Photosensitive composition, transfer film, laminate and manufacturing method therefor, and microled display

Abstract

The present invention provides a photosensitive composition containing a colorant precursor that develops black by stimulation, a transfer film using the photosensitive composition, a laminate, a method for manufacturing the laminate, and a micro LED display.

Description

Technical Field

[0001] The present invention relates to a photosensitive composition, a transfer film, a laminate, a method for manufacturing the same, and a micro LED display. Background Art

[0002] In recent years, in new display manufacturing methods such as micro LED (Light Emission Diode), black partition walls with a high aspect ratio (so-called black matrix) are required.

[0003] Various reports have been made on the black matrix. For example, Japanese Patent Application Laid-Open No. 2022-63445 discloses a technique for forming a black matrix using a photosensitive coloring composition containing carbon black as a color material. Summary of the invention

[0004] Technical issues to be solved by the invention

[0005] However, when carbon black is used as a color material, for example, when a black matrix of a negative pattern is formed, since carbon black absorbs the light (e.g., ultraviolet rays) to be exposed, the incident light gradually attenuates in the film thickness direction of the composition layer for forming the pattern, and due to insufficient polymerization and curing, it is difficult to obtain a pattern with a good shape after development. Therefore, a technology is required that can suppress the absorption of incident light during pattern exposure and transmit the incident light, and finally form a pattern with excellent light-shielding properties.

[0006] The present invention has been accomplished in view of the above-mentioned circumstances.

[0007] An object of one embodiment of the present invention is to provide a photosensitive composition that can form a film having excellent light-shielding properties and has excellent patterning properties.

[0008] Another embodiment of the present invention aims to provide a transfer film, a laminate, a method for producing the same, and a micro LED display using the photosensitive composition.

[0009] Means for solving technical problems

[0010] Specific means for solving the above-mentioned problems include the following embodiments.

[0011] <1> A photosensitive composition comprising a color material precursor that develops black color upon stimulation.

[0012] <2> according to <1> The photosensitive composition, wherein

[0013] The stimulus is at least one selected from the group consisting of heat, light, acid, alkali and free radicals.

[0014] <3> according to <1> The photosensitive composition, wherein

[0015] The above stimulus is heat.

[0016] <4> according to <1> to <3> The photosensitive composition described above further comprises an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator.

[0017] <5> according to <1> to <4> The photosensitive composition according to any one of the preceding claims, wherein

[0018] When a film having a film thickness of 1 μm is formed using the photosensitive composition, the absorbance of the film at a wavelength of 365 nm is 0.1 or less.

[0019] <6> according to <1> to <5> The photosensitive composition according to any one of the preceding claims, wherein

[0020] When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the absorbance of the film at a wavelength of 365 nm is 0.2 or more.

[0021] <7> according to <1> to <6> The photosensitive composition according to any one of the preceding claims, wherein

[0022] When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the average absorbance of the film at a wavelength of 400 nm to 700 nm is 0.2 or more.

[0023] <8> according to <1> to <7> The photosensitive composition according to any one of the preceding claims, wherein

[0024] The color material precursor is a compound represented by the following formula (1).

[0025] [Chemical formula 1]

[0026]

[0027] In formula (1), X 1 , X 2 , X 3 , X 4 , Y 1 and Y 2 Each independently represents an oxygen atom, a sulfur atom or NL 1 .L 1 represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group. 1 , R 2 , R 3 and R 4Each independently represents a hydrogen atom, -OL 2 、-OCO-L 3 , -SL 2 or-OSO-L 3 .L 2 represents a hydrogen atom or an alkyl group, L 3 represents an alkyl group or an amino group. 1 and R 2 At least one of represents a hydrogen atom, R 3 and R 4 At least one of represents a hydrogen atom. A, B and C each independently represent an aromatic ring.

[0028] <9> A photosensitive composition comprising:

[0029] The color material precursor develops black color by at least one stimulus selected from the group consisting of heat, light, acid, alkali and free radicals;

[0030] Alkali soluble resin;

[0031] polymerizable monomers; and

[0032] Photopolymerization initiator,

[0033] The photosensitive composition satisfies all of the following (1) to (3).

[0034] (1) When a film having a film thickness of 1 μm is formed using the photosensitive composition, the absorbance of the film at a wavelength of 365 nm is 0.1 or less.

[0035] (2) When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the absorbance of the film at a wavelength of 365 nm is 0.2 or more.

[0036] (3) When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the average absorbance of the film at a wavelength of 400 nm to 700 nm is 0.2 or more.

[0037] <10> according to <9> The photosensitive composition, wherein

[0038] The color material precursor is a compound represented by the following formula (1).

[0039] [Chemical formula 2]

[0040]

[0041] In formula (1), X 1 , X 2 , X3 , X 4 , Y 1 and Y 2 Each independently represents an oxygen atom, a sulfur atom or NL 1 .L 1 represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group. 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom, -OL 2 、-OCO-L 3 , -SL 2 or-OSO-L 3 .L 2 represents a hydrogen atom or an alkyl group, L 3 represents an alkyl group or an amino group. 1 and R 2 At least one of represents a hydrogen atom, R 3 and R 4 At least one of represents a hydrogen atom. A, B and C each independently represent an aromatic ring.

[0042] <11> A transfer film, comprising:

[0043] Temporary supports; and

[0044] A photosensitive composition layer comprising <1> to <10> The photosensitive composition described above.

[0045] <12> according to <11> The transfer film, wherein

[0046] The photosensitive composition layer has a film thickness of 5 μm or more.

[0047] <13> A method for manufacturing a laminated body, which is a method for manufacturing a laminated body having a black pattern, which comprises: forming a layer containing a black pattern on a substrate; <1> to <10> A process for forming a photosensitive composition layer of the photosensitive composition described in any one of the preceding claims;

[0048] A step of pattern-exposing the photosensitive composition layer; and

[0049] a step of developing the photosensitive composition layer;

[0050] The method for producing the laminated body includes, after the pattern exposure step, the step of developing the color material precursor into black.

[0051] <14> according to <13> The method for manufacturing the laminated body, wherein:

[0052] The film thickness of the black pattern is 5 μm or more.

[0053] <15> A laminate having a black pattern and <13> or <14> The manufacturing method is described.

[0054] <16> according to <15> The laminated body, wherein

[0055] The film thickness of the black pattern is 5 μm or more.

[0056] <17> according to <15> or <16> The laminated body, wherein

[0057] The black pattern has an absorbance of 2.0 or more at a wavelength of 365 nm.

[0058] <18> according to <15> to <17> The laminate according to any one of the preceding claims, wherein

[0059] The black pattern has an average absorbance of 2.0 or more at a wavelength of 400 nm to 700 nm.

[0060] <19> according to <15> to <18> The laminate according to any one of the preceding claims, wherein

[0061] The aspect ratio, which is a ratio of the film thickness of the black pattern to the line width of the bottom, is 1.0 or more.

[0062] <20> A laminated body comprising a substrate and a black pattern,

[0063] The black pattern has a film thickness of 5 μm or more, an aspect ratio of the film thickness to the line width at the bottom of the pattern is 1.0 or more, and an average absorbance at a wavelength of 400 nm to 700 nm is 2.0 or more.

[0064] <21> according to <20> The laminated body, wherein

[0065] The ratio of the line width of the uppermost portion of the black pattern to the line width of the bottom portion is 0.8 to 1.2.

[0066] <22> according to <20> or <21> The laminated body, wherein

[0067] The black pattern includes a color material represented by the following formula (I).

[0068] [Chemical formula 3]

[0069]

[0070] In formula (I), X 1a , X 2a , X 3a , X 4a , Y 1a and Y2a Each independently represents an oxygen atom, a sulfur atom or NI 1a I 1a represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group. A', B' and C' each independently represent an aromatic ring.

[0071] <23> A micro LED display having <20> or <21> The laminated body.

[0072] Effects of the Invention

[0073] According to one embodiment of the present invention, a photosensitive composition capable of forming a film having excellent light-shielding properties and having excellent patterning properties is provided.

[0074] According to another embodiment of the present invention, a transfer film, a laminate, a method for manufacturing the same, and a micro LED display using the photosensitive composition are provided. DETAILED DESCRIPTION

[0075] The following description of the requirements is sometimes made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments and can be implemented with appropriate changes within the scope of the purpose of the present invention.

[0076] In the present invention, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit, respectively.

[0077] In the numerical ranges recorded in stages in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of other numerical ranges recorded in stages. And, in the numerical ranges recorded in the present invention, the upper limit or lower limit recorded in a certain numerical range can be replaced by the value shown in the embodiment.

[0078] In the present invention, when referring to the amount of each component in the composition, if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the amount refers to the total amount of the plurality of components present in the composition.

[0079] In the present invention, a combination of two or more preferred aspects is a more preferred aspect.

[0080] In the present invention, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0081] In the present invention, "transparent" means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, preferably 90% or more.

[0082] In the present invention, "transmittance" is a value measured using a spectrophotometer. As the spectrophotometer, for example, a spectrophotometer (model: U-3310) manufactured by Nitachi, Ltd. can be used. However, the spectrophotometer is not limited thereto.

[0083] In the present invention, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight (Mw; the same applies hereinafter).

[0084] In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (αPC).

[0085] The values ​​measured by GPC are as follows: TSKgel (registered trademark) GMHxL, TSKgel (registered trademark) G4000HxL or TSKgel (registered trademark) G2000HxL [all trade names manufactured by TOSOH CORPORATION] is used as the column, tetrahydrofuran (THF) is used as the eluent, a differential refractometer is used as the detector, and polystyrene is used as the standard substance, and the above-mentioned polystyrene conversion value is measured by a CPC analysis device.

[0086] In the present invention, unless otherwise specified, the ratio of the constituent units of the polymer compound is a mass ratio.

[0087] In the present invention, “(meth)acrylic acid” is a term including both “acrylic acid” and “methacrylic acid”, “(meth)acrylate” is a term including both “acrylate” and “methacrylate”, and “(meth)acryloyloxy” is a term including both “acryloyloxy” and “methacryloyloxy”.

[0088] In the present invention, "alkali-soluble" means that the solubility in 100 g of a 1 mass % sodium carbonate aqueous solution at a liquid temperature of 22°C is 0.1 g or more.

[0089] In the present invention, "water-soluble" means that the solubility in 100 g of water at a liquid temperature of 22° C. and a pH of 7.0 is 0.1 g or more. For example, a "water-soluble resin" refers to a resin that satisfies the above solubility conditions.

[0090] In the present invention, the "solid content" in the composition refers to the components that form the composition layer formed using the composition, and when the composition contains a solvent, it refers to all components other than the solvent. In addition, if it is a component that forms the composition layer, liquid components other than the solvent are also regarded as solid components. In the present invention, "solvent" refers to water and organic solvents.

[0091] In the present invention, "n-" means normal, "s-" means secondary, and "t-" means tertiary.

[0092] In the present invention, “light” refers to, for example, ultraviolet light, visible light, and infrared light.

[0093] In the present invention, “ultraviolet light” refers to light in a wavelength range of 200 nm to less than 400 nm, “visible light” refers to light in a wavelength range of 400 nm to less than 780 nm, and “infrared light” refers to light in a wavelength range of 780 nm to less than 1000 nm.

[0094] In the notation of groups (atomic groups) in the present invention, the notation not indicating substituted or unsubstituted includes not only groups without substitution but also groups with substitution. For example, "alkyl" includes not only groups of alkyl without substitution (also referred to as "unsubstituted alkyl") but also groups of alkyl with substitution (also referred to as "substituted alkyl").

[0095] The "substituent" in the present invention is not particularly limited, and for example, can be arbitrarily selected from the group consisting of a halogen group, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a sulfo group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxyl group, a carbamoyl group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a cyano group, a nitro group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphinyl group, a phosphinyloxy group and a phosphinylamino group.

[0096] More specifically, the substituents in the present invention include, for example, halogen groups (e.g., fluoro, chloro, bromo and iodo), alkyl groups (linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, preferably linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms; for example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl), cycloalkyl groups (e.g., cyclopropyl and cyclopentyl), alkenyl groups (e.g., cyclopentyl and cyclopentyl), and cyclopentyl groups. Straight-chain, branched or cyclic alkenyl groups having 2 to 10 carbon atoms, preferably straight-chain, branched or cyclic alkenyl groups having 2 to 6 carbon atoms; for example, vinyl, allyl and isoprenyl), cycloalkenyl groups (for example, cyclopenten-1-yl), alkynyl groups (alkynyl groups having 2 to 10 carbon atoms, preferably alkynyl groups having 2 to 6 carbon atoms; for example, ethynyl and propargyl), aryl groups (aryl groups having 6 to 12 carbon atoms, preferably aryl groups having 6 to 8 carbon atoms; for example , phenyl, p-tolyl, naphthyl, 3-chlorophenyl and 2-aminophenyl), heterocyclic group (a monovalent group having 1 to 12 carbon atoms, preferably a monovalent group having 2 to 6 carbon atoms, obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound; for example, 1-pyrazolyl, 1-imidazolyl, 2-furanyl, 2-thienyl, 4-pyrimidinyl and 2-benzothiazolyl), cyano, hydroxy, nitro, alkoxy (having one a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms; for example, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a cyclopentyloxy group, a 2-buten-1-yloxy group and a 2-methoxyethoxy group), an aryloxy group (an aryloxy group having 6 to 12 carbon atoms, preferably an aryloxy group having 6 to 8 carbon atoms; for example, a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group and a 3-nitrophenoxy group),

