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 masking material that reduces reflection of light irradiated from a user side to a display [Solution] A photocurable black composition having: (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a photopolymerizable multifunctional monomer, and (D) carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more based on JIS K6217-2:2017. In the case where light is irradiated to a cured coating film of a black coated substrate obtained from the photocurable black composition through a light-transmitting transparent substrate, reflection of the light is suppressed, and thus, occurrence of white blur on the cured coating film can be suppressed.

Description

TECHNICAL FIELD

[0001] The present application relates to a photocurable black composition, a cured product of the photocurable black composition, and a black covered substrate having a cured film of the photocurable black composition, and particularly relates to a photocurable black composition capable of alkali development, a cured product of the photocurable black composition, and a black covered substrate in which a cured film of the photocurable black composition is covered on a transparent substrate. BACKGROUND

[0002] In recent years, instead of disposing analog type vehicle-mounted instruments such as a speedometer in an instrument panel of a vehicle, there is a demand for displaying them on a display. In this case, a peripheral portion of a display region in the display is covered with a film formed of a black resist, and a black matrix is formed in the display region.

[0003] For example, a colored photosensitive resin composition for forming a black matrix is disclosed in Patent Literature 1. Specifically, in order to ensure light shielding property, Patent Literature 1 discloses a colored photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator, and a colorant as a light shielding agent. A black matrix having high light shielding property is formed from the colored photosensitive composition, and is suitable for a color filter, so that it is possible to achieve improvement of contrast of a liquid crystal display, and prevention of light leakage.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent Application Laid-Open No. 2009-168948 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, according to the research by the present inventors and the like, it has been found that, in the case where light is irradiated to a display from the glass surface side of the display formed with a film or a black matrix formed of a black resist having a composition using a colorant such as carbon black or titanium black, which is a commonly used colorant for light shielding, that is, from the side of a user who observes the display, the light is not only reflected in the light irradiation region, but also is diffusely reflected to the surrounding thereof, and sometimes, a phenomenon in which the light irradiation region and the surrounding region thereof are diffusely visible in white color (hereinafter, this phenomenon is also referred to as white color diffusion) occurs. In particular, in the case where a large film region formed of a black resist in an indoor space of a vehicle or the like is irradiated with a light such as an indoor light of the vehicle, the white color diffusion becomes remarkable. If the white color diffusion occurs, it leads to deterioration of visual recognition of the display region of the display and the surrounding thereof.

[0009] The present application has been made in view of the above-described problems, and an object thereof is to provide a photocurable black composition for forming a black shielding material in which reflection of light irradiated from the side of a user to a display is reduced.

[0010] Solution to the problem

[0011] The present inventors have conducted intensive studies in order to achieve the above object. As a result, it has been found that the above object can be achieved by using carbon black having a prescribed nitrogen adsorption specific surface area as a colorant for light shielding, and thus the present invention has been completed.

[0012] That is, it has been found that the above object of the present invention is achieved by a photocurable black composition characterized by having:

[0013] (A) an alkali-soluble resin,

[0014] (B) a photopolymerization initiator,

[0015] (C) a photopolymerizable multifunctional monomer, and

[0016] (D) carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more based on JIS K6217-2:2017.

[0017] It is preferable that the photocurable black composition of the present invention further contain (E) an ester of cellulose and a short-chain fatty acid.

[0018] Further, it is preferable that the (C) photopolymerizable multifunctional monomer contain (C1) an RO-addition photopolymerizable multifunctional monomer and (C2) a lactone-addition photopolymerizable multifunctional monomer, and it is further preferable that the mass ratio (solid content) of the (C1) RO-addition photopolymerizable multifunctional monomer / (C2) lactone-addition photopolymerizable multifunctional monomer be in the range of 0.5 or more and 10 or less.

[0019] Further, it is preferable that the (D) carbon black have a nitrogen adsorption specific surface area of 300 m 2 / g or more and 400 m 2 / g or less based on JIS K6217-2:2017.

[0020] In addition, it is preferable to contain (F) a thermosetting component.

[0021] Further, the above 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 cover substrate characterized by having a transparent substrate and a cured film of the photocurable black composition of the present invention.

[0022] Effects of the invention

[0023] According to the present application, in a case where light is irradiated to a cured coating film formed of a photocurable black composition on a transparent substrate through the transparent substrate, reflection of the light is suppressed, and thus, occurrence of white blur on the cured coating film can be suppressed, and visual recognition can be improved when applied to organic or inorganic EL displays, liquid crystal displays, and the like. DETAILED DESCRIPTION

[0024] <Photocurable black composition>

[0025] The photocurable black composition of the present application has:

[0026] (A) an alkali-soluble resin,

[0027] (B) a photopolymerization initiator,

[0028] (C) a photopolymerizable multifunctional monomer, and

[0029] (D) a carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more based on JIS K6217-2:2017.

[0030] [(A) Alkali-soluble resin]

[0031] The (A) alkali-soluble resin is a resin which is soluble in an alkali developer of the photocurable black composition, that is, a resin which is developable in an alkali.

[0032] The (A) alkali-soluble resin can have an ethylenic unsaturated group, or can not have an ethylenic unsaturated group. The ethylenic unsaturated group refers to a substituent group having an ethylenic unsaturated bond, and examples thereof include a vinyl group and a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloyl group is preferred. Here, the (meth)acryloyl group is a term collectively referring to an acryloyl group and a methacryloyl group.

[0033] As the (A) alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. In particular, if a carboxyl group-containing resin is used, it is more preferred from the viewpoint of developability.

[0034] As the carboxyl group-containing resin, various carboxyl group-containing resins which are conventionally known and which have a carboxyl group in the molecule and further do not have an ethylenic unsaturated group (non-photosensitive) or have the same (photosensitive) can be used.

[0035] As specific examples of the carboxyl group-containing resin which does not have an ethylenic unsaturated group, the following compounds (both oligomers and polymers can be used) can be given.

[0036] (1) Carboxyl group-containing polyurethane resins obtained by polyaddition of aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, and the like, with a diol compound containing a carboxyl group, such as dimethylolpropionic acid, dimethylolbutyric acid, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, a bisphenol A-based epoxy alkane adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

[0037] (2) Carboxyl group-containing polyurethane resins obtained by polyaddition of diisocyanate with a carboxyl group-containing diol compound.

[0038] (3) Carboxyl group-containing resins obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid, with an unsaturated group-containing compound such as styrene, α-methylstyrene, (meth)acrylic acid lower alkyl ester, isobutylene, and the like.

