame retardants, and flame retardant assistants.

[0126] The photocurable black composition of the present invention may also contain an organic solvent used for preparing the photocurable black composition or adjusting the viscosity. Examples of organic solvents that can be used include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or in combination of two or more.

[0127] The photocurable black composition of the present invention may be prepared as a one-liquid system or may be formulated as a two-liquid system. In the case of a two-liquid system, the photopolymerization initiator (B) is blended in a liquid separate from the liquid containing the alkali-soluble resin (A) and the photopolymerizable polyfunctional monomer (C). This is to prevent undesired photopolymerization reactions during storage.

[0128] The photocurable black composition of the present invention can suppress the occurrence of white blur, so that a high-quality display member with improved visibility and a luxurious feel can be obtained. The photocurable black composition of the present invention can also be used to produce shielding images such as printing inks, materials for producing printing proofs, etching resists, solder resists, partitions of organic or inorganic EL display panels, dielectric patterns, electrode (conductor circuit) patterns, wiring patterns of electronic components, conductive pastes, conductive films, black matrices, black seal materials, and black mask materials. In particular, the photocurable black composition of the present invention can be suitably used to provide a light-shielding image (including a black matrix) in the intervals and periphery of a colored pattern and on the external light side of a TFT in order to improve the visibility of a color filter used in a color liquid crystal display device or the like, or as a light-shielding film for a touch panel. Particularly preferably, the composition can be suitably used as a black edge (bezel formation) provided in the periphery of a liquid crystal display device, an EL display device equipped with an organic or inorganic EL, or a display device equipped with a touch panel, a lattice-shaped or stripe-shaped black portion between red, blue, and green colored pixels, or more preferably as a black matrix such as a dot-shaped or line-shaped black pattern for TFT light shielding.

[0129] <Cured product of the photocurable black composition of the present invention, and black-coated substrate> The black coated substrate of the present invention comprises a transparent substrate and a cured coating (cured product) of the photocurable black composition of the present invention applied onto the transparent substrate.

[0130] The transparent substrate is a substrate having a total light transmittance of 50% or more at 400 to 800 nm, and specifically includes a glass substrate or a resin substrate such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyimide (PI), etc., and may have a shape ranging from a plate-like shape to a thin film-like shape. The plate-like shape is not limited to a flat plate-like shape, and may be a concave lens or convex lens-like shape, or a curved shape.

[0131] The photocurable black composition of the present invention can be in the form of a dry film obtained by coating on a carrier film (support) and drying. When forming a dry film, the photocurable black composition of the present invention is diluted with the organic solvent to adjust the viscosity to an appropriate level, and coated on a carrier film in a uniform thickness using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like, and usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to form a dry coating film. There is no particular restriction on the coating film thickness, but it is generally appropriately selected within the range of 0.1 to 100 μm, preferably 0.5 to 50 μm, in terms of the film thickness after drying.

[0132] As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. There is no particular limitation on the thickness of the carrier film, but it is generally appropriately selected in the range of 0.1 to 150 μm.

[0133] In this case, after forming the coating film on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film, etc. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used, and it is sufficient that the adhesive strength between the coating film and the cover film is smaller than the adhesive strength between the coating film and the carrier film when the cover film is peeled off.

[0134] In addition, the photocurable black composition of the present invention is adjusted to a viscosity suitable for the coating method using the organic solvent, and then coated on a transparent substrate by a method such as spray coating, dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating, or die coating, and the organic solvent contained in the composition is evaporated and dried (pre-dried) at a temperature of about 50° C. to 90° C., thereby forming a tack-free dry coating film. In addition, in the case of a dry film obtained by coating the photocurable black composition of the present invention on a carrier film, drying, and winding it up as a film, this is laminated on a transparent substrate by a laminator or the like so that the coating film of the photocurable black composition contacts the transparent substrate, and then peeling off the carrier film, thereby forming a coating layer on the substrate.

[0135] A cured coating can be obtained by photocuring these coating films, for example, by irradiation with active energy rays, and when a thermosetting component (F) is further contained, by heat curing at a temperature of 100° C. to 250° C. That is, a black-coated substrate is obtained, which has a transparent substrate and a cured coating (cured product) of the photocurable black composition of the present invention applied onto the transparent substrate.

[0136] The volatilization drying carried out after application of the photocurable black composition of the present invention can be carried out by a method of counter-contacting hot air in a dryer equipped with a heat source of an air heating type using steam, such as a hot air circulation drying oven, an IR oven, a hot plate, or a convection oven, or by a method of spraying the composition onto a support from a nozzle.