[0097] a heterocyclicoxy group (a heterocyclicoxy group having 1 to 12 carbon atoms, preferably a heterocyclicoxy group having 2 to 6 carbon atoms; for example, 1-phenyltetrazol-5-oxy-2-tetrahydropyranyloxy group), an acyloxy group (an acyloxy group having 1 to 12 carbon atoms, preferably an acyloxy group having 1 to 8 carbon atoms; for example, formyloxy, acetyloxy, pivaloyloxy, benzoyloxy and p-methoxyphenylcarbonyloxy group), a carbamoyloxy group (a carbamoyloxy group having 1 to 10 carbon atoms, preferably a carbamoyloxy group having 1 to 6 carbon atoms; for example, N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinylcarbonyloxy and N,N-dimethylcarbamoyloxy group), , N-octylcarbamoyloxy), alkoxycarbonyloxy (alkoxycarbonyloxy having 2 to 10 carbon atoms, preferably alkoxycarbonyloxy having 2 to 6 carbon atoms; for example, methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy and n-octyloxycarbonyloxy), aryloxycarbonyloxy (aryloxycarbonyloxy having 7 to 12 carbon atoms, preferably aryloxycarbonyloxy having 7 to 10 carbon atoms; for example, phenoxycarbonyloxy and p-methoxyphenoxycarbonyloxy), amino (amino; alkylamino having 1 to 10 carbon atoms, preferably alkylamino having 1 to 6 carbon atoms; anilino having 6 to 12 carbon atoms, preferably anilino having or heterocyclic amino groups having 1 to 12 carbon atoms, preferably heterocyclic amino groups having 2 to 6 carbon atoms; for example, including amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, imidazol-2-ylamino and pyrazol-3-ylamino), acylamino (alkylcarbonylamino groups having 1 to 10 carbon atoms, preferably alkylcarbonylamino groups having 1 to 6 carbon atoms; arylcarbonylamino groups having 6 to 12 carbon atoms, preferably arylcarbonylamino groups having 6 to 8 carbon atoms; or heterocyclic carbonylamino groups having 2 to 12 carbon atoms, preferably heterocyclic carbonylamino groups having 2 to 6 carbon atoms; ylamino; for example, including formylamino, acetylamino, pivaloylamino, benzylamino, pyridine-4-carbonylamino and thiophene-2-carbonylamino), aminocarbonylamino (aminocarbonylamino having 1 to 12 carbon atoms, preferably aminocarbonylamino having 1 to 6 carbon atoms; for example, aminoformylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino and morpholin-4-ylcarbonylamino), alkoxycarbonylamino (alkoxycarbonylamino having 2 to 10 carbon atoms, preferably alkoxycarbonylamino having 2 to 6 carbon atoms; for example, methoxycarbonylamino, ethoxycarbonylamino and tert-butoxycarbonylamino),

[0098] an aryloxycarbonylamino group (an aryloxycarbonylamino group having 7 to 12 carbon atoms, preferably an aryloxycarbonylamino group having 7 to 9 carbon atoms; for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and a 4-methoxyphenoxycarbonylamino group), a sulfamoylamino group (an sulfamoylamino group having 0 to 10 carbon atoms, preferably an sulfamoylamino group having 0 to 6 carbon atoms; for example, a sulfamoylamino group, an N,N-dimethylaminosulfonylamino group, and an N-(2-hydroxyethyl)sulfamoylamino group), an alkylsulfonylamino group (an alkylsulfonylamino group having 1 to 10 carbon atoms, preferably an alkylsulfonylamino group having 1 to 6 carbon atoms; for example, a methylsulfonylamino group and a butylsulfonylamino group), an arylsulfonylamino group ( an arylsulfonylamino group having 6 to 12 carbon atoms, preferably an arylsulfonylamino group having 6 to 8 carbon atoms; for example, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino and p-methylphenylsulfonylamino), a mercapto group, an alkylthio group (an alkylthio group having 1 to 10 carbon atoms, preferably an alkylthio group having 1 to 6 carbon atoms; for example, methylthio, ethylthio and butylthio), an arylthio group (an arylthio group having 6 to 12 carbon atoms, preferably an arylthio group having 6 to 8 carbon atoms; for example, phenylthio, p-chlorophenylthio and m-methoxythio), a heterocyclic thio group (a heterocyclic thio group having 2 to 10 carbon atoms, preferably a heterocyclic thio group having 1 to 6 carbon atoms; for example, 2-benzothiazole The preferred embodiments include sulfamoyl (sulfamoyl having 0 to 10 carbon atoms, preferably sulfamoyl having 0 to 6 carbon atoms; for example, sulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl and N-benzoylsulfamoyl), alkylsulfinyl (alkylsulfinyl having 1 to 10 carbon atoms, preferably alkylsulfinyl having 1 to 6 carbon atoms; for example, methylsulfinyl and ethylsulfinyl), arylsulfinyl (arylsulfinyl having 6 to 12 carbon atoms, preferably arylsulfinyl having 6 to 8 carbon atoms; for example, phenylsulfinyl and p-methylphenylsulfinyl), thiazolylsulfinyl (sulfamoyl having 0 to 10 carbon atoms, preferably sulfamoyl having 0 to 6 carbon atoms; for example, thiazolylsulfinyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl and N-benzoylsulfamoyl), ), alkylsulfonyl (alkylsulfonyl having 1 to 10 carbon atoms, preferably alkylsulfonyl having 1 to 6 carbon atoms; for example, methylsulfonyl and ethylsulfonyl), arylsulfonyl (arylsulfonyl having 6 to 12 carbon atoms, preferably arylsulfonyl having 6 to 8 carbon atoms; for example, phenylsulfonyl and p-chlorophenylsulfonyl), sulfonyl, acyl (formyl; alkylcarbonyl having 2 to 10 carbon atoms, preferably alkylcarbonyl having 2 to 6 carbon atoms; or arylcarbonyl having 7 to 12 carbon atoms, preferably arylcarbonyl having 7 to 9 carbon atoms; for example, acetyl, pivaloyl, 2-chloroacetyl, benzoyl and 2,4-dichlorobenzoyl),

[0099] Alkoxycarbonyl (alkoxycarbonyl having 2 to 10 carbon atoms, preferably alkoxycarbonyl having 2 to 6 carbon atoms; for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl and isobutoxycarbonyl), aryloxycarbonyl (aryloxycarbonyl having 7 to 12 carbon atoms, preferably aryloxycarbonyl having 7 to 9 carbon atoms; for example, phenoxycarbonyl-2-chlorophenoxycarbonyl, 3-nitrophenoxycarbonyl and 4-tert-butylphenoxycarbonyl), carbamoyl (carbamoyl having 1 to 10 carbon atoms) , preferably a carbamoyl group having 1 to 6 carbon atoms; for example, carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-(2-hydroxyethyl)carbamoyl and N-(methylsulfonyl)carbamoyl), an arylazo group (an arylazo group having 6 to 12 carbon atoms, preferably an arylazo group having 6 to 8 carbon atoms; for example, phenylazo and p-chlorophenylazo), a heterocyclic azo group (a heterocyclic azo group having 1 to 10 carbon atoms, preferably a heterocyclic azo group having 1 to 6 carbon atoms azo group; for example, a pyrazole-3-yl azo group, a thiazol-2-yl azo group, and a 5-methylthio-1,3,4-thiadiazol-2-yl azo group), an imide group (an imide group having 2 to 10 carbon atoms, preferably an imide group having 4 to 8 carbon atoms; for example, a succinimide group and a phthalimide group), a phosphine group (a phosphine group having 2 to 12 carbon atoms, preferably a phosphine group having 2 to 6 carbon atoms; for example, a dimethylphosphine group, a diphenylphosphine group, and a methylphenoxyphosphine group), an oxygen phosphine group (a phosphine group having 2 to 12 carbon atoms, preferably a phosphine group having 2 to 6 carbon atoms; for example, a dimethylphosphine group, a diphenylphosphine group, and a methylphenoxyphosphine group), a The invention also includes a phosphinyl group having 2 to 12 carbon atoms, preferably a phosphinyl group having 2 to 6 carbon atoms; for example, a phosphinyl group and a diethoxyphosphinyl group), a phosphinyloxy group (a phosphinyloxy group having 2 to 12 carbon atoms, preferably a phosphinyloxy group having 2 to 6 carbon atoms; for example, a diphenoxyphosphinyloxy group and a dibutoxyphosphinyloxy group), and a phosphinylamino group (a phosphinylamino group having 2 to 12 carbon atoms, preferably a phosphinylamino group having 2 to 6 carbon atoms; for example, a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group).

[0100] When these groups are further substituted, they may further contain a substituent. When these groups are substituted with two or more substituents, these substituents may be the same or different.

[0101] [Photosensitive composition]

[0102] The photosensitive composition of the present invention contains a color material precursor that develops black color upon stimulation.

[0103] In the present invention, “a color material precursor that develops black color upon stimulation” is also referred to as a “specific color material precursor.” Since the photosensitive composition of the present invention contains a specific color material precursor, a film having excellent light-shielding properties can be formed and has excellent patterning properties.

[0104] Carbon black is known as a colorant for forming a black matrix. However, when a composition containing carbon black as a colorant is used, for example, to form a black matrix of a negative pattern, since carbon black absorbs the light (for example, ultraviolet rays) to be exposed, the incident light gradually attenuates in the film thickness direction of the composition layer for forming the pattern, and due to insufficient polymerization curing, it is difficult to obtain a well-shaped pattern after development.

[0105] In contrast, since the photosensitive composition of the present invention contains a color material precursor that develops black upon stimulation, and the period of color development can be controlled according to the timing of stimulation, it is possible, for example, to perform pattern exposure before the color material precursor develops black, and to stimulate the color material precursor to develop black after the pattern exposure. According to the photosensitive composition of the present invention, by performing pattern exposure before the color material precursor develops black, the absorption of incident light can be suppressed and the incident light can be transmitted during pattern exposure, so a pattern with a good shape can be obtained after development. Furthermore, after the pattern exposure, the color material precursor develops black upon stimulation, thereby providing the pattern with excellent light-shielding properties.

[0106] <Specific color material precursor>

[0107] The photosensitive composition of the present invention contains a color material precursor (ie, a specific color material precursor) that develops black color when stimulated.

[0108] The “color material precursor that develops black color upon stimulation” in the present invention is preferably a compound that satisfies the following requirements A, B, and C.

[0109] (Requirement A)

[0110] For a solution obtained by dissolving 1.1 mg of the compound before color development in 50 mL of tetrahydrofuran (THF), the average value of the molar absorption coefficient (ε) at any continuous 100 nm in the wavelength range of 400 nm to 700 nm (the so-called average molar absorption coefficient) in the absorption spectrum measured using a spectrophotometer is 400 L / (mol·cm) or less.

[0111] The average molar absorption coefficient in requirement A is preferably 200 L / (mol·cm) or less, and more preferably 100 L / (mol·cm) or less.

[0112] The average value of the molar absorption coefficient (ε) at continuous 100 nm in the wavelength range of 400 nm to 700 nm can be obtained by calculating the molar absorption coefficient at each wavelength for every 1 nm and taking the arithmetic average of the molar absorption coefficients in the continuous 100 nm range (for example, 421 nm to 520 nm, 560 nm to 659 nm, etc.). The same applies to requirement C described later.

[0113] “The average value of the molar absorption coefficient (ε) at any continuous 100 nm in the wavelength range of 400 nm to 700 nm is 400 L / (mol·cm) or less” means that, within the wavelength range of 400 nm to 700 nm, even if any continuous 100 nm range is selected, the average molar absorption coefficient of the continuous 100 nm range is 400 L / (mol·cm) or less.

[0114] (Requirement B)

[0115] The maximum absorption wavelength of a solution obtained by dissolving 1.1 mg of the colored compound in 50 mL of tetrahydrofuran (THF) was measured using a spectrophotometer. The solution showed a wavelength of 400 nm to 700 nm.

[0116] The number of the maximum absorption wavelengths within the wavelength range of 400 nm to 700 nm is preferably 2 or more.

[0117] The upper limit of the number of the maximum absorption wavelengths in the wavelength range of 400 nm to 700 nm is not particularly limited, and examples thereof include 10 or less, 5 or less, and 3 or less.

[0118] When two or more maximum absorption wavelengths exist within the wavelength range of 400 nm to 700 nm, the maximum absorption wavelengths preferably exist at a distance of 100 nm or more, and more preferably exist at a distance of 200 nm or more.

[0119] In the above-mentioned maximum absorption wavelength within the wavelength range of 400 nm to 700 nm, the molar absorption coefficient (ε) at the wavelength with maximum absorption is preferably 3000 L / (mol·cm) or more, more preferably 4000 L / (mol·cm) or more, and further preferably 5000 L / (mol·cm) or more.

[0120] Furthermore, in the above-mentioned maximum absorption wavelength within the wavelength range of 400 nm to 700 nm, the molar absorption coefficient (ε) at the wavelength with maximum absorption is preferably 100,000 L / (mol·cm) or less, more preferably 40,000 L / (mol·cm) or less, and further preferably 20,000 L / (mol·cm) or less.

[0121] (Requirement C)

[0122] For a solution obtained by dissolving 1.1 mg of the colored compound in 50 mL of tetrahydrofuran (THF), the average value of the molar absorption coefficient (ε) at any continuous 100 nm in the wavelength range of 400 nm to 700 nm (i.e., the average molar absorption coefficient) in the absorption spectrum measured using a spectrophotometer is 2000 L / (mol·cm) or more.

[0123] The average molar absorption coefficient in requirement C is preferably 3000 L / (mol·cm) or more, and more preferably 4000 L / (mol·cm) or more.

[0124] “The average value of the molar absorption coefficient (ε) at any continuous 100 nm in the wavelength range of 400 nm to 700 nm is 2000 L / (mol·cm) or more” means that, within the wavelength range of 400 nm to 700 nm, even if any continuous 100 nm range is selected, the average molar absorption coefficient of the continuous 100 nm range is 2000 L / (mol·cm) or more.

[0125] The "stimulus" in the present invention includes both direct factors and indirect factors for causing the color material precursor to develop black. That is, the stimulus can directly act on the color material precursor and cause the color material precursor to develop black by changing the structure of the color material precursor, or it can act as a trigger for causing the structure of the color material precursor to change, and the stimulus itself does not directly act on the color material precursor to change the structure of the color material precursor.

[0126] The stimulus is not particularly limited as long as it can directly or indirectly cause the color material precursor to develop black color.

[0127] The stimulus is preferably at least one selected from the group consisting of heat, light, acid, alkali, and free radicals, more preferably heat or acid, and even more preferably heat.

[0128] The type of the specific color material precursor is not particularly limited.

[0129] The specific color material precursor is preferably a compound that develops black color by acid or heat, more preferably a compound that develops black color by heat, and still more preferably a compound that develops black color by thermal oxidation (so-called thermal oxidation).

[0130] When the formed film is applied to a device, a compound that develops black color by heat is more preferable than a compound that develops black color by acid because a problem due to acid is less likely to occur.

[0131] Examples of specific color material precursors include colorless coloring matter compounds (so-called leuco dyes). Leuco dyes are compounds that develop color when exposed to acid or the like, and specifically, a lactone ring in a molecule reacts with an acid to open a ring and develop color.

[0132] The above reaction in the leuco dye is a reversible reaction, and when a base comes into contact with the lactone ring in the ring-opened state, the ring is closed and decolorization occurs.

[0133] As the leuco dye, any known leuco dye can be used without particular limitation as long as it develops black color.