[0039] (4) Carboxyl group-containing polyester resins obtained by reacting a 2-functional epoxy resin or a 2-functional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, and the like, and adding a dibasic anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like, to the resulting hydroxyl group.

[0040] (5) Carboxyl group-containing resins obtained by ring-opening of an epoxy resin or an oxetane resin, and reacting the resulting hydroxyl group with a polybasic anhydride.

[0041] (6) Carboxyl group-containing resins obtained by reacting a polyol resin or the like reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule, i.e., a polyphenol compound, with an epoxy alkane such as an oxirane, an oxetane, and the like, and reacting the resulting polyol resin or the like reaction product with a polybasic anhydride.

[0042] In addition, as specific examples of the carboxyl group-containing resins having an ethylenic unsaturated group, the following compounds (both oligomers and polymers) can be given. Note that the ethylenic unsaturated bond in the carboxyl group-containing resins is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

[0043] (7) Carboxyl group-containing photosensitive polyurethane resins obtained by polyaddition of aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, and the like, with a diol compound containing a carboxyl group, such as dimethylolpropionic acid, dimethylolbutyric acid, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based epoxy alkane adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

[0044] (8) A carboxyl group-containing photosensitive polyurethane resin obtained by polyaddition of a (meth)acrylate or a partial anhydride-modified product thereof of a diisocyanate, a 2-functional epoxy resin of a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol X type epoxy resin, a bisphenol Z type epoxy resin, etc., with a carboxyl group-containing diol compound.

[0045] (9) A carboxyl group-containing photosensitive polyurethane resin in which a compound having one hydroxyl group and one or more (meth)acryloyl groups in a molecule, such as a hydroxyalkyl (meth)acrylate, is added to the resin of (7) or (8) above and terminal (meth)acryloylation is performed.

[0046] (10) A carboxyl group-containing photosensitive polyurethane resin in which a compound having one isocyanate group and one or more (meth)acryloyl groups in a molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, is added to the resin of (8) or (9) above and terminal (meth)acryloylation is performed.

[0047] (11) A carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic anhydride to a hydroxyl group present in a side chain.

[0048] (12) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin in which a hydroxyl group of a 2-functional (solid) epoxy resin is further epoxidized with epichlorohydrin with (meth)acrylic acid and adding a dibasic anhydride to a generated hydroxyl group.

[0049] (13) A carboxyl group-containing polyester photosensitive resin obtained by reacting a 2-functional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and adding a dibasic anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc., to a generated primary hydroxyl group.

[0050] (14) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule, i.e., a polyphenol compound, with an alkylene oxide such as an ethylene oxide, a propylene oxide, etc., to obtain a reaction product such as a polyol resin, reacting the obtained reaction product such as a polyol resin with an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid, and further reacting the obtained reaction product with a polybasic anhydride.

[0051] (15) A carboxyl group-containing photosensitive resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as an ethylene carbonate, a propylene carbonate, etc., to obtain a reaction product, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic anhydride.

[0052] (16) The carboxyl group-containing photosensitive resin obtained by further adding to the carboxyl group-containing resin of the above (3) a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule.

[0053] The carboxyl group-containing photosensitive resin can also be used a resin other than those described in (7) to (16), and one kind can be used alone or a plurality of kinds can be used in mixture. In particular, the carboxyl group-containing photosensitive resin described in (16) is preferably used.

[0054] 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, a modified unsaturated monocarboxylic acid in which chain extension is performed between the unsaturated group and the carboxylic acid, such as β-carboxyethyl (meth)acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, an unsaturated monocarboxylic acid having an ester bond by modification with a lactone or the like, a modified unsaturated monocarboxylic acid having an ether bond, and a further modified unsaturated monocarboxylic acid containing two or more carboxyl groups such as maleic acid in the molecule. Two or more kinds thereof can be used in mixture.

[0055] In addition, in (16), the unsaturated group-containing compound is preferably a (meth)acrylate, 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, hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate modified with caprolactone, and hydroxyl group-containing (meth)acrylates such as methoxy diethylene glycol (meth)acrylate, ethoxy diethylene glycol (meth)acrylate, isooctyloxy diethylene glycol (meth)acrylate, phenoxy triethylene glycol (meth)acrylate, methoxy triethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, and diol-modified (meth)acrylates. Two or more kinds thereof can be used in mixture. Note that in the present specification, the (meth)acrylate is a term collectively referring to acrylate and methacrylate.

[0056] Further, in (16), as the compound having one or more (meth)acryloyl groups and one oxirane ring in one molecule, only the compound having an ethylenically unsaturated group and an oxirane ring in one molecule can be mentioned, such as glycidyl (meth)acrylate, α-methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylbutyl (meth)acrylate, 3,4-epoxycyclohexylmethyl acrylamide, and the like. Of these, 3,4-epoxycyclohexylmethyl (meth)acrylate is preferred. These (b) compounds having an oxirane ring and an ethylenically unsaturated group in one molecule can be used alone or in a mixture of two or more.

[0057] The carboxyl group-containing resin described above can be either photosensitive or non-photosensitive. That is, the carboxyl group-containing resin has a plurality of carboxyl groups in the side chain of the main chain polymer, and thus can be developed using a dilute aqueous alkali solution.

[0058] Further, the acid value of the carboxyl group-containing resin is appropriately in the range of 20 to 200 mgKOH / g, and more preferably in the range of 40 to 150 mgKOH / g. In the case where the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film becomes good, and the alkali development becomes good. On the other hand, in the case where the acid value is 200 mgKOH / g or less, the dissolution of the exposed portion by the developer can be suppressed, and thus the line can be made finer than necessary, and depending on the case, the exposed portion and the unexposed portion can be distinguished without being dissolved and peeled off by the developer, and the resist pattern can be drawn well.

[0059] Further, the weight average molecular weight of the carboxyl group-containing resin described above varies depending on the resin skeleton, and is generally in the range of 2000 to 150000, and further preferably in the range of 5000 to 100000. In the case where the weight average molecular weight is 2000 or more, the non-stick performance is good, the resistance to development of the coating film after exposure is good, the film loss during development is suppressed, and the resolution also becomes good. On the other hand, in the case where the weight average molecular weight is 150000 or less, the development is good, and the storage stability is also excellent.

[0060] The compounding amount of the carboxyl group-containing resin is appropriately in the range of 10 to 95% by mass, and preferably in the range of 10 to 80% by mass, with respect to the total mass (solid content) of the photocurable black composition. In the case where the compounding amount of the carboxyl group-containing resin is in the range of 10% by mass or more and 95% by mass or less with respect to the total mass (solid content) of the photocurable black composition, the film strength is good, and the viscosity of the photocurable black composition is moderate and the coatability and the like are improved.