[0137] The exposure machine used for the active energy ray irradiation may be any machine equipped with a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and capable of irradiating ultraviolet rays in the range of 350 to 450 nm. In addition, a direct imaging machine (for example, a direct imaging machine that directly irradiates active energy rays to draw an image based on CAD data from a computer) may also be used. The light source of the direct imaging machine may be any machine that uses light with a maximum wavelength in the range of 350 to 410 nm. The exposure dose for forming an image varies depending on the film thickness, etc., but is generally 20 to 1000 mJ / cm. 2 , preferably 20 to 800 mJ / cm 2 The range may be:

[0138] The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like, and the developing solution may be an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like. EXAMPLES

[0139] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" refers to parts by mass unless otherwise specified.

[0140] <1. Preparation of Photocurable Black Compositions of Examples 1 to 7 and Comparative Examples 1 to 3> The materials shown in Table 1 were blended and mixed with a stirrer to prepare a first liquid, and the materials shown in Table 1 were blended and mixed with a stirrer to prepare a second liquid. The first and second liquids were then mixed and stirred to prepare a photocurable black composition.

[0141] [Table 1]

[0142] *1: A radical curing acrylic polymer containing acryloyl and carboxyl groups diluted in a high boiling solvent (solid content 46%) (Cyclomer P(ACA)Z250: manufactured by Daicel Allnex Corporation) *2: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO H: manufactured by IGM Resins BV) *3: EO-added trimethylolpropane triacrylate (Laromer LR8863: manufactured by BASF Japan) *4: ε-caprolactone modified dipentaerythritol hexaacrylate (DPCA-60: manufactured by Nippon Kayaku Co., Ltd.) *5: Nitrogen adsorption specific surface area: 370m 2 / g of carbon black (#2650: manufactured by Mitsubishi Chemical Corporation) *6: Nitrogen adsorption specific surface area: 320m 2 / g of carbon black (#2350: manufactured by Mitsubishi Chemical Corporation) *7: Nitrogen adsorption specific surface area: 260m 2 / g of carbon black (#980: manufactured by Mitsubishi Chemical Corporation) *8: Nitrogen adsorption specific surface area: 88m 2 / g of carbon black (#52: manufactured by Mitsubishi Chemical Corporation) *9: Cellulose acetate butyrate diluted with DPM (dipropylene glycol monomethyl ether) (solid content 30%) (CAB-551-0.2: manufactured by Eastman Chemical Co.) *10: Leveling agent whose main component is a polyacrylate compound (BYK-361N: manufactured by BYK Japan) *11: Dipropylene glycol monomethyl ether *12: Propylene glycol monomethyl ether *13: Solid bisphenol A type epoxy resin (jER (registered trademark) 1001: manufactured by Mitsubishi Chemical Corporation) diluted with carbitol acetate (solid content 75%) *14: Liquid hydrogenated bisphenol A type epoxy resin (YX8034: manufactured by Mitsubishi Chemical Corporation) *15: Dimeric oxime ester photopolymerization initiator (TOE-04-A3: manufactured by Nippon Chemical Industry Co., Ltd.) *16: Propylene carbonate

[0143] <2. Preparation of hardened coating (hardened product) and its evaluation> 2-1. Creation of cured film (cured product) The surface of a glass substrate (Eagle XG, 1.1 mm thick, manufactured by Corning) was degreased with alcohol, and the photocurable black compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were applied to the degreased surface using a spray coater (air spray method) so that the dry film thickness was about 10 μm. Then, the substrate was dried at 90° C. for 30 minutes in a hot air circulation drying oven, and exposed to ultraviolet light at 1500 mJ / cm using an exposure device (HMW680GW, manufactured by ORC). 2 The exposure was performed at .

[0144] Then, a 1% by mass Na2CO3 aqueous solution at 30°C was sprayed for 60 seconds at a spray pressure of 0.2 MPa to develop the film, and then it was heated in a UV conveyor oven at 1000 mj / cm 2 After post-UV treatment at 40° C., post-curing was performed for 1 hour at 150° C. to form a black-coated substrate having a glass substrate and a cured coating (cured product) of the photocurable black composition applied on the glass substrate.

[0145] 2-2.OD value (optical density) The cured coating side of the black-coated substrate formed in "2-1. Preparation of the cured coating (cured product)" was attached to a transmission densitometer (X-Rite 361T, manufactured by Sakata Inx Engineering Co., Ltd.) to evaluate the OD value. The black-coated substrate was attached to the transmission densitometer with the glass substrate side facing the light source.