[0134] Examples of the colorless dye that develops a black color include 2'-anilino-6'-(dibutylamino)-3'-methylfluoran, 2'-anilino-3'-methyl-6'-(dipentylamino)spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one, 2'-anilino-6'-dibutylamino-3'-methylspiro[phthalide-3,9'-[9H]xanthen], 2'-anilino-6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalide-3,9'-[9H]xanthen], and 2-(anilino)-3-methyl-6-[ethyl(p-tolyl)amino]spiro[9H-xanthen-9,1'(3'H)-isobenzofuran]-3'-one.

[0135] Among these, as a leuco dye, 2'-anilino-3'-methyl-6'-(dipentylamino)spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one is preferred.

[0136] Examples of commercially available leuco dyes include BLACK 305 (CAS No. 129473-78-5), BLACK 400 (CAS No. 89331-94-2), S-205 (CAS No. 70516-41-5) and ETAC (CAS No. 59129-79-2) manufactured by Fukui Yamada Chemical Co., Ltd. and 2'-anilino-6'-(dibutylamino)-3'-methylfluoran manufactured by Tokyo Chemical Industry Co., Ltd.

[0137] When the photosensitive composition of the present invention contains a leuco dye as a specific color material precursor, it is preferred to contain a compound that absorbs red and / or green light from the viewpoint of forming a film with better light-shielding properties. As such compounds, compounds such as the EX COLOR series manufactured by NIPPON SHOKUBAI CO., LTD., and the FDG series and FDR series manufactured by Fukui Yamada Chemical Co., Ltd. can be cited.

[0138] When the photosensitive composition of the present invention contains the above-mentioned compound, the content of the above-mentioned compound in the photosensitive composition is not particularly limited and can be appropriately set according to the purpose. For example, it is preferably adjusted so that the average absorbance of the formed film at a wavelength of 400nm to 700nm is 2.0 or more.

[0139] Examples of the specific color material precursor include compounds represented by the following formula (1).

[0140] [Chemical formula 4]

[0141]

[0142] In formula (1), X 1 , X 2 , X 3 , X 4 , Y 1 and Y 2 Each independently represents an oxygen atom, a sulfur atom or NL 1 .L 1 represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group. 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom, -OL 2 、-OCO-L 3 , -SL 2 or-OSO-L 3 .L 2 represents a hydrogen atom or an alkyl group, L 3 represents an alkyl group or an amino group. 1 and R 2 At least one of represents a hydrogen atom, R 3 and R 4 At least one of represents a hydrogen atom. A, B and C each independently represent an aromatic ring.

[0143] The compound represented by formula (1) is a compound that develops black color by heat (specifically, thermal oxidation). The mechanism by which the compound represented by formula (1) develops black color is not clear, but the present inventors believe as follows.

[0144] It is believed that when the compound represented by formula (1) is heated, it reacts with oxygen in the air and changes its structure to an oxidized form, thereby developing a black color. That is, it is believed that the oxidized form is black. Specifically, for example, it is believed that the compound represented by formula (1) reacts with oxygen in the air, and R 1 , R 2 , R 3 and R4 Desorption (e.g. dehydration, dealcoholization, etc.), R 1 With R 2 Between 3 With R 4 The single bonds between them become double bonds, and the conjugation is extended, thereby changing to a structure that absorbs visible light and appears black.

[0145] The above reaction of the compound represented by formula (1) is irreversible, unlike leuco dyes, and thus is less likely to fade. Therefore, from the viewpoint of reducing the risk of fading of the pattern, the compound represented by formula (1) is more preferred as the specific color material precursor.

[0146] Hereinafter, the compound represented by formula (1) will be described in detail.

[0147] X 1 , X 2 , X 3 and X 4 Preferred is an oxygen atom.

[0148] In formula (1), the two Y 1 They may be the same or different, but are preferably the same.

[0149] Y 1 Preferred is an oxygen atom.

[0150] In formula (1), the two Y 2 They may be the same or different, but are preferably the same.

[0151] Y 2 Preferably NL 1 .

[0152] L is preferably a hydrogen atom, an alkyl group, an acyl group or an alkoxycarbonyl group, and more preferably an alkyl group, an acyl group or an alkoxycarbonyl group.

[0153] By L 1 The alkyl group represented by may or may not have a substituent. 1 The alkyl group represented by may be a linear alkyl group, may be a branched alkyl group, or may be an alkyl group having a cyclic structure.

[0154] By L 1 The alkyl group represented by is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

[0155] As L 1 The alkyl group represented by is, for example, preferably a sec-butyl group, an n-hexyl group, a 2-ethoxyethyl group, a methoxycarbonylmethyl group, an isopropyl group, an n-pentyl group or a 2-ethylhexyl group.

[0156] By L 1The acyl group represented is preferably an acyl group having 2 to 30 carbon atoms, and more preferably an acyl group having 2 to 15 carbon atoms.

[0157] As L 1 The acyl group represented by is, for example, preferably acetyl, 2-ethylhexanoyl, 3,3,5-trimethylhexanoyl, propionyl, butyryl, isobutyryl or pivaloyl.

[0158] By L 1 The alkoxycarbonyl group represented is preferably an alkoxycarbonyl group having 1 to 30 carbon atoms in the alkoxy moiety.

[0159] As L 1 The alkoxycarbonyl group represented by is preferably, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a 9-fluorenylmethoxycarbonyl group, a benzyloxycarbonyl group or a 2,2,2-trichloroethoxycarbonyl group.

[0160] When R 1 and R 2 When one of L is a hydrogen atom, the other is preferably a hydrogen atom or a hydroxyl group (ie, L 2 -OL is a hydrogen atom 2 ), more preferably a hydrogen atom.

[0161] When R 3 and R 4 When one of L is a hydrogen atom, the other is preferably a hydrogen atom or a hydroxyl group (ie, L 2 -OL is a hydrogen atom 2 ), more preferably a hydrogen atom.

[0162] L 2 Preferred is a hydrogen atom.

[0163] By L 2 The alkyl group represented by may or may not have a substituent. 2 The alkyl group represented by may be a linear alkyl group, may be a branched alkyl group, or may be an alkyl group having a cyclic structure.

[0164] By L 2 The alkyl group represented by is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

[0165] As L 2 The alkyl group represented by is, for example, preferably a methyl group, an ethyl group, a propyl group or a 2-ethylhexyl group.

[0166] By L 3 The alkyl group represented by may or may not have a substituent. 3The alkyl group represented by may be a linear alkyl group, may be a branched alkyl group, or may be an alkyl group having a cyclic structure.

[0167] By L 3 The alkyl group represented by is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

[0168] As L 3 The alkyl group represented by is, for example, preferably a methyl group, an ethyl group, a propyl group or a 2-ethylhexyl group.

[0169] The aromatic ring represented by A and the aromatic ring represented by B may be the same or different. The aromatic ring represented by A and B may or may not have a substituent. The aromatic ring represented by A and B may be, for example, an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring thereof.

[0170] When the aromatic ring represented by A and B is an aromatic hydrocarbon ring, the aromatic hydrocarbon ring represented by A and B is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.

[0171] When the aromatic ring represented by A and B is an aromatic hydrocarbon ring, the aromatic hydrocarbon ring represented by A and B is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, and further preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms.

[0172] When the aromatic ring represented by A and B is an aromatic hydrocarbon ring, the aromatic hydrocarbon ring represented by A is preferably, for example, a benzene ring, a naphthalene ring or an anthracene ring, and more preferably a benzene ring.

[0173] When the aromatic ring represented by A and B is an aromatic heterocyclic ring, the aromatic heterocyclic ring represented by A and B is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.

[0174] When the aromatic ring represented by A and B is an aromatic heterocycle, the aromatic heterocycle represented by A and B is preferably an aromatic heterocycle containing one or more heteroatoms selected from the group consisting of oxygen atoms, sulfur atoms and nitrogen atoms in the ring. The number of heteroatoms in the aromatic heterocycle is preferably 1 or 2, more preferably 1.

[0175] When the aromatic ring represented by A and B is an aromatic heterocyclic ring, the aromatic heterocyclic ring represented by A and B is preferably, for example, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring or a pyridine ring, and more preferably a thiophene ring.

[0176] The aromatic ring represented by C may or may not have a substituent.

[0177] Examples of the aromatic ring represented by C include a benzene ring and a heterocyclic ring.

[0178] Examples of the heterocyclic ring include a pyridine ring and a pyrazine ring.

[0179] As the aromatic ring represented by C, a benzene ring is preferred.

[0180] In formula (1), X 1 , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 and R 4 For example, the following aspect A is preferred, and aspect B is more preferred.

[0181] Method A: X 1 , X 2 , X 3 and X 4 is an oxygen atom, R 1 and R 2 One of them is a hydrogen atom and the other is a hydroxyl group. 3 and R 4 One of them is a hydrogen atom and the other is a hydroxyl group.

[0182] Method B: X 1 , X 2 , X 3 and X 4 is an oxygen atom, R 1 , R 2 , R 3 and R 4 For hydrogen atoms.

[0183] A preferred embodiment of the compound represented by formula (1) is as follows: X 1 , X 2 , X 3 and X 4 is an oxygen atom, Y 1 and Y 2 are independently an oxygen atom, a sulfur atom or NL 1 , L 1 is a hydrogen atom, an alkyl group, an acyl group or an alkoxycarbonyl group, R 1 or R 2 One of them is a hydrogen atom and the other is a hydroxyl group. 3 or R 4 One of them is a hydrogen atom, the other is a hydroxyl group, A and B are each independently a benzene ring or a thiophene ring, and C is a benzene ring.

[0184] A more preferred embodiment of the compound represented by formula (1) is as follows: X 1 , X 2 , X 3 and X 4is an oxygen atom, Y 1 is an oxygen atom, Y 2 For NL 1 , L 1 is an alkyl group, an acyl group or an alkoxycarbonyl group, R 1 , R 2 , R 3 and R 4 is a hydrogen atom, A and B are benzene rings, and C is a benzene ring.

[0185] Specific examples of the compound represented by formula (1) are described below. However, the compound represented by formula (1) is not limited to the following specific examples. In addition, "Me" represents a methyl group.

[0186] [Chemical formula 5]

[0187]

[0188] [Chemical formula 6]

[0189]

[0190] [Chemical formula 7]

[0191]

[0192] [Chemical formula 8]

[0193]

[0194] [Chemical formula 9]

[0195]

[0196] [Chemical formula 10]

[0197]

[0198] [Chemical formula 11]

[0199]

[0200] [Chemical formula 12]

[0201]

[0202] [Chemical formula 13]

[0203]

[0204] As the compound represented by formula (1), among the above specific examples, at least one selected from the group consisting of compounds (1) to (16), compounds (25) to (32) and compound (65) is also preferred, at least one selected from the group consisting of compounds (1) to (16) and compound (65) is more preferred, at least one selected from the group consisting of compounds (1) to (3), compound (5), compound (7) and compound (8) is further preferred, and at least one selected from the group consisting of compounds (1) to (3), compound (5), compound (7) and compound (8) is particularly preferred.

[0205] The heating temperature for coloring the compound represented by the formula (1) black is preferably, for example, 80° C. to 260° C.

[0206] The method for producing the compound represented by formula (1) is not particularly limited.

[0207] The compound represented by the formula (1) can be produced by referring to a known method.

[0208] The compound represented by formula (1) can be manufactured by, for example, referring to known literature, synthesizing an indigo derivative using indigo as a starting material, then reacting the synthesized indigo derivative with 3,7-dihydrobenzo[1,2-b:4,5-b′]difuran-2,6-dione in an organic solvent in the presence of an acid catalyst, and reducing the compound obtained by the reaction.

[0209] The synthesis method of isatin derivatives is described in, for example, J. Am. Chem. Soc. 2015, 137, 15947-15956, Journal of Medicinal Chemistry, 2008, 51, 4932-4947, Chemistry-A European Journal, 2021, 27, 4302-4306, Org. Lett., 2021, 23, 2273-2278, etc. The descriptions of these documents are incorporated into this specification by reference.

[0210] Examples of the organic solvent include ether-based organic solvents, preferably tetrahydrofuran (THF) and / or 1,4-dioxane, and more preferably tetrahydrofuran (THF).

[0211] As a reduction method of the compound obtained by the reaction, for example, a method using a reducing agent such as zinc powder, trifluoroacetic acid, acetic acid, hydrochloric acid, etc. can be cited. In addition, the reduction can be a contact reduction using a palladium catalyst. As a reduction method, preferably, a reduction using zinc powder (so-called zinc reduction) or a contact reduction using a palladium catalyst is used, and zinc reduction is more preferred.

[0212] The reaction temperature is not particularly limited, but is, for example, preferably 20°C to 40°C, more preferably 30°C to 40°C.

[0213] The reaction time is not particularly limited, but is, for example, preferably 1 to 6 hours, more preferably 1 to 2 hours.

[0214] The compound represented by formula (1) can be preferably produced by the method described in Examples below.

[0215] The photosensitive composition according to the present invention may contain only one specific color material precursor, or may contain two or more specific color material precursors.

[0216] The content of the specific color material precursor in the photosensitive composition involved in the present invention is not particularly limited, but for example, from the viewpoint of more excellent effects of the present invention, it is preferably 1 mass % to 20 mass %, more preferably 2 mass % to 15 mass %, and further preferably 3 mass % to 10 mass % relative to the total solid content of the photosensitive composition.

[0217] <Components other than specific color material precursors>

[0218] In addition to the specific color material precursor, the photosensitive composition of the present invention may also contain an alkali-soluble resin, a polymerizable monomer and a photopolymerization initiator. In addition, the photosensitive composition of the present invention may contain additives such as heterocyclic compounds, aliphatic thiol compounds, thermal crosslinking compounds, surfactants, polymerization inhibitors, hydrogen-donating compounds, solvents, etc.

[0219] Hereinafter, these components will be described in detail.

[0220] (Alkali soluble resin)

[0221] The photosensitive composition according to the present invention may contain an alkali-soluble resin.

[0222] Examples of the alkali-soluble resin include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, polyurethane resins, epoxy acrylate resins obtained by reaction of epoxy resins with (meth)acrylic acid, and acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins with acid anhydrides.

[0223] As a preferable aspect of the alkali-soluble resin, a (meth)acrylic resin is mentioned from the viewpoint of being excellent in alkali developability and film-forming property.

[0224] In the present invention, the (meth)acrylic resin refers to a resin containing a structural unit derived from a (meth)acrylic compound.

[0225] The content of the structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on all the structural units of the (meth)acrylic resin.

[0226] The (meth)acrylic resin may be composed only of constituent units derived from a (meth)acrylic compound, or may contain constituent units derived from a polymerizable monomer other than a (meth)acrylic compound. That is, the upper limit of the content of constituent units derived from a (meth)acrylic oxide compound relative to all constituent units of the (meth)acrylic resin is 100% by mass or less.