[0061] In addition, in the present application, as the (A) alkali-soluble resin, either of a photosensitive carboxyl group-containing resin and a carboxyl group-containing resin not having photosensitivity can be used, or they can be used in admixture.

[0062] The mixing ratio can be arbitrary as long as the equivalent of the olefinic unsaturated bond of the (A) alkali-soluble resin is 1200 or more.

[0063] The photosensitive carboxyl group-containing resin and the carboxyl group-containing resin not having photosensitivity can be used other than the above, and one kind each can be used alone or a plurality of kinds can be used in admixture. Among the carboxyl group-containing resins, a resin not having an aromatic ring is excellent in light resistance, and is therefore particularly preferred.

[0064] As the phenolic resin, a phenolic resin having various skeletons synthesized using a compound having a phenolic hydroxyl group, such as a compound having a biphenyl skeleton or a phenylene skeleton or both of these skeletons, or a phenolic hydroxyl group-containing compound, such as phenol, o-cresol, p-cresol, m-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, and the like, can be used.

[0065] For example, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene-type novolak resin, a Xylok-type novolak resin, a terpene-modified novolak resin, a polyvinylphenol, a bisphenol F, a bisphenol S-type novolak resin, a poly-p-hydroxystyrene, a condensate of a naphthol and an aldehyde, a condensate of a dihydroxynaphthalene and an aldehyde, and the like, which are well-known conventional phenolic resins, can be used.

[0066] They can be used alone or in combination of two or more.

[0067] As a commercial product of the above-mentioned phenolic resin, HF1H60 (manufactured by Meiji Chemical Co., Ltd.), PHENOLITE TD-2090, PHENOLITE TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), BESMOL CZ-256-A (manufactured by DIC Corp.), Shonol BRG-555, Shonol BRG-556 (manufactured by Showa Denko K.K.), CGR-951 (manufactured by Maruzen Petrochemical Co., Ltd.), or CST70, CST90, S-1P, S-2P (manufactured by Maruzen Petrochemical Co., Ltd.) of a polyvinylphenol, and the like can be mentioned. These phenolic resins can be used alone or in combination of two or more as appropriate.

[0068] In the present application, as the (A) alkali-soluble resin, either one of a carboxyl group-containing resin and a phenol resin, or a mixture thereof can be used, as long as the conditions that the equivalent of ethylenic unsaturation is 1200 or more, or that no ethylenic unsaturated group is present, are satisfied.

[0069] Further, the photocurable black composition used in the present application further contains a photopolymerization initiator described below.

[0070] [(B) Photopolymerization initiator]

[0071] The (B) photopolymerization initiator polymerizes the (meth)acrylate by irradiation of energy rays. As the (B) photopolymerization initiator, conventionally known compounds such as benzophenone-based, acetophenone-based, aminophenone-based, benzoin ether-based, benzyl ketal-based, acylphosphine oxide-based, oxime ether-based, oxime ester-based, and titanocene-based compounds can be given.

[0072] As the (B) photopolymerization initiator, an oxime ester-based photopolymerization initiator containing a structural moiety represented by General Formula (I) shown below is preferable. The aforementioned oxime ester-based photopolymerization initiator is more preferably a dimeric oxime ester-based photopolymerization initiator. Further, the aforementioned oxime ester-based photopolymerization initiator preferably has a carbazole structure, and further preferably is a dimeric oxime ester-based photopolymerization initiator having a carbazole structure. Further, as the aminophenone-based photopolymerization initiator, an α-aminophenone-based photopolymerization initiator containing a structural moiety represented by General Formula (II) shown below can be given. As the acylphosphine oxide-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator containing a structural moiety represented by General Formula (III) can be given. As the titanocene-based photopolymerization initiator, a titanocene-based photopolymerization initiator represented by General Formula (IV) can be given.

[0073]

[0074] In General Formula (I), R 1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanol group, or a benzoyl group. R 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanol group, or a benzoyl group.

[0075] The phenyl group represented by R 1 and R 2 optionally has a substituent, and as the substituent, for example, an alkyl group having a carbon number of 1 to 6, a phenyl group, a halogen atom, or the like can be given.

[0076] As the alkyl group represented by R 1 and R 2 , an alkyl group having a carbon number of 1 to 20 is preferable, and one or more oxygen atoms can be contained in the alkyl chain. Further, it can be substituted with one or more hydroxyl groups.

[0077] As the alkanol group represented by R 1 and R2 a cycloalkyl group represented by R

[0078] R 1 and R 2 an alkanol group represented by R

[0079] R 1 and R 2 a benzoyl group represented by R

[0080] In General Formula (II), R 3 and R 4 each independently represent an alkyl group having a carbon number of 1 to 12 or an arylalkyl group, R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 6, or can be combined to form a cyclic alkyl ether group.

[0081] In General Formula (III), R 7 and R 8 each independently represent an alkyl group having a carbon number of 1 to 10, a cyclohexyl group, a cyclopentyl group, an aryl group or a halogen atom, an aryl group substituted with an alkyl group or an alkoxy group, or a carbonyl group having a carbon number of 1 to 20 (wherein the case in which both are carbonyl groups having a carbon number of 1 to 20 is excluded).

[0082] In General Formula (IV), R 9 and R 10 each independently represent a halogen atom, an aryl group, a halogenated aryl group, a heterocyclic ring-containing halogenated aryl group.

[0083] As the oxime ester-based photopolymerization initiator containing the structural moiety represented by General Formula (I), there can be mentioned, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), a compound represented by the following Formula (I-1), 2-(acetyloxyiminomethyl)thioxanthone-9-ketone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime) and a compound represented by the following General Formula (I-2), and the like oxime ester-based compounds having a carbazole skeleton.

[0084]

[0085] In General Formula (I-2), R 11 has the same meaning as R 1 in General Formula (I), R 12 and R 14 each independently have the same meaning as R 2 in General Formula (I). R 13represents a hydrogen atom, an alkyl group having a carbon number of 1 to 12, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanol group having a carbon number of 2 to 12, an alkoxycarbonyl group having a carbon number of 2 to 12 (in the case where the alkyl group constituting the alkoxyl group has a carbon number of 2 or more, the alkyl group can be substituted with one or more hydroxyl groups and can have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxy carboxyl group.

[0086] Such an oxime ester-based photopolymerization initiator is preferred because it can improve the sensitivity of the photocurable black composition of the present application for exposure for direct imaging, and is excellent in resolution. In addition, the oxime ester-based photopolymerization initiator is particularly preferably a dimer.