[0146] 2-3. Reflectance (Y value) SCE / SCI (%) For the black coated substrate formed in "2-1. Creation of the cured coating (cured product)", the Y value of the XYZ color system was measured using a color difference meter (CM-2600d (light source wavelength: 360-740 nm), manufactured by Konica Minolta). The Y value was measured using the SCE (specular reflected light excluded) method, which is an evaluation of color close to that seen with the naked eye because specular reflected light is removed and only diffuse reflected light is measured, and the SCI (specular reflected light included) method, which is an evaluation of the color of the material itself regardless of the surface condition because specular reflected light is included in the measurement. The measurements were performed on the glass substrate surface of the black coated substrate.

[0147] It can be said that the lower the reflectance (Y value) SCE / SCI (%), the more the occurrence of white blur is suppressed.

[0148] 2-4.Resolution A black coated substrate was formed under the same conditions as those in "2-1. Preparation of cured coating (cured product)" except that a negative pattern with a line width of 20 to 300 μm in the light-shielding portion was used during exposure.

[0149] For each of the black coated substrates formed in Examples 1 to 7 and Comparative Examples 1 to 3, the width of the linear cured product remaining on the glass substrate was measured, and the smallest width among the remaining linear cured products was recorded as an evaluation item for resolution (L / S). The smaller the resolution (L / S) width, the better the resolution that allows the formation of finer lines, which is evaluated as the photocurable black composition.

[0150] 2-5.Developability A black coated substrate was formed under the same conditions as those in "2-1. Preparation of cured coating (cured product)" except that a negative pattern with a line width of 20 to 300 μm in the light-shielding portion was used during exposure.

[0151] For each of the black-coated substrates formed in Examples 1 to 7 and Comparative Examples 1 to 3, the area on the glass substrate that was covered by the light-shielding portion of the negative pattern, was left unexposed, and was developed with alkali. The area was visually observed to evaluate whether development residue was observed. The evaluation criteria were as follows. ◎: No residue was observed. ○: Some residue was observed. ×: Residue was observed throughout the entire surface.

[0152] 2-6. Tackiness Each of the photocurable black compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was applied to the entire surface of a glass substrate by screen printing, dried in a hot air circulation type drying oven at 90°C for 30 minutes, and cooled to room temperature. A PET film was pressed onto the glass substrate on which the photocurable black composition was applied, and then the film was peeled off to evaluate the adhesion state of the film. The evaluation criteria are as follows. : The film does not stick at all. ○: The film sticks slightly, but no pressure marks remain on the ink. △: Pressure marks from the film remain on the ink. ×: Ink transfers to the film.

[0153] Table 2 below shows the evaluation results of OD value (optical density), reflectance, resolution, developability and tackiness.

[0154] [Table 2]

[0155] As shown in Table 2, the reflectance (Y value) SCE / SCI (%) of Examples 1 and 2 is very small compared to Comparative Examples 1 and 2. This indicates that the nitrogen adsorption specific surface area is 300 m 2 It can be seen that white blur is suppressed when carbon black having a carbon black content of 1000 ppm or more is used. In addition, since Example 1 has improved tackiness compared to Example 5, it can be seen that the incorporation of (E) an ester of cellulose and a short-chain fatty acid improves tackiness.

Claims

1. (A) an alkali-soluble resin; (B) a photopolymerization initiator; (C) a photopolymerizable multifunctional monomer; (D) Nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300 m ２ / g or more of carbon black; (E) an ester of cellulose and a short chain fatty acid; 1. A photocurable black composition comprising:

2. 2. The photocurable black composition according to claim 1, wherein the photopolymerizable multifunctional monomer (C) comprises (C1) an RO addition photopolymerizable multifunctional monomer and (C2) a lactone addition photopolymerizable multifunctional monomer.

3. 3. The photocurable black composition according to claim 2, wherein a mass ratio (solid content) of the RO addition photopolymerizable multifunctional monomer (C1) to the lactone addition photopolymerizable multifunctional monomer (C2) is in the range of 0.5 or more and 10 or less.

4. (D) Carbon black, 300 m ２ / g or more 400m ２ The photocurable black composition according to claim 1 or 2, characterized in that it has a nitrogen adsorption specific surface area based on JIS K6217-2:2017 of not more than 1 / g.

5. The photocurable black composition according to any one of claims 1 to 4, further comprising (F) a thermosetting component.

6. A cured product of the photocurable black composition according to any one of claims 1 to 5.

7. A black-coated substrate comprising a transparent substrate and a cured coating of the photocurable black composition according to any one of claims 1 to 5 applied onto the transparent substrate.

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