[0227] As a (meth)acrylic acid compound, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile are mentioned, for example.

[0228] Examples of the (meth)acrylate include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, and alkyl (meth)acrylates are preferred.

[0229] Examples of (meth)acrylamide include acrylamides such as diacetone acrylamide.

[0230] The alkyl group of the (meth)acrylic acid alkyl ester may be linear or branched.

[0231] Specific examples of the alkyl (meth)acrylate include alkyl (meth)acrylates having an alkyl group having 1 to 12 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

[0232] As the alkyl (meth)acrylate, an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

[0233] The (meth)acrylic resin may contain a structural unit other than the structural unit derived from the (meth)acrylic compound.

[0234] The polymerizable monomer for forming a structural unit other than a structural unit derived from a (meth)acrylic compound is not particularly limited as long as it is a compound other than a (meth)acrylic compound copolymerizable with a (meth)acrylic compound.

[0235] Examples of the compound other than the (meth)acrylic acid compound copolymerizable with the (meth)acrylic acid compound include styrene compounds which may have a substituent at the α position or on the aromatic ring, such as styrene, vinyl toluene, and α-methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester and the like, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and the like.

[0236] The (meth)acrylic resin may contain only one type of structural unit derived from these polymerizable monomers, or may contain two or more types of structural units derived from these polymerizable monomers.

[0237] Furthermore, from the viewpoint of making the alkali developability better, the (meth)acrylic resin preferably contains a structural unit having an acid group. Examples of the acid group include a carboxyl group, a sulfone group, a phosphoric acid group, and a phosphonic acid group.

[0238] The (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably contains a structural unit derived from the above-mentioned (meth)acrylic acid.

[0239] When the (meth)acrylic resin contains a constituent unit having an acid group in a (meth)acrylic resin (preferably a constituent unit derived from (meth)acrylic acid; the same applies hereinafter), the content of the constituent unit having an acid group in the (meth)acrylic resin is preferably 10% by mass or more relative to all the constituent units in the (meth)acrylic resin from the viewpoint of excellent developability. From the viewpoint of excellent alkali resistance, the upper limit of the content of the constituent unit having an acid group in the (meth)acrylic resin relative to all the constituent units in the (meth)acrylic resin is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0240] It is more preferable that the (meth)acrylic resin contains a structural unit derived from the above-mentioned alkyl (meth)acrylate.

[0241] When the (meth)acrylic resin contains a structural unit derived from an alkyl (meth)acrylate, the content of the structural unit derived from an alkyl (meth)acrylate in the (meth)acrylic resin is preferably 1% by mass to 90% by mass, more preferably 1% by mass to 50% by mass, and even more preferably 1% by mass to 30% by mass, relative to all the structural units in the (meth)acrylic resin.

[0242] The (meth)acrylic resin is preferably a resin containing both a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate, and more preferably a resin consisting only of a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate.

[0243] Furthermore, the (meth)acrylic resin may be an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate.

[0244] From the viewpoint of achieving more excellent effects of the present invention, the (meth)acrylic resin preferably contains at least one selected from the group consisting of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylates, and preferably contains both constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylates.

[0245] From the viewpoint of achieving a more excellent effect of the present invention, the total content of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate in the (meth)acrylic resin is preferably 40% by mass or more, and more preferably 60% by mass or more, relative to all constituent units of the (meth)acrylic resin. For example, the upper limit of the total content of constituent units derived from methacrylic acid and constituent units derived from alkyl methacrylate in the (meth)acrylic resin relative to all constituent units of the (meth)acrylic resin may be 100% by mass or less, and preferably 80% by mass or less.

[0246] From the viewpoint of achieving more excellent effects of the present invention, the (meth)acrylic resin may contain at least one constituent unit selected from the group consisting of constituent units derived from methacrylic acid and constituent units derived from methacrylic acid alkyl esters, and at least one constituent unit selected from the group consisting of constituent units derived from acrylic acid and constituent units derived from acrylate alkyl esters.

[0247] The (meth)acrylic resin preferably has an ester group at the terminal, from the viewpoint of excellent developability of a photosensitive composition layer formed using the photosensitive composition.

[0248] The terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. The (meth)acrylic resin having an ester group at the terminal can be synthesized by using a radical polymerization initiator having an ester group.

[0249] For example, from the viewpoint of developability, the alkali-soluble resin is preferably a resin having an acid value of 60 mgKOH / g or more.

[0250] Furthermore, from the viewpoint of easily forming a strong film by thermal cross-linking with a cross-linking component by heating, for example, the alkali-soluble resin is more preferably a resin having a carboxyl group having an acid value of 60 mgKOH / g or more (so-called carboxyl-containing resin), and particularly preferably a (meth) acrylic resin having a carboxyl group having an acid value of 60 mgKOH / g or more (so-called carboxyl-containing (meth) acrylic resin).

[0251] When the alkali-soluble resin is a resin having a carboxyl group, for example, a heat-crosslinkable compound such as a blocked isocyanate compound is added to perform heat crosslinking, thereby increasing the three-dimensional crosslinking density. In addition, if the carboxyl group of the resin having a carboxyl group is anhydrided and hydrophobized, the wet heat resistance can be improved.

[0252] As the (meth) acrylic resin containing a carboxyl group having an acid value of 60 mgKOH / g or more, there is no particular limitation as long as the above-mentioned acid value condition is satisfied, and it can be appropriately selected from known (meth) acrylic resins. As the (meth) acrylic resin containing a carboxyl group having an acid value of 60 mgKOH / g or more, for example, the (meth) acrylic resin containing a carboxyl group having an acid value of 60 mgKOH / g or more in the polymer described in paragraph

[0025] of Japanese Patent Publication No. 2011-95716 and the (meth) acrylic resin containing a carboxyl group having an acid value of 60 mgKOH / g or more in the polymer described in paragraphs

[0033] to

[0052] of Japanese Patent Publication No. 2010-237589 can be preferably used.

[0253] Another preferred embodiment of the alkali-soluble resin is a styrene-acrylic acid copolymer.

[0254] In the present invention, the styrene-acrylic acid copolymer refers to a resin containing a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic acid compound.

[0255] For example, the total content of the constituent units derived from the styrene compound and the constituent units derived from the (meth)acrylic acid compound in the styrene-acrylic acid copolymer is preferably 30% by mass or more, more preferably 50% by mass or more, based on all constituent units of the styrene-acrylic acid copolymer.

[0256] For example, the content of the structural units derived from the styrene compound in the styrene-acrylic acid copolymer is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 5% to 80% by mass, based on all the structural units of the styrene-acrylic acid copolymer.

[0257] For example, the content of the structural units derived from the (meth)acrylic acid compound in the styrene-acrylic acid copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% to 95% by mass, based on all structural units of the styrene-acrylic acid copolymer.

[0258] From the viewpoint of achieving more excellent effects of the present invention, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably contains a structural unit having an aromatic ring structure.

[0259] Examples of the monomer forming the structural unit having an aromatic ring structure include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer).

[0260] As the monomer forming the structural unit having an aromatic ring structure, a monomer having an aralkyl group or styrene is preferred.

[0261] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl and substituted or unsubstituted benzyl groups, and a substituted or unsubstituted benzyl group is preferred.

[0262] As a monomer which has a phenylalkyl group, phenethyl (meth)acrylate is mentioned, for example.

[0263] Examples of the monomer having a benzyl group include (meth)acrylates having a benzyl group [e.g., benzyl (meth)acrylate and benzyl (meth)acrylate chloride] and vinyl monomers having a benzyl group [e.g., vinylbenzyl chloride and vinylbenzyl alcohol], and benzyl (meth)acrylate is preferred.

[0264] From the viewpoint of achieving more excellent effects of the present invention, the alkali-soluble resin more preferably contains a structural unit represented by the following formula (S) (ie, a structural unit derived from styrene).

[0265] [Chemical formula 14]

[0266]

[0267] When the alkali-soluble resin contains a constituent unit having an aromatic ring structure, from the viewpoint of achieving a more excellent effect of the present invention, the content of the constituent unit having an aromatic ring structure in the alkali-soluble resin is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, and further preferably 20% by mass to 60% by mass relative to all the constituent units of the alkali-soluble resin.

[0268] From the viewpoint of achieving more excellent effects of the present invention, the content of the constituent units having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and further preferably 20 mol% to 60 mol%, relative to all constituent units of the alkali-soluble resin.

[0269] From the viewpoint of achieving a more excellent effect of the present invention, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, further preferably 20 mol% to 60 mol%, and particularly preferably 20 mol% to 50 mol%, relative to all the structural units of the alkali-soluble resin.

[0270] In the present invention, when the content of a "constituent unit" is specified by a molar ratio, the "constituent unit" has the same meaning as a "monomer unit". In addition, in the present invention, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

[0271] From the viewpoint of achieving a more excellent effect of the present invention, the alkali-soluble resin preferably contains a constituent unit having an aliphatic hydrocarbon ring structure. The aliphatic hydrocarbon ring structure may be a monocyclic ring or a polycyclic ring. The alkali-soluble resin may contain a constituent unit having a ring structure formed by condensing two or more aliphatic hydrocarbon rings.

[0272] Examples of the aliphatic hydrocarbon ring include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isophorone ring.

[0273] Examples of the monomer that forms the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.

[0274] Furthermore, from the viewpoint of achieving more excellent effects of the present invention, the alkali-soluble resin more preferably contains a structural unit represented by the following formula (Cy), and further preferably contains a structural unit represented by the above formula (S) and a structural unit represented by the following formula (Cy).

[0275] [Chemical formula 15]

[0276]

[0277] In the formula (Cy), R M represents a hydrogen atom or a methyl group, R Cy It represents a monovalent group having an aliphatic hydrocarbon ring structure.

[0278] R in formula (Cy) M Preferred is methyl.

[0279] From the viewpoint of further improving the effect of the present invention, R in the formula (Cy) Cy It is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, and still more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

[0280] From the viewpoint of further improving the effect of the present invention, R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a cyclopentane ring structure, a cyclohexane ring structure, a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure or an isophorone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, further preferably a tetrahydrodicyclopentadiene ring structure.

[0281] Furthermore, from the viewpoint of further improving the effect of the present invention, R in formula (Cy) Cy The aliphatic hydrocarbon ring structure in is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and more preferably a ring structure in which 2 to 4 aliphatic hydrocarbon rings are condensed.

[0282] Furthermore, from the viewpoint of further improving the effect of the present invention, R in formula (Cy) Cy It is preferably a group in which the oxygen atom of -C(=O)O- in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure, that is, an aliphatic hydrocarbon ring group, more preferably a cyclohexyl group or a dicyclopentyl group, and still more preferably a dicyclopentyl group.

[0283] The alkali-soluble resin may contain only one type of constituent unit having an aliphatic hydrocarbon ring structure, or may contain two or more types of constituent units having an aliphatic hydrocarbon ring structure.

[0284] When the alkali-soluble resin contains a constituent unit having an aliphatic hydrocarbon ring structure, from the viewpoint of achieving a more excellent effect of the present invention, the content of the constituent unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and further preferably 20% by mass to 70% by mass relative to all the constituent units of the alkali-soluble resin.

[0285] Furthermore, from the viewpoint of achieving more excellent effects of the present invention, the content of the constituent units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 60 mol %, and further preferably 20 mol % to 50 mol %, relative to all constituent units of the alkali-soluble resin.

[0286] From the viewpoint of achieving more excellent effects of the present invention, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, and further preferably 20 mol% to 50 mol%, relative to all the structural units of the alkali-soluble resin.

[0287] When the alkali-soluble resin contains constituent units having an aromatic ring structure and constituent units having an aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, the total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further preferably 40% by mass to 75% by mass, relative to all the constituent units of the alkali-soluble resin.

[0288] From the viewpoint of achieving a more excellent effect of the present invention, the total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and even more preferably 40 mol% to 60 mol%, relative to all the constituent units of the alkali-soluble resin.

[0289] From the viewpoint of achieving a more excellent effect of the present invention, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and further preferably 40 mol% to 60 mol%, relative to all the structural units of the alkali-soluble resin.

[0290] From the viewpoint of achieving better effects of the present invention, the molar amount nS of the constituent unit represented by the above formula (S) in the alkali-soluble resin and the molar amount nCy of the constituent unit represented by the above formula (Cy) preferably satisfy the relationship shown by the following formula (SCy), more preferably satisfy the relationship shown by the following formula (SCy-1), and further preferably satisfy the relationship shown by the following formula (SCy-2).

[0291] 0.20≤nS / (nS+nCy)≤0.80...Formula (SCy)

[0292] 0.30≤nS / (nS+nCy)≤0.75...Formula (SCy-1)

[0293] 0.40≤nS / (nS+nCy)≤0.70...Formula (SCy-2)

[0294] From the viewpoint of achieving a more excellent effect of the present invention, the alkali-soluble resin preferably contains a constituent unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonic group, a phosphonic acid group, and a phosphoric acid group, and a carboxyl group is preferred. As the constituent unit having an acid group, a constituent unit derived from (meth) acrylic acid shown below is preferred, and a constituent unit derived from methacrylic acid is more preferred.

[0295] [Chemical formula 16]

[0296]

[0297] When the alkali-soluble resin contains a structural unit having an acid group, it may contain only one kind of structural unit having an acid group, or may contain two or more kinds of structural units having an acid group.

[0298] When the alkali-soluble resin contains a structural unit having an acid group, from the viewpoint of more excellent effects of the present invention, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and further preferably 10% by mass to 30% by mass relative to all the structural units of the alkali-soluble resin.

[0299] From the viewpoint of achieving more excellent effects of the present invention, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 to 70 mol %, more preferably 10 to 50 mol %, and further preferably 20 to 40 mol % relative to all structural units of the alkali-soluble resin.

[0300] From the viewpoint of achieving more excellent effects of the present invention, the content of the structural units derived from (meth)acrylic acid in the alkali-soluble resin is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%, based on all the structural units of the alkali-soluble resin.

[0301] From the viewpoint of achieving more excellent effects of the present invention, the alkali-soluble resin preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

[0302] As the reactive group, a radical polymerizable group is preferred, and an ethylenically unsaturated group is more preferred. Furthermore, when the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably contains a structural unit having an ethylenically unsaturated group in a side chain.

[0303] In the present invention, the "main chain" means the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and the "side chain" means an atomic group branched from the main chain.

[0304] As the ethylenically unsaturated group, an allyl group or a (meth)acryloyloxy group is more preferred.

[0305] Examples of the structural unit having a reactive group include the following, but are not limited thereto.

[0306] [Chemical formula 17]

[0307]

[0308] The alkali-soluble resin may contain only one type of constituent unit having a reactive group, or may contain two or more types of constituent units having a reactive group.