[0087] As the oxime ester-based photopolymerization initiator which is a dimer, more preferably a compound represented by the following general formula (I-3) is used.

[0088]

[0089] In the general formula (I-3), R 23 represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, or a naphthyl group. R 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 benzofuranyl group, or a benzothiophenyl group.

[0090] Ar represents a single bond, or an alkylene group having a carbon number of 1 to 10, a vinylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thiophenylene group, a furanylene group, a 2,5-pyrrolylene group, a 4,4'-stilbenylene group, or a 4,2'-styrylene group.

[0091] n represents an integer of 0 to 1.

[0092] As the alkyl group represented by R 23 , an alkyl group having a carbon number of 1 to 17 is preferred.

[0093] As the alkoxy group represented by R 23 , an alkoxy group having a carbon number of 1 to 8 is preferred.

[0094] The phenyl group represented by R 23 may optionally have a substituent, and as the substituent, for example, an alkyl group (preferably, an alkyl group having a carbon number of 1 to 17), an alkoxy group (preferably, an alkoxy group having a carbon number of 1 to 8), an amino group, an alkylamino group (preferably, an alkyl group having a carbon number of 1 to 8), or a dialkylamino group (preferably, an alkyl group having a carbon number of 1 to 8), or the like can be given.

[0095] The naphthyl group represented by R 23 may optionally have a substituent, and as the substituent, the same groups as the above-mentioned substituents which the phenyl group represented by R 23 may have can be given.

[0096] as R 21 and R 22 represent an alkyl group, preferably an alkyl group having a carbon number of 1 to 17.

[0097] as R 21 and R 22 represent an alkoxy group, preferably an alkoxy group having a carbon number of 1 to 8.

[0098] as R 21 and R 22 represent a phenyl group, which optionally has a substituent, as the substituent, for example, an alkyl group (preferably an alkyl group having a carbon number of 1 to 17), an alkoxy group (preferably an alkoxy group having a carbon number of 1 to 8), an amino group, an alkylamino group (preferably an alkyl group having a carbon number of 1 to 8), or a dialkylamino group (preferably an alkyl group having a carbon number of 1 to 8), and the like.

[0099] as R 21 and R 22 represent a naphthyl group, which optionally has a substituent, as the substituent, the same groups as the above-mentioned substituents that the phenyl group represented by R 21 and R 22 can have.

[0100] Further, in General Formula (I-3), it is preferable that R 21 , R 23 each independently be a methyl group or an ethyl group, R 22 be a methyl group or a phenyl group, Ar be a single bond, or be a phenylene group, a naphthylene group, or a thiophenylene group, and n be 0.

[0101] As the compound represented by General Formula (I-3), the following compounds are more preferable.

[0102]

[0103] In the case of using such an oxime ester-based photopolymerization initiator, the sensitivity to exposure is improved, and in addition, if used in combination with an acylophosphine oxide-based photopolymerization initiator containing a structural moiety represented by General Formula (III) or the like, the cross-sectional shape of the cured film of the photocurable black composition becomes good, and thus is preferable.

[0104] As the α-aminoacetophenone-based photopolymerization initiator containing a structural moiety represented by General Formula (II), 2-methyl-l-(4-methylthiophenyl)-2-morpholino-l-propanone, 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-l-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-l-[4-(4-morpholinyl)phenyl]-l-butanone, N,N-dimethylaminoacetophenone, and the like can be given, and as commercially available products, Omnirad 907, Omnirad 369, Omnirad 379, and the like manufactured by IGM Resins B.V. can be given.

[0105] As the acylphosphine oxide-based photopolymerization initiator containing a structural moiety represented by General Formula (III), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and the like can be given, and as commercially available products, Omnirad TPO, Omnirad 819, and the like manufactured by IGM Resins B.V. can be given.

[0106] As the titanocene-based photopolymerization initiator represented by General Formula (IV), bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium can be given.

[0107] As commercially available products of the oxime ester-based photopolymerization initiator, IRGACURE OXE01 (1-[4-(phenylthio)-1.2-octanedione 2-(O-benzoyl oxime)]), IRGACURE OXE02 (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyl oxime)) manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, TR-PBG-304 manufactured by Changzhou Qiangli Electronic New Material Co., Ltd., TOE-04-A3 manufactured by Japan Chemical Industry Co., Ltd., and the like can be given.

[0108] (B) The photopolymerization initiator is 1 mass part or more and 30 mass parts or less, preferably 3 mass parts or more and 25 mass parts or less, further preferably 4 mass parts or more and 20 mass parts or less, relative to 100 mass parts (solid content) of (A) the alkali-soluble resin.

[0109] The compounding amount of (B) the photopolymerization initiator is 1 mass part or more and 30 mass parts or less, relative to 100 mass parts (solid content) of (A) the alkali-soluble resin, whereby the resolution becomes good.

[0110] [(C) Photopolymerizable multifunctional monomer]

[0111] The photocurable black composition of the present application contains a publicly 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, and the photocurable black composition is cured.

[0112] As the compound used as the aforementioned photopolymerizable multifunctional monomer, for example, commonly known polyesters (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, and the like can be mentioned. Specifically, diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, and the like; polyacrylates of polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trihydroxyethyl isocyanurate, and the like, or oxirane adducts, propylene oxide adducts, or ε-caprolactone adducts thereof; polyacrylates of phenoxyl acrylates, bisphenol A diacrylate, and oxirane adducts or propylene oxide adducts of these phenols; polyacrylates of glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and the like; acrylates and methacrylates of at least any one of polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, and the like, which are directly acrylated, or urethane acrylated with the aid of diisocyanates, and the like can be mentioned.

[0113] (C) The photopolymerizable multifunctional monomer preferably contains (C1) an RO-addition photopolymerizable multifunctional monomer and (C2) a lactone-addition photopolymerizable multifunctional monomer. Note that, in the present application, RO refers to an alkylene oxide, and as the alkylene oxide, ethylene oxide (EO) and propylene oxide (PO) are contained. Also, in the present application, the lactone contains γ-butyrolactone, δ-valerolactone, ε-caprolactone, and methylated ε-caprolactone.

[0114] (C1) The RO-addition photopolymerizable multifunctional monomer can be mentioned, for example, ethylene oxide adducts, propylene oxide adducts of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, and the like; ethylene oxide adducts, propylene oxide adducts of polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trihydroxyethyl isocyanurate, and the like.

[0115] (C2) The lactone-addition photopolymerizable multifunctional monomer can be mentioned, for example, ε-caprolactone adducts of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, and the like; ε-caprolactone adducts of polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trihydroxyethyl isocyanurate, and the like.

[0116] (C) In the case where the (C) photopolymerizable multifunctional monomer contains (C1) an RO-addition photopolymerizable multifunctional monomer and (C2) a lactone-addition photopolymerizable multifunctional monomer, the mass ratio (solid content) of the (C1) RO-addition photopolymerizable multifunctional monomer to the (C2) lactone-addition photopolymerizable multifunctional monomer in the photocurable black composition of the present application is in the range of 0.5 or more and 10 or less, preferably in the range of 0.5 or more and 7 or less, particularly preferably in the range of 1 or more and 5 or less. The mass ratio (solid content) of the (C1) RO-addition photopolymerizable multifunctional monomer to the (C2) lactone-addition photopolymerizable multifunctional monomer is in the range of 0.5 or more and 10 or less, whereby resolution becomes good.

[0117] Further, the (C) photopolymerizable multifunctional monomer preferably has 3 or more ethylenically unsaturated groups in 1 molecule, further preferably 3 or more and 6 or less ethylenically unsaturated groups in 1 molecule.

[0118] The compounding amount of the (C) photopolymerizable multifunctional monomer is in the range of 5 parts by mass or more and 50 parts by mass or less, preferably in the range of 5 parts by mass or more and 40 parts by mass or less, relative to the total of 100 parts by mass (solid content) of the (A) alkali-soluble resin.

[0119] When the compounding amount is in the range of 5 parts by mass or more and 50 parts by mass or less, resolution becomes good.

[0120] Note that a photopolymerizable monofunctional monomer can be contained in addition to the (C) photopolymerizable multifunctional monomer. As the photopolymerizable monofunctional monomer, for example, a hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate can be cited.

[0121] Further, the photocurable black composition of the present application preferably contains (D) a carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more based on JIS K6217-2:2017.

[0122] [(D) a carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more based on JIS K6217-2:2017]

[0123] (D) a carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more based on JIS K6217-2:2017 imparts a light-shielding property required for a black shielding material (black cover substrate) obtained from the photocurable black composition, and an effect of suppressing so-called white haze.

[0124] (D) a carbon black having a nitrogen adsorption specific surface area of 300 m 2As commercially available products of carbon black having a specific surface area of 300 m2 / g or more, #2300, #2350, #2600, #2650 (all manufactured by Mitsubishi Chemical Corporation) can be given.

[0125] In addition, the nitrogen adsorption specific surface area based on JIS K6217-2:2017 is preferably 300 m 2 / g or more and 400 m 2 / g or less.

[0126] (D) The nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300 m 2 The compounding amount of carbon black having a specific surface area of 300 m2 / g or more is preferably in the range of 8 parts by mass or more and 40 parts by mass or less, and more preferably in the range of 10 parts by mass or more and 30 parts by mass or less, and particularly preferably in the range of 10 parts by mass or more and 20 parts by mass or less, with respect to the total mass (solid content) of the photocurable black composition.

[0127] (D) The nitrogen adsorption specific surface area based on JIS K6217-2:2017 is 300 m

[0128] [(E) Ester of cellulose and short-chain fatty acid]

[0129] The photocurable black composition of the present application preferably contains (E) an ester of cellulose and a short-chain fatty acid. In the present application, the short-chain fatty acid refers to one having a carbon number of 4 or less, and in the ester of cellulose and a short-chain fatty acid, not only one in which the hydrogen of the hydroxyl group of the cellulose molecule is completely replaced with an acyl group, but also one in which a hydroxyl group remains in the cellulose molecule.

[0130] By containing (E) an ester of cellulose and a short-chain fatty acid in the photocurable black composition of the present application, the resistance to development is improved, and the tackiness (finger dryness) of the cured product is improved.

[0131] As the ester of (E) cellulose and a short-chain fatty acid, cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP) can be given, as commercially available products of cellulose acetate butyrate (CAB), CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-381-0.1, CAB-381-0.5 (all, manufactured by Eastman Company), and the like can be given, as commercially available products of cellulose acetate propionate (CAP), CAP-504-0.2, CAP-482-0.5 (all, manufactured by Eastman Company), and the like can be given.

[0132] In the case of compounding the ester of (E) cellulose and a short-chain fatty acid, the compounding amount is preferably in the range of 2 parts by mass or more and 15 parts by mass or less with respect to the total mass (solid content) of the photocurable black composition.

[0133] By the compounding amount of the ester of (E) cellulose and a short-chain fatty acid being in the range of 2 parts by mass or more and 15 parts by mass or less with respect to the total mass (solid content) of the photocurable black composition, the resistance to development is improved, and the tackiness (finger dryness) of the cured product is improved.

[0134] [(F) thermally curable component]

[0135] For the photocurable black composition of the present application, from the viewpoint of improving the heat resistance and shape stability of the cured product thereof, it is preferable that the photocurable black composition is subjected to thermal curing in addition to photocuring, and therefore, the photocurable black composition of the present application preferably contains a (F) thermally curable component.

[0136] As the (F) thermally curable component, a commonly known thermally curable resin such as an isocyanate compound (including blocked isocyanate compounds), an amino resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, an epoxy compound, a multifunctional oxetane compound, a cyclic sulfide resin, and the like can be used.

[0137] In the present application, an epoxy resin is particularly preferably used.

[0138] As the epoxy resin, a commonly known multifunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin can be a liquid, or a solid or a semi-solid. Here, the liquid, the solid, and the semi-solid each refer to the state of the epoxy resin at 30°C.