[0309] When the alkali-soluble resin contains a constituent unit having a reactive group, from the viewpoint of achieving a more excellent effect of the present invention, the content of the constituent unit having a reactive group in the alkali-soluble resin is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass relative to all the constituent units of the alkali-soluble resin.

[0310] From the viewpoint of achieving more excellent effects of the present invention, the content of the constituent units having reactive groups in the alkali-soluble resin is preferably 5 to 70 mol %, more preferably 10 to 60 mol %, and further preferably 20 to 50 mol %, relative to all constituent units of the alkali-soluble resin.

[0311] Examples of methods for introducing reactive groups into alkali-soluble resins include methods of reacting compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic anhydride with functional groups such as hydroxyl groups, carboxyl groups, primary amino groups, secondary amino groups, acetoacetyl groups, and sulfonic groups.

[0312] As a preferred example of a method for introducing a reactive group into an alkali-soluble resin, there can be mentioned a method in which a polymer having a carboxyl group is synthesized by a polymerization reaction, and then glycidyl (meth)acrylate is reacted with a part of the carboxyl groups of the obtained polymer by a polymer reaction to introduce a (meth)acryloyloxy group into the polymer. By this method, an alkali-soluble resin having a (meth)acryloyloxy group in a side chain can be obtained.

[0313] The polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably 80°C to 90°C.

[0314] As the polymerization initiator used in the polymerization reaction, an azo-based initiator is preferred, and for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferred.

[0315] The polymer reaction is preferably performed at a temperature of 80°C to 110°C.

[0316] In the polymer reaction, a catalyst such as an ammonium salt is preferably used.

[0317] As the alkali-soluble resin, the polymers shown below are preferred from the viewpoint of achieving more excellent effects of the present invention. The content ratio (a to d) and weight average molecular weight Mw of each structural unit shown below can be appropriately changed depending on the purpose.

[0318] [Chemical formula 18]

[0319]

[0320] Preferred values ​​of the content ratio of the above-mentioned structural units are shown below.

[0321] a: 20% to 60% by mass

[0322] b: 10% to 50% by mass

[0323] c: 5% to 25% by mass

[0324] d: 10% to 50% by mass

[0325] [Chemical formula 19]

[0326]

[0327] Preferred values ​​of the content ratio of the above-mentioned structural units are shown below.

[0328] a: 20% to 60% by mass

[0329] b: 10% to 50% by mass

[0330] c: 5% to 25% by mass

[0331] d: 10% to 50% by mass

[0332] [Chemical formula 20]

[0333]

[0334] Preferred values ​​of the content ratio of the above-mentioned structural units are shown below.

[0335] a: 30% to 65% by mass

[0336] b: 1% to 20% by mass

[0337] c: 5% to 25% by mass

[0338] d: 10% to 50% by mass

[0339] [Chemical formula 21]

[0340]

[0341] Preferred values ​​of the content ratio of the above-mentioned structural units are shown below.

[0342] a: 1% to 20% by mass

[0343] b: 20% to 60% by mass

[0344] c: 5% to 25% by mass

[0345] d: 10% to 50% by mass

[0346] The alkali-soluble resin may include a polymer (hereinafter also referred to as “polymer X”) containing a structural unit having a carboxylic acid anhydride structure.

[0347] The carboxylic acid anhydride structure may be any of a chain carboxylic acid anhydride structure and a cyclic carboxylic acid anhydride structure, but is preferably a cyclic carboxylic acid anhydride structure.

[0348] The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and still more preferably a 5-membered ring.

[0349] The structural unit having a carboxylic acid anhydride structure is preferably a structural unit containing a divalent group formed by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit in which a monovalent group formed by removing one hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a divalent linking group.

[0350] [Chemical formula 22]

[0351]

[0352] In formula P-1, R A1a represents a substituent, n 1a R A1a Can be the same or different, Z 1a represents a divalent group forming a ring containing -C(=O)-OC(=O)-, n 1a Indicates an integer greater than 0.

[0353] As R Ala The substituent represented by is, for example, an alkyl group.

[0354] As Z 1a , preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and further preferably an alkylene group having 2 carbon atoms.

[0355] n 1a represents an integer greater than 0. 1a When it represents an alkylene group having 2 to 4 carbon atoms, n 1a It is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

[0356] When n 1a When it represents an integer greater than 2, there are multiple R Ala can be the same or different. Also, there are multiple R A1a They may be bonded to each other to form a ring, but preferably are not bonded to each other to form a ring.

[0357] As the structural unit having a carboxylic acid anhydride structure, a structural unit derived from an unsaturated carboxylic acid anhydride is preferred, a structural unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferred, a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is further preferred, a structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and a structural unit derived from maleic anhydride is most preferred.

[0358] Specific examples of the structural unit having a carboxylic acid anhydride structure are given below, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples.

[0359] In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH2OH group or a CF3 group, and Me represents a methyl group.

[0360] [Chemical formula 23]

[0361]

[0362] [Chemical formula 24]

[0363]

[0364] The polymer X may contain only one type of structural unit having a carboxylic acid anhydride structure, or may contain two or more types of structural units having a carboxylic acid anhydride structure.

[0365] The total content of the structural units having a carboxylic anhydride structure in the polymer X is preferably 0 to 60 mol %, more preferably 5 to 40 mol %, and further preferably 10 to 35 mol % relative to all structural units of the polymer X.

[0366] When the photosensitive composition contains a polymer X, the composition may contain only one type of polymer X, or may contain two or more types of polymer X.

[0367] When the photosensitive composition contains a polymer X, from the viewpoint of more excellent effects of the present invention, the content of the polymer X in the photosensitive composition is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, further preferably 0.5% by mass to 20% by mass, and further preferably 1% by mass to 20% by mass, relative to the total solid content of the photosensitive composition.

[0368] From the viewpoint of more excellent effects of the present invention, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, further preferably 10,000 to 50,000, particularly preferably 15,000 to 30,000.

[0369] The acid value of the alkali-soluble resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 200 mgKOH / g, further preferably 60 mgKOH / g to 150 mgKOH / g, particularly preferably 70 mgKOH / g to 130 mgKOH / g.

[0370] The acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070:1992.

[0371] From the viewpoint of developability, the dispersion degree of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0372] When the photosensitive composition according to the present invention contains an alkali-soluble resin, the composition may contain only one kind of alkali-soluble resin or two or more kinds of alkali-soluble resins.

[0373] When the photosensitive composition involved in the present invention contains an alkali-soluble resin, from the viewpoint of more excellent effects of the present invention, the content of the alkali-soluble resin in the photosensitive composition is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further preferably 30% by mass to 70% by mass relative to the total solid content of the photosensitive composition.

[0374] (Polymerizable Monomer)

[0375] The photosensitive composition according to the present invention may contain a polymerizable monomer.

[0376] The polymerizable monomer is a monomer having a polymerizable group.

[0377] Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group, and a radical polymerizable group is preferred.

[0378] The polymerizable monomer preferably contains a radical polymerizable monomer having an ethylenically unsaturated group.

[0379] As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferred.

[0380] One preferred embodiment of the polymerizable monomer includes a compound represented by the following formula (M) (also simply referred to as "compound M").

[0381] Q 2 -R 1 -Q 1 ......Formula (M)

[0382] In formula (M), Q 1 and Q 2 Each independently represents a (meth)acryloyloxy group, R 1 It represents a divalent linking group having a chain structure.

[0383] From the viewpoint of ease of synthesis, Q in formula (M) 1 and Q 2 The same groups are preferred.

[0384] Furthermore, from the viewpoint of reactivity, Q in formula (M) 1 and Q 2 An acryloyloxy group is preferred.

[0385] As R in formula (M) 1 From the viewpoint of more excellent effects of the present invention, alkylene, alkyleneoxyalkylene (-L 1 -OL 1 -) or polyalkyleneoxyalkylene (-(L 1 -O) p -L 1 -), more preferably a hydrocarbon group or a polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, further preferably an alkylene group having 4 to 20 carbon atoms, and particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

[0386] The hydrocarbon group only needs to have a chain structure in at least a part. There is no particular limitation on the part other than the chain structure. For example, it can be any one of a branched, cyclic or straight-chain alkylene group having 1 to 5 carbon atoms, an arylene group, an ether bond and a combination thereof. An alkylene group or a group composed of two or more alkylene groups and one or more arylene groups is preferred. An alkylene group is more preferred, and a straight-chain alkylene group is further preferred.

[0387] L 1 Each independently represents an alkylene group, preferably an ethylene group, a propylene group or a butylene group, and more preferably an ethylene group or a 1,2-propylene group.

[0388] p represents an integer of 2 or more, and is preferably an integer of 2-10.

[0389] From the viewpoint of further improving the effect of the present invention, the connection Q in formula (M) 1 With Q 2 The number of atoms in the shortest connecting chain between them is preferably 3 to 50, more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.

[0390] In the present invention, "connect Q 1 With Q 2 The number of atoms in the shortest chain between 1 R 1 Atoms in Q 2 R 1 The shortest number of atoms connected to the atoms in the string.

[0391] Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol / propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers may also be used as a mixture.

[0392] From the viewpoint of more excellent effects of the present invention, the compound M is preferably at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate, more preferably at least one compound selected from the group consisting of 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate, and still more preferably at least one compound selected from the group consisting of 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

[0393] One preferred embodiment of the polymerizable monomer is a bifunctional or higher-functional ethylenically unsaturated compound.

[0394] In the present invention, the "bifunctional or higher-functional ethylenically unsaturated compound" refers to a compound having two or more ethylenically unsaturated groups in one molecule.

[0395] As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferred.

[0396] As the ethylenically unsaturated compound, a (meth)acrylate compound is preferred.

[0397] The bifunctional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

[0398] Examples of the bifunctional ethylenically unsaturated compound other than the compound M include tricyclodecane dimethanol di(meth)acrylate, dioxanediol di(meth)acrylate, and 1,4-cyclohexanediol di(meth)acrylate.

[0399] Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), tricyclodecane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), and dioxaneethanol diacrylate (trade name: KAYARAD (registered trademark) R-604, manufactured by Nippon Kayaku Co., Ltd.).

[0400] The trifunctional or higher-functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.

[0401] Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri / tetra / penta / hexa) (meth)acrylate, pentaerythritol (tri / tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerol tri(meth)acrylate skeleton.

[0402] In the present invention, “(tri / tetra / penta / hexa) (meth)acrylate” is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate, and “(tri / tetra) (meth)acrylate” is a concept including tri(meth)acrylate and tetra(meth)acrylate.

[0403] Examples of the polymerizable monomer include caprolactone-modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.], alkylene oxide-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., etc.) and ethoxylated glyceryl triacrylate (NK Ester A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., etc.).

[0404] As the polymerizable monomer, a urethane (meth)acrylate compound can also be mentioned.

[0405] Examples of the urethane (meth)acrylate include urethane di(meth)acrylates. Examples of the urethane di(meth)acrylate include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates.

[0406] Furthermore, as the urethane (meth) acrylate, trifunctional or higher urethane (meth) acrylates can also be mentioned. As the lower limit of the number of functional groups, hexafunctional or higher is more preferred, and octafunctional or higher is further preferred. As the upper limit of the number of functional groups, 20 functional groups or lower is preferred.

[0407] Examples of trifunctional or higher-functional urethane (meth)acrylates include 8UX-015A (trade name) manufactured by Taisei Fine Chemical Co., Ltd., UA-32P (trade name), U-15HA (trade name), and UA-1100H (trade name) manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., AH-600 (trade name) manufactured by KYOEISHA CHEMICAL CO., LTD., and UA-306H (trade name), UA-306T (trade name), UA-306I (trade name), UA-510H (trade name), and UX-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0408] One preferred embodiment of the polymerizable monomer is an ethylenically unsaturated compound having an acid group.

[0409] Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group.

[0410] The acid group is preferably a carboxyl group.

[0411] Examples of the ethylenically unsaturated compound having an acid group include tri- to tetra-functional ethylenically unsaturated compounds having an acid group [compounds obtained by introducing a carboxyl group into a pentaerythritol tri- and tetra-acrylate (PETA) skeleton (acid value: 80 mgKOH / g to 120 mgKOH / g)], and penta- to hexa-functional ethylenically unsaturated compounds having an acid group (compounds obtained by introducing a carboxyl group into a dipentaerythritol penta- and hexa-acrylate (DPHA) skeleton [acid value: 25 mgKOH / g to 70 mgKOH / g)].

[0412] The trifunctional or higher-functional ethylenically unsaturated compound having an acid group may be used together with a bifunctional ethylenically unsaturated compound having an acid group, as required.

[0413] As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic acid anhydrides thereof is preferred.

[0414] When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or higher-functional ethylenically unsaturated compounds having a carboxyl group and carboxylic anhydrides thereof, developability and film strength are further improved.

[0415] The bifunctional or higher-functional ethylenically unsaturated compound containing a carboxyl group is not particularly limited and can be appropriately selected from known compounds.

[0416] Examples of the bifunctional or higher-functional ethylenically unsaturated compound having a carboxyl group include ARONIX (registered trademark) TO-2349 [manufactured by TOAGOSEI CO., LTD.], ARONIX (registered trademark) M-520 [manufactured by TOAGOSEI CO., LTD.], and ARONIX (registered trademark) M-510 [manufactured by TOAGOSEI CO., LTD.].

[0417] As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs

[0025] to

[0030] of JP-A-2004-239942 is preferred, and the contents described in the publication are incorporated into the present specification.

[0418] Examples of the polymerizable monomer include compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound, carbamate monomers such as (meth)acrylate compounds having a carbamate bond, phthalic acid compounds such as γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, and alkyl (meth)acrylates.

[0419] These can be used alone or in combination of two or more.

[0420] Examples of the compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol include bisphenol A (meth)acrylate compounds such as 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane; polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups; polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups; and polyethylene polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups. diol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane diethoxy tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethylolpropane tetraethoxy tri(meth)acrylate, trimethylolpropane pentaethoxy tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0421] The compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol is preferably an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure, and more preferably tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate.

[0422] Examples of the polymerizable monomer include caprolactone-modified compounds of ethylenically unsaturated compounds [e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. and A-9300-1CL manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.], alkylene oxide-modified compounds of ethylenically unsaturated compounds [e.g., KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., and EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD.] and ethoxylated glyceryl triacrylate [e.g., A-GLY-9E manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.].

[0423] As the polymerizable monomer (particularly, an ethylenically unsaturated compound), a polymerizable monomer having an ester bond is also preferred from the viewpoint of excellent developability of a photosensitive composition layer formed using the photosensitive composition.