[0139] As the epoxy resin, for example, jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, EPICLON 850, EPICLON 850-S, EPICLON 1050, EPICLON 2055 manufactured by DIC Corporation, EPOTOTO YD-011, YD-013, YD-127, YD-128 manufactured by New Japan Chemical Co., Ltd., D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by Dow Chemical Company, Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd., etc. (all are trade names) bisphenol A type epoxy resins; jERYL903 manufactured by Mitsubishi Chemical Corporation, EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOTO YDB-400, YDB-500 manufactured by New Japan Chemical Co., Ltd., D.E.R.542 manufactured by Dow Chemical Company, Sumi-Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., etc. (all are trade names) brominated epoxy resins; jER152, jER154 manufactured by Mitsubishi Chemical Corporation, D.E.N.431, D.E.N.438、DIC Corporation's EPICLON N-730, EPICLON N-770, EPICLON N-865, Nippon Steel Chemical Co., Ltd.'s EPOTOTO YDCN-701, YDCN-704, Nippon Kayaku Co., Ltd.'s EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd.'s Sumi-Epoxy ESCN-195X, ESCN-220, Nippon Steel Chemical Co., Ltd.'s YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A, DIC Corporation's EPICLON N-680, EPICLON N-690, EPICLON N-695 (all trade names), and the like phenol novolak type epoxy resins; DIC Corporation's EPICLON 830, Mitsubishi Chemical Corporation's jER807, Nippon Steel Chemical Co., Ltd.'s EPOTOTO YDF-170, YDF-175, YDF-2004 (all trade names), and the like bisphenol F type epoxy resins; Nippon Steel Chemical Co., Ltd.'s EPOTOTO ST-2004, ST-2007, ST-3000 (trade name), Mitsubishi Chemical Corporation's YX8034, and the like hydrogenated bisphenol A type epoxy resins; Mitsubishi Chemical Corporation's jER604, Nippon Steel Chemical Co., Ltd.'s EPOTOTO YH-434, Sumitomo Chemical Co., Ltd.'s Sumi-Epoxy ELM-120 (all trade names), and the like glycidyl amine type epoxy resins; hydantoin type epoxy resins; Daicel Chemical Industry Ltd.'s CELLOXIDE 2021 (trade name), and the like alicyclic epoxy resins; Mitsubishi Chemical Corporation's YL-933, Nippon Kayaku Co., Ltd.'s T.E.N., EPPN-501, EPPN-502, etc. (all are trade names) of trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 (all are trade names) of biphenol type or bisphenol type epoxy resin or a mixture thereof manufactured by Mitsubishi Chemical Corporation; EBPS-200 manufactured by Nichigo, EPX-30 manufactured by ADEKA, EXA-1514 (trade name) manufactured by DIC Corporation, etc. of bisphenol S type epoxy resin; jER 157S (trade name) manufactured by Mitsubishi Chemical Corporation, etc. of bisphenol A novolak type epoxy resin; jERYL-931, etc. (all are trade names) of tetrahydroxyphenylethane type epoxy resin manufactured by Mitsubishi Chemical Corporation; TEPIC, etc. (all are trade names) of heterocyclic type epoxy resin manufactured by Nissan Chemical Industries, Ltd.; BLEMMER DGT, etc. of phthalic acid diglycidyl ester resin manufactured by Nippon Oil Corporation; ZX-1063, etc. of tetraglycidyl xylene acyl ethane resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700, etc. of naphthalene ring-containing epoxy resin manufactured by DIC Corporation; HP-7200, HP-7200H, etc. of epoxy resin having dicyclopentadiene skeleton manufactured by DIC Corporation; CP-50S, CP-50M, etc. of glycidyl methacrylate copolymer type epoxy resin manufactured by Nippon Oil Corporation; and copolymer epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; CTBN-modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc., but are not limited to these.

[0140] These epoxy resins are various in liquid, solid, semi-solid at 30°C, but one kind can be used alone, or two or more kinds can be used in combination. In addition, the epoxy resin is used in combination with other publicly known thermosetting components described above.

[0141] In the case of compounding (F) thermosetting component, the compounding amount is preferably in the range of 30 parts by mass or more and 120 parts by mass or less, and further preferably in the range of 40 parts by mass or more and 80 parts by mass or less, with respect to 100 parts by mass (solid content) of (A) alkali-soluble resin.

[0142] [Leveling agent]

[0143] The photocurable black composition of the present application preferably contains a leveling agent. The leveling agent is used to adjust the flowability of the photocurable black composition, and to make the coating film of the photocurable black composition flat. As the leveling agent, a surfactant can be mentioned, and a leveling agent in which a polyacrylate compound is the main component is preferably used.

[0144] As the leveling agent in which a polyacrylate compound is the main component, BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-381, BYK-392, BYK-394, BYK-3441 (all of which are manufactured by BYK Japan K.K. and BYK is a registered trademark) can be mentioned.

[0145] In the case where the photocurable black composition of the present application contains a leveling agent, the compounding amount thereof is preferably in the range of 0.05 parts by mass or more and 5 parts by mass or less, and further preferably in the range of 0.1 parts by mass or more and 3 parts by mass or less, with respect to the total mass (solid content) of the photocurable black composition.

[0146] [Other Components]

[0147] In the photocurable black composition of the present application, further, a known and commonly used polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, a known and commonly used inorganic filler such as barium sulfate, barium titanate, silicon oxide powder, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, a known and commonly used thickening agent such as microfine silica, organic bentonite, montmorillonite, a known and commonly used additive such as a defoaming agent of silicone type, fluorine type, an antioxidant, a photopolymerization sensitizer, a light stabilizer, a dispersant, a curing accelerator, a flame retardant, a flame retardant aid, and the like can be compounded as needed.

[0148] In addition, the photocurable black composition of the present application can also contain an organic solvent used for preparing the photocurable black composition and adjusting the viscosity. As the organic solvent, for example, ketones such as methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, 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, propylene carbonate, aliphatic hydrocarbons such as octane, decane, petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha, and the like can be used. These organic solvents can be used alone or in combination of two or more.

[0149] The photocurable black composition of the present application can be adjusted to a single liquid system, or can be composed as a two-liquid system. In the case of forming a two-liquid system, the (B) photopolymerization initiator is compounded in a liquid different from the liquid containing the (A) alkali-soluble resin and the (C) photopolymerizable multifunctional monomer. This is because in order to prevent an undesirable photopolymerization reaction at the time of storage.

[0150] The photocurable black composition of the present application, since it can suppress the occurrence of white blur, can obtain a high-quality, high-class display member with improved visual recognition. The photocurable black composition of the present application can be used in the production of printing ink, color correction materials for printing, etching resists, solder resists, partitions of organic or inorganic EL display panels, dielectric patterns, electrode (conductor circuit) patterns, wiring patterns of electronic components, conductive paste, conductive film, black matrix, black sealing material, black mask material, and the like, and in particular, the photocurable black composition of the present application, in order to improve the visual recognition of color filters used in color liquid crystal display devices and the like, can be suitably used for providing a light-shielding image (including a black matrix) in the partitions of colored patterns, the peripheral portions, and the outer light side of TFTs, and the like, or a light-shielding film for a touch panel. It is particularly preferable to be used as a black matrix for a black frame provided in the peripheral portion of a liquid crystal display device, an EL display device provided with organic or inorganic EL, a display device provided with a touch panel, a lattice-shaped or striped black portion between colored pixels of red, blue, and green, and further preferably a dot-shaped or linear black pattern for TFT light shielding.