[0424] The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoint of excellent effects of the present invention, an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure is preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate is more preferred.

[0425] From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and an ethylenically unsaturated compound having a tetramethylolmethane structure or a trimethylolpropane structure.

[0426] Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate.

[0427] One preferred embodiment of the polymerizable monomer is a polymerizable compound having an aliphatic hydrocarbon ring structure (preferably a bifunctional ethylenically unsaturated compound).

[0428] As the polymerizable monomer, a polymerizable compound having a ring structure formed by condensing two or more aliphatic hydrocarbon rings (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure) is preferred, a bifunctional ethylenically unsaturated compound having a ring structure formed by condensing two or more aliphatic hydrocarbon rings is more preferred, and tricyclodecane dimethanol di(meth)acrylate is further preferred.

[0429] As the aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects of the present invention, a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an isophorone structure is preferred.

[0430] The molecular weight of the polymerizable monomer is not particularly limited, but is, for example, preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0431] Among the polymerizable monomers contained in the photosensitive composition, the proportion of the polymerizable monomer having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less relative to the content of all the polymerizable monomers contained in the photosensitive composition.

[0432] As one preferred embodiment of the photosensitive composition, the photosensitive composition preferably contains a difunctional or higher ethylenically unsaturated compound as a polymerizable monomer, more preferably contains a trifunctional or higher ethylenically unsaturated compound, and further preferably contains a trifunctional or tetrafunctional ethylenically unsaturated compound.

[0433] Furthermore, as one of the preferred aspects of the photosensitive composition, the photosensitive composition preferably contains the following bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure as a polymerizable monomer and the following resin having a structural unit containing an aliphatic hydrocarbon ring as an alkali-soluble resin.

[0434] Furthermore, as one of the preferred aspects of the photosensitive composition, the photosensitive composition preferably contains compound M and an ethylenically unsaturated compound having an acid group as polymerizable monomers, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a multifunctional ethylenically unsaturated compound having a carboxylic acid group as polymerizable monomers, and further preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a succinic acid-modified product of dipentaerythritol pentaacrylate as a polymerizable monomer.

[0435] Furthermore, as one of the preferred aspects of the photosensitive composition, the photosensitive composition preferably contains compound M and an ethylenically unsaturated compound having an acid group as polymerizable monomers, and a thermally crosslinkable compound described later, and more preferably contains compound M and an ethylenically unsaturated compound having an acid group as polymerizable monomers, and a blocked isocyanate compound described later.

[0436] Furthermore, as one of the preferred aspects of the photosensitive composition, from the viewpoint of development residue inhibition and rust prevention, the photosensitive composition preferably contains a difunctional ethylenically unsaturated compound [preferably a difunctional (meth)acrylate compound] and a trifunctional or higher ethylenically unsaturated compound [preferably a trifunctional or higher (meth)acrylate compound].

[0437] The mass ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the trifunctional or higher-functional ethylenically unsaturated compound is preferably 10:90 to 90:10, and more preferably 30:70 to 70:30.

[0438] The ratio of the content of the bifunctional ethylenically unsaturated compound to the total content of all ethylenically unsaturated compounds is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass.

[0439] The content of the bifunctional ethylenically unsaturated compound in the photosensitive composition is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 40% by mass, relative to the total solid content of the photosensitive composition.

[0440] Furthermore, as one of the preferred embodiments of the photosensitive composition, the photosensitive composition preferably contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention.

[0441] Furthermore, as one of the preferred embodiments of the photosensitive composition, from the viewpoints of substrate adhesion, development residue inhibition and rust resistance, the photosensitive composition preferably contains compound M and an ethylenically unsaturated compound having an acid group, more preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an ethylenically unsaturated compound having an acid group, further preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound and an ethylenically unsaturated compound having an acid group, and particularly preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, a trifunctional or higher ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group and a carbamate (meth) acrylate compound.

[0442] Furthermore, as one of the preferred aspects of the photosensitive composition, from the viewpoints of substrate adhesion, development residue suppression and rust resistance, the photosensitive composition preferably contains 1,9-nonanediol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, more preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group, further preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate and an ethylenically unsaturated compound having a carboxylic acid group, and particularly preferably contains 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group and a urethane acrylate compound.

[0443] The photosensitive composition may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

[0444] The content of the difunctional or higher-functional ethylenically unsaturated compounds in the ethylenically unsaturated compounds is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass, relative to the total content of all ethylenically unsaturated compounds contained in the photosensitive composition.

[0445] When the photosensitive composition of the present invention contains a polymerizable monomer, it may contain only one polymerizable monomer (particularly, an ethylenically unsaturated compound) or may contain two or more polymerizable monomers.

[0446] When the photosensitive composition involved in the present invention contains a polymerizable monomer, the content of the polymerizable monomer (especially, an ethylenically unsaturated compound) in the photosensitive composition is preferably 1 mass % to 70 mass %, more preferably 5 mass % to 70 mass %, further preferably 5 mass % to 60 mass %, and particularly preferably 5 mass % to 50 mass %, relative to the total solid content of the photosensitive composition.

[0447] (Photopolymerization Initiator)

[0448] The photosensitive composition according to the present invention may contain a photopolymerization initiator.

[0449] The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

[0450] The photopolymerization initiator may be a photoradical polymerization initiator.

[0451] Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an “oxime-based photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, also referred to as an “α-aminoalkylphenone-based photopolymerization initiator”), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as an “α-hydroxyalkylphenone-based polymerization initiator”), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an “acylphosphine oxide-based photopolymerization initiator”), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an “N-phenylglycine-based photopolymerization initiator”).

[0452] The photopolymerization initiator preferably includes at least one selected from the group consisting of oxime photopolymerization initiators, α-aminoalkylphenone photopolymerization initiators, α-hydroxyalkylphenone photopolymerization initiators, and N-phenylglycine photopolymerization initiators, and more preferably includes at least one selected from the group consisting of oxime photopolymerization initiators, α-aminoalkylphenone photopolymerization initiators, and N-phenylglycine photopolymerization initiators.

[0453] Furthermore, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs

[0031] to

[0042] of JP-A-2011-95716 and paragraphs

[0064] to

[0081] of JP-A-2015-014783 may be used.

[0454] Examples of commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF], IRGACURE (registered trademark) OXE03 (manufactured by BASF), IRGACURE (registered trademark) OXE04 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad (registered trademark) 379EG, IGM Resins BV], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad (registered trademark) 907, manufactured by IGM Resins BV], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad (registered trademark) 127, manufactured by IGM Resins BV.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad (registered trademark) 369, manufactured by IGM Resins BV], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad (registered trademark) 1173, manufactured by IGM Resins BV], 1-hydroxycyclohexylphenyl ketone [trade name: Omnirad (registered trademark) 184, manufactured by IGM Resins BV], 2,2-dimethoxy-1,2-diphenylethane-1-one [trade name: Omnirad (registered trademark) 651, manufactured by IGM Resins BV], etc., oxime ester-based photopolymerization initiator [trade name: Lunar (registered trademark) 6, manufactured by DKSH Management Ltd.], 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-305, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acetyl oxime) (trade name: TR-PBG-326, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazole-3-yl)-propane-1,2-dione-2-(O-benzoyl oxime) (trade name: TR-PBG-391, manufactured by Changzhou Tronly New Electronic Materials Co., LTD.), APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropane-1-one, manufactured by Shenzhen UV-ChemTech Ltd.), etc.

[0455] When the photosensitive composition according to the present invention contains a photopolymerization initiator, the composition may contain only one type of photopolymerization initiator or two or more types of photopolymerization initiators.

[0456] When the photosensitive composition of the present invention contains two or more photopolymerization initiators, it preferably contains a photopolymerization initiator and at least one selected from the group consisting of α-aminoalkylphenone-based photopolymerization initiators and α-hydroxyalkylphenone-based polymerization initiators.

[0457] When the photosensitive composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator in the photosensitive composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more relative to the total solid content of the photosensitive composition. The upper limit of the content of the photopolymerization initiator in the photosensitive composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less relative to the total solid content of the photosensitive composition.

[0458] (Acid Generator)

[0459] When the photosensitive composition according to the present invention contains a color material precursor that develops black color by acid, the composition may contain an acid generator.

[0460] The acid generator may be a photoacid generator or a thermal acid generator, but is preferably a photoacid generator.

[0461] The photoacid generator is a compound that can generate an acid when irradiated with radiation such as ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams.

[0462] As the photoacid generator, a compound that generates an acid by being sensitive to active light with a wavelength of 300 nm or more (preferably a wavelength of 300 nm to 450 nm) is preferred. In addition, a photoacid generator that is not directly sensitive to active light with a wavelength of 300 nm or more can also be preferably used in combination with a sensitizer as long as it is sensitive to active light with a wavelength of 300 nm or more and generates an acid by being used in combination with a sensitizer.

[0463] The photoacid generator preferably generates an acid with a pKa of 4 or less, more preferably generates an acid with a pKa of 3 or less, and further preferably generates an acid with a pKa of 2 or less. The lower limit of pKa is not particularly limited, but is preferably -10 or more, for example.

[0464] Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

[0465] Examples of the ionic photoacid generator include onium salt compounds, quaternary ammonium salt compounds, etc. Examples of the onium salt compound include diaryliodonium salt compounds, triarylsulfonium salt compounds, etc.

[0466] The ionic photoacid generator is preferably an onium salt compound, and more preferably at least one selected from the group consisting of diaryliodonium salt compounds and triarylsulfonium salt compounds.

[0467] As the ionic photoacid generator, for example, those described in paragraphs

[0114] to

[0133] of JP-A-2014-85643 can also be preferably used.

[0468] Examples of the nonionic photoacid generator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.

[0469] Specific examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imidosulfonate compound include the compounds described in paragraphs

[0083] to

[0088] of JP-A-2011-221494.

[0470] Specific examples of the oxime sulfonate compound include the compounds described in paragraphs

[0084] to

[0088] of International Publication No. 2018 / 179640.

[0471] From the viewpoint of sensitivity, for example, the photoacid generator is preferably at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and is more preferably an oxime sulfonate compound.

[0472] When the photosensitive composition according to the present invention contains an acid generator, the composition may contain only one type of acid generator or two or more types of acid generators.

[0473] When the photosensitive composition of the present invention contains an acid generator, the content of the acid generator is preferably 0.2% by mass to 5.0% by mass, and more preferably 0.5% by mass to 3.0% by mass, based on the total solid content of the photosensitive composition, from the viewpoint of the color development of the color material precursor that develops black color by acid.

[0474] (Sensitizer)

[0475] The photosensitive composition according to the present invention may contain a sensitizer.

[0476] The sensitizer has functions such as further increasing the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0477] Examples of the sensitizer include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, p-methylthiodimethylaniline, N-phenylglycine, tributyltin acetate, and trithiane.

[0478] When the photosensitive composition according to the present invention contains a sensitizer, it may contain only one type of sensitizer or may contain two or more types of sensitizers.

[0479] When the photosensitive composition of the present invention contains a sensitizer, the content of the sensitizer in the photosensitive composition is preferably 0.01 to 1% by mass, more preferably 0.02 to 0.5% by mass, based on the total solid content of the photosensitive composition.

[0480] (Heterocyclic Compounds)

[0481] The photosensitive composition according to the present invention may contain a heterocyclic compound.

[0482] The heterocyclic ring of the heterocyclic compound may be either a monocyclic ring or a polycyclic ring.

[0483] Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom.

[0484] The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

[0485] Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

[0486] The heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds, and more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds and benzoxazole compounds.

[0487] Preferred specific examples of the heterocyclic compound are shown below.

[0488] Examples of the triazole compound and the benzotriazole compound include the following compounds.

[0489] [Chemical formula 25]

[0490]

[0491] [Chemical formula 26]

[0492]

[0493] As the tetrazole compound, the following compounds can be exemplified.

[0494] [Chemical formula 27]

[0495]

[0496] [Chemical formula 28]

[0497]

[0498] As the thiadiazole compound, the following compounds can be exemplified.

[0499] [Chemical formula 29]

[0500]

[0501] As the triazine compound, the following compounds can be exemplified.

[0502] [Chemical formula 30]

[0503]

[0504] Examples of the rhodanine compound include the following compounds.

[0505] [Chemical formula 31]

[0506]

[0507] As the thiazole compound, the following compounds can be exemplified.

[0508] [Chemical formula 32]

[0509]

[0510] As the benzothiazole compound, the following compounds can be exemplified.

[0511] [Chemical formula 33]

[0512]

[0513] As the benzimidazole compound, the following compounds can be exemplified.

[0514] [Chemical formula 34]

[0515]

[0516] [Chemical formula 35]

[0517]

[0518] As the benzoxazole compound, the following compounds can be exemplified.

[0519] [Chemical formula 36]

[0520]

[0521] When the photosensitive composition according to the present invention contains a heterocyclic compound, it may contain only one heterocyclic compound or may contain two or more heterocyclic compounds.

[0522] When the photosensitive composition involved in the present invention contains a heterocyclic compound, the content of the heterocyclic compound in the photosensitive composition is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, further preferably 0.30% by mass to 8.0% by mass, and particularly preferably 0.50% by mass to 5.0% by mass, relative to the total solid content of the photosensitive composition.

[0523] (Aliphatic thiol compound)

[0524] The photosensitive composition according to the present invention may contain an aliphatic thiol compound.

[0525] When the photosensitive composition contains an aliphatic thiol compound, an ene-thiol reaction proceeds between the aliphatic thiol compound and the radical polymerizable compound having an ethylenically unsaturated group, whereby cure shrinkage of the obtained film is suppressed and stress of the film is relaxed.

[0526] As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher-functional aliphatic thiol compound) is preferred.

[0527] As the aliphatic thiol compound, a polyfunctional aliphatic thiol compound is preferred from the viewpoint of the adhesion of the formed pattern (particularly, the adhesion after exposure).

[0528] In the present invention, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

[0529] As the polyfunctional aliphatic thiol compound, a low molecular weight compound having a molecular weight of not less than 100 is preferred. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and further preferably 150 to 1,000.

[0530] The number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably difunctional to decafunctional, more preferably difunctional to octafunctional, and still more preferably difunctional to hexafunctional, from the viewpoint of adhesion of the pattern to be formed.

[0531] Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, ... 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptopropionyloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyrate), 1,3,5-tris(3 tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid and bis(mercaptoethyl) ether.

[0532] Among these, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

[0533] Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0534] When the photosensitive composition according to the present invention contains an aliphatic thiol compound, the composition may contain only one type of the aliphatic thiol compound or may contain two or more types of the aliphatic thiol compounds.