[0151] Cured product of the photocurable black composition of the present application, and black-covered substrate

[0152] The black-covered substrate of the present application has a transparent substrate, and a cured film (cured product) of the photocurable black composition of the present application coated on the transparent substrate.

[0153] The transparent substrate is a substrate having a total light transmittance of 400 to 800 nm of 50% or more, and specifically, a glass substrate, or a resin substrate such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyimide (PI), and the like can be mentioned, and as the shape, a plate to a film can be mentioned. Note that, as a plate, it is not limited to a flat plate, but can be a concave lens, a convex lens shape, a curved shape.

[0154] The photocurable black composition of the present application can form a dry film state in which the photocurable black composition is coated on a support film (carrier) and dried. At the time of dry film formation, the photocurable black composition of the present application is diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate level, and is coated on a support film in a uniform thickness using a comma coater, a doctor blade coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like, and is generally dried at a temperature of 50 to 130°C for 1 to 30 minutes, whereby a dry coating film can be formed. The coating film thickness is not particularly limited, and in general, it is appropriate to select a range of 0.1 to 100 μm, preferably 0.5 to 50 μm, in terms of the film thickness after drying.

[0155] As the support film, a plastic film can be used, and a polyester film such as polyethylene terephthalate, a polyimide film, a polyamide-imide film, a polypropylene film, a polystyrene film, or the like is preferably used. The thickness of the support film is not particularly limited, and in general, it is appropriate to select a range of 0.1 to 150 μm.

[0156] In this case, after the film formation on the support film is completed as a coating film, a peelable cover film is preferably laminated on the surface of the coating film for the purpose of preventing dust or the like from adhering to the surface of the coating film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, provided that the adhesion between the coating film and the cover film is smaller than the adhesion between the coating film and the support film at the time of peeling the cover film.

[0157] In addition, after the photocurable black composition of the present application is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, the composition is coated on a transparent substrate by a method such as a spray coating method, a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method, a curtain coating method, a die coating method, or the like, and then the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of about 50 to 90°C, whereby a dry coating film which is not tacky can be formed. In the case where the photocurable black composition of the present application is coated on a support film and dried to form a dry film in the form of a thin film, the dry film is attached to a transparent substrate in such a manner that the coating film of the photocurable black composition contacts the transparent substrate using a laminator or the like, and then the support film is peeled, whereby a layer of the coating film can be formed on the substrate.

[0158] These coating films are photocured by, for example, irradiation of active energy rays, and in the case where a (F) thermal curing component is further contained, the coating film is further heated to a temperature of 100 to 250°C to be thermally cured, whereby a cured coating film (cured product) can be obtained. That is, a black cover substrate having a transparent substrate and a cured coating film (cured product) of the photocurable black composition of the present application coated on the transparent substrate can be obtained.

[0159] The volatile drying after coating the photocurable black composition of the present application can be performed using a method in which a heat source having an air heating method using steam, such as a hot air circulating type drying furnace, an IR furnace, a hot plate, a convection oven, etc. is brought into contact with the hot air convection in the drying machine, and a method in which a nozzle is blown onto a support.

[0160] As an exposure machine used in the active energy ray irradiation, a device in which a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like is mounted to irradiate ultraviolet rays in the range of 350 to 450 nm, and further a direct drawing device (for example, a direct imaging device in which an image is drawn by directly irradiating an active energy ray from a computer using CAD data) can be used. As a light source of the direct drawing machine, a light having a maximum wavelength in the range of 350 to 410 nm can be used. The exposure amount for image formation varies depending on the film thickness, etc., and can be set to the range of 20 to 1000 mJ / cm 2 , preferably 20 to 800 mJ / cm 2 .

[0161] In addition, as a developing method, an immersion method, a spray method, a spray method, a brush coating method, etc. can be used, and as a developing solution, an aqueous alkali solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used.

[0162] Example

[0163] Hereinafter, the present application will be specifically described by examples, but the present application is not limited only to these examples. Note that, in the following, "parts" means mass parts unless otherwise specified.

[0164] <1. Preparation of photocurable black compositions of Examples 1 to 7 and Comparative Examples 1 to 3>

[0165] Each of the materials shown in Table 1 was compounded and mixed in a blender to prepare a first liquid, and each of the materials shown in Table 1 was similarly compounded and mixed in a blender to prepare a second liquid. Thereafter, the first liquid and the second liquid were mixed and stirred to prepare a photocurable black composition.

[0166] [Table 1]

[0167]

[0168] *1: High-boiling solvent-diluted product of radical-curable acryl polymer containing acryloyl and carboxyl groups (solid content 46%) (Cyclomer P(ACA) Z250: manufactured by DAICEL-ALLNEX LTD.)

[0169] *2: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO H: manufactured by IGM Resins B.V.)

[0170] *3: EO-addition trimethylolpropane triacrylate (LAROMER LR8863: manufactured by BASF Japan Ltd.)

[0171] *4: hexaacrylate of ε-caprolactone-modified dipentaerythritol (DPCA-60: manufactured by Nippon Kayaku Co., Ltd.)

[0172] *5: carbon black having a nitrogen adsorption specific surface area of 370 m 2 / g (#2650: manufactured by Mitsubishi Chemical Corporation)

[0173] *6: carbon black having a nitrogen adsorption specific surface area of 320 m 2 / g (#2350: manufactured by Mitsubishi Chemical Corporation)

[0174] *7: carbon black having a nitrogen adsorption specific surface area of 260 m 2 / g (#980: manufactured by Mitsubishi Chemical Corporation)

[0175] *8: carbon black having a nitrogen adsorption specific surface area of 88 m 2 / g (#52: manufactured by Mitsubishi Chemical Corporation)

[0176] *9: DPM (dipropylene glycol monomethyl ether) diluted product of cellulose acetate butyrate (solid content 30%) (CAB-551-0.2: manufactured by Eastman Chemical Company)

[0177] *10: leveling agent using a polyacrylate compound as a main component (BYK-361N: manufactured by BYK Japan K.K.)

[0178] *11: dipropylene glycol monomethyl ether

[0179] *12: propylene glycol monomethyl ether

[0180] *13: carbitol acetate diluted product of a solid bisphenol A type epoxy resin (jER (registered trademark) 1001: manufactured by Mitsubishi Chemical Corporation) (solid content 75%)

[0181] *14: Liquid hydroquinone type epoxy resin (YX8034: manufactured by Mitsubishi Chemical Corporation)

[0182] *15: Dimer oxime ester-based photopolymerization initiator (TOE-04-A3: manufactured by Japan Chemical Industry Co., Ltd.)

[0183] *16: Propylene carbonate

[0184] <2. Production of cured coating film (cured product) and evaluation thereof>

[0185] 2-1. Production of cured coating film (cured product)

[0186] The surface of a glass substrate (EAGLE XG 1.1 mm thick, manufactured by Corning Inc.) was subjected to degreasing treatment with alcohol, and each of the photocurable black compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 was applied to the surface thereof after the degreasing treatment with an air spray type spray coater so that the DRY film thickness became about 10 μm. Thereafter, the glass substrate was dried in a hot air circulating type drying oven at 90°C for 30 minutes, and was subjected to exposure in an exposure device (HMW680GW, manufactured by ORC Co.) at 1500 mJ / cm 2 with ultraviolet light.

[0187] Then, 1 mass% Na2CO3 aqueous solution at 30°C was applied for 60 seconds under a spray pressure of 0.2 MPa, and after development, the glass substrate was subjected to post-UV treatment on a UV transmission belt oven at 1000 mj / cm 2 After the post-UV treatment, the glass substrate was subjected to post-curing at 150°C for 1 hour, whereby a black cover substrate having a glass substrate and a cured coating film (cured product) of the photocurable black composition applied to the glass substrate was formed.

[0188] 2-2. OD value (optical density)

[0189] The cured coating film side of the black cover substrate formed in "2-1. Production of cured coating film (cured product)" was mounted on a transmittance meter (X-Rite 361T, manufactured by Sakata Inx Engineering Co.), and the OD value was evaluated. Note that the black cover substrate was mounted on the transmittance meter with the glass substrate side facing the light source.

[0190] 2-3. Reflectance (Y value) SCE / SCI (%)

[0191] For the black cover substrate formed in "2-1. Production of cured film (cured product)", the Y value of XYZ colorimetric system was measured with a color difference meter (CM-2600d (light source wavelength: 360 to 740 nm), manufactured by Konica Minolta, Inc.). The Y value was measured in the SCE (specular component excluded) mode for measuring only diffuse reflection light in order to remove specular reflection light, so as to approximate the evaluation of color as seen by the eye, and the SCI (specular component included) mode for measuring including specular reflection light, so as to evaluate the color of the raw material itself regardless of the surface state. Note that the measurement was performed with respect to the glass substrate surface of the black cover substrate.

[0192] The lower the value of the reflectance (Y value) SCE / SCI (%), the more it can be said that the occurrence of white blur is suppressed.

[0193] 2-4. Resolution

[0194] A negative pattern having a line width of 20 to 300 μm of the light-shielding portion was used at the time of exposure, and otherwise, the black cover substrate was formed under the same conditions as those of "2-1. Production of cured film (cured product)".

[0195] For each of the black cover substrates of Examples 1 to 7 and Comparative Examples 1 to 3 formed, the width of the linear cured product remaining on the glass substrate was measured, and the smallest width among the widths of the linear cured product remaining was recorded as an evaluation item of resolution (L / S). The smaller the width of the resolution (L / S), the better the photocurable black composition was evaluated to have a resolution capable of forming a finer line.

[0196] 2-5. Developability

[0197] A negative pattern having a line width of 20 to 300 μm of the light-shielding portion was used at the time of exposure, and otherwise, the black cover substrate was formed under the same conditions as those of "2-1. Production of cured film (cured product)".

[0198] For each of the black cover substrates of Examples 1 to 7 and Comparative Examples 1 to 3 formed, the area on the glass substrate developed in the alkali was visually observed with the area covered with the light-shielding portion of the negative pattern being unexposed, and it was evaluated whether or not the developed residue was visible in the area. The evaluation criteria are as described below.

[0199] : No residue was visible.

[0200] : Residue was visible in part.

[0201] : Residue was visible in the whole.

[0202] 2-6. Adhesiveness

[0203] Each of the photocurable black compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was screen-printed on a glass substrate, and dried in a hot air circulation type drying oven at 90°C for 30 minutes, and then naturally cooled to room temperature. A PET film was pressed against the glass substrate on which the photocurable black composition was coated, and then the state of adhesion of the film when the film was peeled off was evaluated. The evaluation criteria were as follows.

[0204] : The film was not at all adhered.

[0205] : The film was slightly adhered, but the film did not leave a trace of pressure bonding on the ink.

[0206] : The film left a trace of pressure bonding on the ink.

[0207] : The ink was transferred to the film.

[0208] The evaluation results of the OD value (optical density), reflectance, resolution, developability and adhesion are shown in Table 2 below.

[0209] [Table 2]

[0210]

[0211] As shown in Table 2, the reflectance (Y value) SCE / SCI (%) became very small in Examples 1 to 2 as compared with Comparative Examples 1 to 2, and thus it was found that white blur was suppressed when carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more was used. In addition, the adhesion was improved in Example 1 as compared with Example 5, and thus it was found that the adhesion was improved by compounding (E) cellulose ester with a short-chain fatty acid.

Claims

1. A photocurable black composition, characterized by, having: (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a photopolymerizable multifunctional monomer, (D) Carbon black having a nitrogen adsorption specific surface area of 300 m 2 / g or more, (E) an ester of cellulose with a short-chain fatty acid, and a leveling agent, the compounding amount of the (D) carbon black is 10 parts by mass or more and 30 parts by mass or less, in terms of solid content, relative to the total mass of the photocurable black composition, the compounding amount of the (E) ester of cellulose with a short-chain fatty acid is 2 parts by mass or more and 15 parts by mass or less, in terms of solid content, relative to the total mass of the photocurable black composition, the compounding amount of the leveling agent is 0.05 parts by mass or more and 5 parts by mass or less, in terms of solid content, relative to the total mass of the photocurable black composition.

2. The photocurable black composition according to claim 1, characterized by The (C) photopolymerizable multifunctional monomer contains: (C1) an RO-addition photopolymerizable multifunctional monomer and (C2) a lactone-addition photopolymerizable multifunctional monomer.

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

4. The photocurable black composition according to claim 1 or 2, characterized by, (D) The carbon black has a nitrogen adsorption specific surface area based on JIS K6217-2:2017 of 300 m 2 / g or more and 400 m 2 / g or less.

5. The photocurable black composition according to claim 1 or 2, characterized by, It further contains (F) a thermocurable component.

6. A cured product, which is a cured product of the photocurable black composition described in any one of claims 1 to 5.

7. A black covered substrate, characterized in that, having: a transparent substrate, and a cured film of the photocurable black composition described in any one of claims 1 to 5 coated on the transparent substrate.

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