[0535] When the photosensitive composition involved in the present invention contains an aliphatic thiol compound, the content of the aliphatic thiol compound in the photosensitive composition is preferably 5 mass % or more, more preferably 5 mass % to 50 mass %, further preferably 5 mass % to 30 mass %, and particularly preferably 8 mass % to 20 mass %, relative to the total solid content of the photosensitive composition.

[0536] (Thermal cross-linking compound)

[0537] The photosensitive composition according to the present invention preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

[0538] In the present invention, the thermally crosslinkable compound having an ethylenically unsaturated group described below is not treated as an ethylenically unsaturated compound but as a thermally crosslinkable compound.

[0539] Examples of the thermally crosslinkable compound include epoxy compounds, oxetane compounds, methylol compounds, and blocked isocyanate compounds.

[0540] From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, the thermally crosslinkable compound is preferably a blocked isocyanate compound.

[0541] Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when at least one of the alkali-soluble resin and the radical polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease and the function as a protective film tends to be enhanced. In addition, the blocked isocyanate compound refers to a "compound having a structure in which the isocyanate group of the isocyanate is protected (so-called masking) by a blocking agent".

[0542] The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is, for example, preferably 90°C to 160°C, and more preferably 100°C to 150°C.

[0543] The dissociation temperature of the blocked isocyanate refers to "the temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter."

[0544] As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited thereto.

[0545] Examples of the end-capping agent having a dissociation temperature of 100 to 160° C. include active methylene compounds [(malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc., compounds having a structure represented by -C(=N-0H)- in the molecule).

[0546] Among these, as the terminal blocking agent having a dissociation temperature of 90° C. to 160° C., for example, at least one compound selected from the group consisting of oxime compounds and pyrazole compounds is preferred from the viewpoint of storage stability.

[0547] For example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer target, the blocked isocyanate compound preferably has an isocyanurate structure.

[0548] The blocked isocyanate compound having an isocyanurate structure is obtained by, for example, isocyanurating hexamethylene diisocyanate to thereby protect it.

[0549] Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferred in that the dissociation temperature can be easily set within a preferred range and development residue can be easily reduced compared to compounds not having an oxime structure.

[0550] The blocked isocyanate compound may have a polymerizable group.

[0551] The polymerizable group is not particularly limited, and a known polymerizable group can be used, but a radical polymerizable group is preferred.

[0552] Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloyloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.

[0553] Among these, as the polymerizable group, an ethylenically unsaturated group is preferred, a (meth)acryloyloxy group is more preferred, and an acryloyloxy group is further preferred.

[0554] As the blocked isocyanate compound, a commercially available product can be used.

[0555] Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, and Karenz (registered trademark) MOI-BP [all manufactured by SHOWA DENKO KK], and blocked Duranate series [for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) SBN-70D, and Duranate (registered trademark) WT32-B75P manufactured by Asahi Kasei Chemicals Corporation].

[0556] From the viewpoint of achieving more excellent effects of the present invention, the photosensitive composition preferably contains a blocked isocyanate compound having an NCO value of 4.5 mmol / g or more (hereinafter also referred to as a “first blocked isocyanate compound”).

[0557] The NCO value of the first blocked isocyanate compound is preferably 5.0 mmol / g or more, more preferably 5.3 mmol / g or more. In addition, from the viewpoint of a more excellent effect of the present invention, the upper limit of the NCO value of the first blocked isocyanate compound is preferably 8.0 mmol / g or less, more preferably 6.0 mmol / g or less, further preferably 5.8 mmol / g or less, and particularly preferably 5.7 mmol / g or less.

[0558] The NCO value of the blocked isocyanate compound in the present invention refers to the number of moles of isocyanate groups contained per 1 g of the blocked isocyanate compound, and is a value calculated from the structural formula of the blocked isocyanate compound.

[0559] From the viewpoint of achieving more excellent effects of the present invention, the first blocked isocyanate compound preferably has a ring structure.

[0560] Examples of the ring structure include an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, and a heterocyclic ring. From the viewpoint of achieving a more excellent effect of the present invention, an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring are preferred, and an aliphatic hydrocarbon ring is more preferred.

[0561] Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring and a cyclohexane ring, and among them, a cyclohexane ring is preferred.

[0562] Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and among them, a benzene ring is preferred.

[0563] Specific examples of the heterocyclic ring include an isocyanurate ring.

[0564] When the first blocked isocyanate compound has a ring structure, the number of rings is preferably 1 to 2, more preferably 1, from the viewpoint of achieving more excellent effects of the present invention.

[0565] When the first blocked isocyanate compound contains a condensed ring, the number of rings constituting the condensed ring is calculated. For example, the number of rings in the naphthalene ring is counted as 2.

[0566] The number of blocked isocyanate groups in the first blocked isocyanate compound is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2, from the viewpoint of excellent strength of the pattern formed and further excellent effects of the present invention.

[0567] The first blocked isocyanate compound is preferably a blocked isocyanate compound represented by the following formula Q, from the viewpoint of achieving more excellent effects of the present invention.

[0568] B 1 -A 1 -L 1 -A 2 -B 2 ......Formula Q

[0569] In formula Q, B 1 and B 2 Each independently represents a blocked isocyanate group.

[0570] The blocked isocyanate group is not particularly limited, but from the viewpoint of more excellent effects of the present invention, a group in which the isocyanate group is blocked with an oxime compound is preferred, and a group in which the isocyanate group is blocked with methyl ethyl ketoxime is more preferred (specifically, a group represented by *-NH-C(=O)-ON=C(CH3)-C2H5. * represents the same as A 1 or A 2 bonding position. ).

[0571] B 1 and B 2 The same groups are preferred.

[0572] In formula Q, A 1 and A 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 10 carbon atoms is preferred.

[0573] The alkylene group may be linear, branched or cyclic, and is preferably linear.

[0574] The number of carbon atoms of the alkylene group is 1 to 10, and preferably 1 to 5, more preferably 1 to 3, and even more preferably 1, from the viewpoint of further improving the effect of the present invention.

[0575] A 1 and A 2 The same groups are preferred.

[0576] In formula Q, L1 represents a divalent linking group.

[0577] Specific examples of the divalent linking group include divalent hydrocarbon groups.

[0578] Specific examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, and a group in which two or more of these groups are linked.

[0579] The divalent saturated hydrocarbon group may be linear, branched or cyclic, and is preferably cyclic from the viewpoint of achieving more excellent effects of the present invention.

[0580] The divalent saturated hydrocarbon group has preferably 4 to 15 carbon atoms, more preferably 5 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms, from the viewpoint of achieving more excellent effects of the present invention.

[0581] The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. The divalent aromatic hydrocarbon group may have a substituent (for example, an alkyl group).

[0582] As the divalent linking group, a linear, branched or cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, a group formed by linking a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms and a linear alkylene group having 1 to 3 carbon atoms, preferably a divalent aromatic hydrocarbon group which may have a substituent or a group formed by linking a divalent aromatic hydrocarbon group and a linear alkylene group having 1 to 3 carbon atoms, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms or a phenylene group which may have a substituent, further preferably a cyclohexylene group or a phenylene group which may have a substituent, and particularly preferably a cyclohexylene group.

[0583] The blocked isocyanate compound represented by the formula Q is particularly preferably a blocked isocyanate compound represented by the following formula QA, from the viewpoint of achieving more excellent effects of the present invention.

[0584] B 1a -A 1a -L la -A 2a -B 2a ...Formula QA

[0585] In formula QA, B 1a and B 2a Each independently represents a blocked isocyanate group.

[0586] B 1a and B 2a The preferred embodiment is the same as B in formula Q 1 and B 2 same.

[0587] In formula QA, A 1a and A2a Each independently represents a divalent linking group.

[0588] A 1a and A 2a The preferred embodiment of the divalent linking group in formula Q is the same as that of A 1 and A 2 same.

[0589] In formula QA, L 1a It represents a cyclic divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group.

[0590] L 1a The number of carbon atoms in the cyclic divalent saturated hydrocarbon group is preferably 5 to 10, more preferably 5 to 8, further preferably 5 to 6, and particularly preferably 6.

[0591] L 1a The preferred embodiment of the divalent aromatic hydrocarbon group in formula Q is the same as L 1 same.

[0592] L 1a It is preferably a cyclic divalent saturated hydrocarbon group, more preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, further preferably a cyclic divalent saturated hydrocarbon group having 5 to 10 carbon atoms, particularly preferably a cyclic divalent saturated hydrocarbon group having 5 to 6 carbon atoms, and most preferably a cyclohexylene group.

[0593] When L 1a In the case of a cyclohexylene group, the blocked isocyanate compound represented by the formula QA may be an isomer mixture of a cis-isomer and a trans-isomer.

[0594] The mass ratio of the cis isomer to the trans isomer is preferably cis isomer / trans isomer=10 / 90 to 90 / 10, more preferably cis isomer / trans isomer=40 / 60 to 60 / 40.

[0595] Specific examples of the first blocked isocyanate compound are shown below, but the first blocked isocyanate compound is not limited to these.

[0596] [Chemical formula 37]

[0597]

[0598] When the photosensitive composition according to the present invention contains a thermally crosslinkable compound, the composition may contain only one thermally crosslinkable compound or may contain two or more thermally crosslinkable compounds.

[0599] When the photosensitive composition of the present invention contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound in the photosensitive composition is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total solid content of the photosensitive composition.

[0600] (Surfactant)

[0601] The photosensitive composition according to the present invention may contain a surfactant.

[0602] Examples of the surfactant include surfactants described in paragraph

[0017] of Japanese Patent No. 4502784 and paragraphs

[0060] to

[0071] of Japanese Unexamined Patent Application Publication No. 2009-237362.

[0603] Examples of the surfactant include hydrocarbon-based surfactants, fluorine-based surfactants, and silicone-based surfactants.

[0604] From the viewpoint of improving environmental compatibility, the surfactant preferably contains no fluorine atom.

[0605] As the surfactant, a hydrocarbon-based surfactant or a silicone-based surfactant is preferred.

[0606] Examples of commercially available fluorine-based surfactants include MEGAFAC (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, and F-568. , F-575, F-780, EXP.MFS-330, EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21 [the above is DIC Corporation], Fluorad (registered trademark) FC430, FC431 and FC171 (all manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40 (all manufactured by AGC Inc.), PolyFox (registered trademark) PF636, PF656, PF6320, PF6520 and PF7002 (all manufactured by OMNOVA Solutions Inc.], Ftergent (registered trademark) 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683 [all manufactured by NEOS COMPANY LIMITED] and U-120E [manufactured by Uni-chem Co., Ltd.].

[0607] Furthermore, as the fluorine-based surfactant, an acrylic compound can also be preferably used, which has a molecular structure containing a functional group (the functional group contains a fluorine atom) and when heat is applied, a part of the functional group containing a fluorine atom is broken and the fluorine atom is volatilized. As such a fluorine-based surfactant, MEGAFAC DS series manufactured by DIC Corporation can be cited [Chemical Industry Daily (February 22, 2016), Nikkei Industry News (February 23, 2016)], for example, MEGAFAC (registered trademark) DS-21.

[0608] Furthermore, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

[0609] Furthermore, a block polymer can also be used as the fluorine-based surfactant.

[0610] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer compound containing a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a constituent unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy or propyleneoxy) can also be preferably used.

[0611] Furthermore, as the fluorine-based surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in the side chain can also be used. Examples of such fluorine-based surfactants include MEGAFAC (registered trademark) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

[0612] From the viewpoint of improving environmental adaptability, the fluorine-based surfactant is preferably a surfactant derived from an alternative material of a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS).

[0613] Examples of the hydrocarbon-based surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.

[0614] Examples of commercially available hydrocarbon surfactants include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2, Tetronic (registered trademark) 304, 701, 704, 901, 904, and 150R1, HYDROPALAT (registered trademark) WE 3323 [all manufactured by BASF], Solsperse (registered trademark) 20000 [all manufactured by Lubrizol Japan Limited.], NCW-101, NCW-1001, and NCW-1002 [all manufactured by FUJIFILM WakoPure Chemical Corporation], PIONIN (registered trademark) D-1105, D-6112, D-6112-W, and D-6315 [all manufactured by Takemoto Oil & Fat Co., Ltd.], OLFINE (registered trademark) E1010 and Surfynol (registered trademark) 104, 400 and 440 [all manufactured by Nissin Chemical Co., Ltd.].

[0615] Examples of silicone surfactants include linear polymers composed of siloxane bonds, modified siloxane polymers having an organic group introduced into a side chain or a terminal, polymers having a structural unit having a hydrophilic group in a side chain and a structural unit having a siloxane bond-containing group in a side chain, etc. Among these, as silicone surfactants, polymers having a structural unit having a hydrophilic group in a side chain and a structural unit having a siloxane bond-containing group in a side chain are preferred.

[0616] The polymer may be a random copolymer or a block copolymer.

[0617] Examples of the structural unit having a hydrophilic group in a side chain include structural units derived from a monomer represented by the following formula.

[0618] [Chemical formula 38]

[0619]

[0620] In the formula, R 4 represents a hydrogen atom or a methyl group, R 5 represents a hydrogen atom or a methyl group, n represents an integer of 1 to 4, and m represents an integer of 1 to 100.

[0621] Examples of the structural unit having a siloxane bond-containing group in a side chain include structural units derived from a monomer represented by the following formula.

[0622] [Chemical formula 39]

[0623]

[0624] In the formula, R each independently represents an alkyl group having 1 to 3 carbon atoms, 1 represents a hydrogen atom or a methyl group, L 1 represents a divalent organic group or a single bond.

[0625] Furthermore, as the structural unit having a siloxane bond-containing group in a side chain, there can also be mentioned structural units derived from a monomer represented by the following formula.

[0626] [Chemical formula 40]

[0627]

[0628] In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 1 to 10 carbon atoms, R3 represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 5 to 50.

[0629] Examples of commercially available silicone surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 [all manufactured by DIC Corporation], DOWSIL (registered trademark) 8032ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 [all manufactured by Dow Corning Toray Co., Ltd. manufacturing], X-22-4952, 42. KF-643, X-22-6191, P-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322 , KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626 and KP-652 [the above are Shin-Etsu Chemical Co., Ltd.], F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 [all manufactured by Momentive Performance Materials Inc.], BYK300, BYK306, BYK307, BYK310, BYK320, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 and BYK323 [all manufactured by BYK Chemie], etc.

[0630] Furthermore, as the surfactant, a nonionic surfactant is preferred.

[0631] When the photosensitive composition according to the present invention contains a surfactant, it may contain only one type of surfactant or two or more types of surfactants.

[0632] When the photosensitive composition of the present invention contains a surfactant, the content of the surfactant in the photosensitive composition is preferably 0.01% to 3.0% by mass, more preferably 0.01% to 1.0% by mass, and further preferably 0.05% to 0.80% by mass, relative to the total solid content of the photosensitive composition.

[0633] (Inhibitor)

[0634] The photosensitive composition according to the present invention may contain a polymerization inhibitor.

[0635] The polymerization inhibitor refers to a compound having a function of delaying or inhibiting a polymerization reaction.

[0636] The polymerization inhibitor is not particularly limited, and for example, a known compound used as a polymerization inhibitor can be used.

[0637] Examples of the polymerization inhibitor include phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, Hindered phenol compounds such as pentaerythritol tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propene; nitroso compounds or their salts such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 4-benzoquinone; phenol compounds such as 4-methoxyphenol, 4-methoxy-1-naphthol, and tert-butylcatechol; metal salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate, etc.

[0638] Among these, as the polymerization inhibitor, from the viewpoint of more excellent effect of the present invention, at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or their salts and hindered phenol compounds is preferred, and at least one selected from the group consisting of phenothiazine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid], [ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), p-methoxyphenol and N-nitrosophenylhydroxylamine aluminum salt is more preferred.

[0639] When the photosensitive composition according to the present invention contains a polymerization inhibitor, the composition may contain only one polymerization inhibitor or two or more polymerization inhibitors.

[0640] When the photosensitive composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.01% by mass to 3.0% by mass, and even more preferably 0.02% by mass to 2.0% by mass, relative to the total solid content of the photosensitive composition.

[0641] Furthermore, when the photosensitive composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive composition is preferably 0.005% to 5.0% by mass, more preferably 0.01% to 3.0% by mass, and further preferably 0.01% to 1.0% by mass, relative to the total mass of the polymerizable monomers.

[0642] (Hydrogen donating compound)

[0643] The photosensitive composition according to the present invention may contain a hydrogen donating compound.

[0644] The hydrogen-donating compound has functions of further increasing the sensitivity of the photopolymerization initiator to actinic rays and suppressing the polymerization inhibition of the polymerizable compound caused by oxygen.

[0645] Examples of the hydrogen-donating compound include amines and amino acid compounds.

[0646] Examples of the amines include compounds described in "Journal of Polymer Society" by MR Sander et al., Vol. 10, p. 3173 (1972), JP-44-020189, JP-51-082102, JP-52-134692, JP-59-138205, JP-60-084305, JP-62-018537, JP-64-033104, and Research Disclosure No. 33825.

[0647] More specifically, examples of the amines include 4,4′-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (another name: colorless crystal violet), triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

[0648] From the viewpoint of achieving more excellent effects of the present invention, the amine is preferably at least one selected from the group consisting of 4,4′-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane.

[0649] Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0650] From the viewpoint of achieving more excellent effects of the present invention, N-phenylglycine is preferred as the amino acid compound.

[0651] In addition, as hydrogen-donating compounds, for example, organic metal compounds described in Japanese Patent Publication No. 48-042965 (for example, tributyltin acetate), hydrogen donors described in Japanese Patent Publication No. 55-034414, and sulfur compounds described in Japanese Patent Application Laid-Open No. 6-308727 (for example, trithiane) can also be cited.

[0652] When the photosensitive composition according to the present invention contains a hydrogen donating compound, it may contain only one hydrogen donating compound or may contain two or more hydrogen donating compounds.

[0653] When the photosensitive composition involved in the present invention contains a hydrogen donating compound, from the viewpoint of improving the curing rate by the balance between the polymerization growth rate and the chain transfer, the content of the hydrogen donating compound in the photosensitive composition is preferably 0.01 mass % to 10.0 mass %, more preferably 0.01 mass % to 8.0 mass %, and further preferably 0.03 mass % to 5.0 mass % relative to the total solid content of the photosensitive composition.

[0654] (Solvent)

[0655] The photosensitive composition according to the present invention may contain a solvent.

[0656] The solvent may be water or an organic solvent, but an organic solvent is preferred.

[0657] Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol methyl ethyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol.

[0658] The solvent may be an organic solvent having a boiling point of 180°C to 250°C (so-called high boiling point solvent).

[0659] When the photosensitive composition according to the present invention contains a solvent, it may contain only one solvent or two or more solvents.

[0660] When the photosensitive composition of the present invention contains a solvent, the content of the solvent in the photosensitive composition is preferably 20% to 95% by mass, more preferably 60% to 95% by mass, and further preferably 70% to 95% by mass, relative to the total mass of the photosensitive composition.

[0661] (Other ingredients)

[0662] The photosensitive composition according to the present invention may contain components other than the above components (also referred to as "other components").

[0663] Examples of other components include colorants (eg, pigments and dyes), antioxidants, and particles (eg, metal oxide particles).

[0664] Furthermore, other additives described in paragraphs

[0058] to

[0071] of JP-A-2000-310706 may also be mentioned as other components.

[0665] -Colorants-

[0666] The photosensitive composition according to the present invention may contain a colorant (a pigment, a dye, etc.), but preferably contains substantially no colorant, for example, from the viewpoint of transparency.

[0667] When the photosensitive composition according to the present invention contains a colorant, the content of the colorant in the photosensitive composition is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total solid content of the photosensitive composition.

[0668] - Antioxidants -

[0669] The photosensitive composition according to the present invention may contain an antioxidant.

[0670] As antioxidants, for example, there can be mentioned 3-pyrazolidinones such as 1-phenyl-3-pyrazolidinone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidinone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine, and p-phenylenediamine.

[0671] Among these, as the antioxidant, 3-pyrazolidinones are preferred, and 1-phenyl-3-pyrazolidinone is more preferred, from the viewpoint of achieving more excellent effects of the present invention.

[0672] When the photosensitive composition of the present invention contains an antioxidant, the content of the antioxidant in the photosensitive composition is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.01% by mass or more relative to the total solid content of the photosensitive composition. The upper limit is not particularly limited, but is preferably 1% by mass or less, for example.

[0673] -particle-

[0674] The photosensitive composition according to the present invention may contain particles.

[0675] As the particles, metal oxide particles are preferred.

[0676] The metal in the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te.

[0677] For example, from the viewpoint of transparency of the cured film, the average primary particle size of the particles is preferably 1 nm to 200 nm, and more preferably 3 nm to 80 nm.

[0678] The average primary particle size of the particles is calculated by measuring the particle sizes of 200 random particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, if the shape of the particles is not spherical, the longest side is used as the particle size.

[0679] When the photosensitive composition of the present invention contains particles, the composition may contain only one kind of particles having different metal species, sizes, etc., or may contain two or more kinds of particles having different metal species, sizes, etc.

[0680] When the photosensitive composition involved in the present invention does not contain particles or the photosensitive composition involved in the present invention contains particles, the content of particles relative to the total solid content of the photosensitive composition is preferably greater than 0 mass% and less than 35 mass%, more preferably, no particles are contained, or the content of particles relative to the total solid content of the photosensitive composition is greater than 0 mass% and less than 10 mass%, further preferably, no particles are contained, or the content of particles relative to the total solid content of the photosensitive composition is greater than 0 mass% and less than 5 mass%, further preferably, no particles are contained, or the content of particles relative to the total solid content of the photosensitive composition is greater than 0 mass% and less than 1 mass%, and particularly preferably, no particles are contained.

[0681] When a film having a thickness of 1 μm is formed using the photosensitive composition of the present invention, the absorbance of the film at a wavelength of 365 nm (hereinafter also referred to as "absorbance A1") is preferably 0.1 or less, more preferably 0.08 or less, further preferably 0.06 or less, and particularly preferably 0.04 or less from the viewpoint of patterning properties. The lower limit is not particularly limited, and for example, 0.001 or more can be cited.

[0682] The absorbance of the film at a wavelength of 365 nm being 0.1 or less indicates that the film in a state where the specific color material precursor is not colored black by stimulation has excellent transmittance to light at a wavelength of 365 nm. If the absorbance of the film at a wavelength of 365 nm is 0.1 or less, during exposure, the incident light gradually attenuates in the film thickness direction of the film (i.e., the photosensitive composition layer) formed using the photosensitive composition, and for example, in the case of a negative type, it is difficult to produce a phenomenon such as insufficient polymerization curing, and there is a tendency to easily obtain a pattern with a good shape.

[0683] When the photosensitive composition of the present invention is used and a specific color material precursor is stimulated to develop black color to form a black film with a film thickness of 1 μm, the absorbance of the film at a wavelength of 365 nm (hereinafter also referred to as "absorbance A2") is preferably 0.14 or more, more preferably 0.16 or more, further preferably 0.18 or more, and particularly preferably 0.2 or more. The upper limit is not particularly limited, and for example, 4.0 or less can be cited.

[0684] The ratio of absorbance A2 to absorbance A1 (absorbance A2 / absorbance A1) is preferably 5.0 or more, more preferably 7.0 or more.

[0685] When the photosensitive composition of the present invention is used and a specific color material precursor is stimulated to develop black color to form a black film with a film thickness of 1 μm, the average absorbance of the film at a wavelength of 400 nm to 700 nm is preferably 0.14 or more, more preferably 0.16 or more, further preferably 0.18 or more, and particularly preferably 0.2 or more. The upper limit is not particularly limited, and for example, 4.0 or less can be cited.

[0686] The absorbance of the film at a wavelength of 365 nm and the average absorbance at a wavelength of 400 nm to 700 nm are both 0.14 or more, indicating that the film, in a state where the specific color material precursor develops black color under stimulation, has excellent light-shielding properties against light with wavelengths in the ultraviolet to visible regions.

[0687] In the present invention, "absorbance" is a value measured using a spectrophotometer.

[0688] As the spectrophotometer, for example, an ultraviolet-visible spectrophotometer (model: UV-1800) manufactured by SHIMADZU CORPORATION can be used. However, the spectrophotometer is not limited to this.

[0689] A preferred embodiment of the photosensitive composition of the present invention is the following embodiment: it contains: a color material precursor that develops black color by at least one stimulus selected from the group consisting of heat, light, acid, base and free radicals, an alkali-soluble resin, a photopolymerizable monomer and a photopolymerization initiator, and satisfies all of the following (1) to (3).

[0690] (1) When a film having a film thickness of 1 μm is formed using the photosensitive composition, the absorbance of the film at a wavelength of 365 nm is 0.1 or less.

[0691] (2) When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the absorbance of the film at a wavelength of 365 nm is 0.2 or more.

[0692] (3) When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the average absorbance of the film at a wavelength of 400 nm to 700 nm is 0.2 or more.

[0693] <<Viscosity of Photosensitive Composition>>

[0694] For example, from the viewpoint of coating properties, the viscosity of the photosensitive composition of the present invention at 25° C. is preferably 1 to 50 mPa·s, more preferably 2 to 40 mPa·s, and even more preferably 3 to 30 mPa·s.

[0695] The viscosity of the photosensitive composition according to the present invention is measured using a viscometer.

[0696] As the viscometer, for example, a viscometer (trade name: VISCOMETER TV-22) manufactured by TOKI SANGYO CO., LTD. can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

[0697] 《Surface tension of photosensitive compositions》

[0698] For example, from the viewpoint of coating properties, the surface tension of the photosensitive composition of the present invention at 25° C. is preferably 5 to 100 mN / m, more preferably 10 to 80 mN / m, and even more preferably 15 to 40 mN / m.

[0699] The surface tension of the photosensitive composition according to the present invention is measured using a surface tensiometer.

[0700] As the surface tensiometer, for example, a surface tensiometer (trade name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be preferably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

[0701] <<Application of photosensitive composition>>

[0702] The photosensitive composition according to the present invention can be used in various applications.

[0703] The photosensitive composition according to the present invention can form a film having excellent light-shielding properties and has excellent patterning properties, and therefore can be used for applications such as a black matrix (so-called black partition wall).

[0704] [Transfer film]

[0705] The transfer film according to the present invention comprises a temporary support and a photosensitive composition layer containing the photosensitive composition according to the present invention.

[0706] The transfer film according to the present invention may have a composition layer other than the photosensitive composition layer (so-called other composition layer).

[0707] The transfer film according to the present invention may have a structure including a protective film on a photosensitive composition layer or other composition layer, for example.

[0708] The photosensitive composition layer, the other composition layer, and the protective film may each be a single layer or may be a multilayer of two or more layers.

[0709] The transfer film according to the present invention preferably has a structure of temporary support / photosensitive composition layer / protective film.

[0710] In the transfer film involved in the present invention, when the photosensitive composition layer has a structure with other composition layers on the side opposite to the temporary support side, the total thickness of the other composition layers arranged on the side opposite to the temporary support side of the photosensitive composition layer (total film thickness) is preferably 0.1% to 30%, and more preferably 0.1% to 20% relative to the thickness of the photosensitive composition layer (film thickness).

[0711] From the viewpoint of suppressing the generation of bubbles in the laminating step described later, the maximum width of the corrugations of the transfer film of the present invention is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 60 μm or less. In addition, the lower limit of the maximum width of the corrugations is 0 μm or more, preferably 0.1 μm or more, and more preferably 1 μm or more.

[0712] The maximum width of the corrugations of the transfer film is a value measured in the following procedure.

[0713] First, cut the transfer film into a size of 20 cm in length and 20 cm in width in a direction perpendicular to the main surface to prepare a test sample. In addition, when the transfer film has a protective film, peel off the protective film. Next, place the above test sample on a smooth and horizontal stage so that the surface of the temporary support is opposite to the stage. After standing, use a laser microscope (for example, VK-9700SP manufactured by KEYENCE CORPORATION) to scan the surface of the test sample in a 10 cm square range in the center of the test sample to obtain a three-dimensional surface image, and subtract the minimum concave height from the maximum convex height observed in the obtained three-dimensional surface image. Perform the above operation for 10 test samples, and use the arithmetic mean value as the "maximum width of the corrugation of the transfer film".

[0714] Hereinafter, the structure of the transfer film according to the present invention will be described in detail.

[0715] <Temporary Support>

[0716] The transfer film according to the present invention has a temporary support.

[0717] The temporary support is a member that supports the photosensitive composition layer and is finally removed by a peeling treatment.

[0718] The temporary support may be a single-layer structure or a multi-layer structure.

[0719] The temporary support is preferably a film, more preferably a resin film. The temporary support is preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure or under pressure and heating.

[0720] Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a polymethyl methacrylate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.

[0721] Among these, a polyethylene terephthalate film is preferred as the temporary support.

[0722] Furthermore, the film used as a temporary support preferably has no deformation such as wrinkles, or no damage.

[0723] From the viewpoint of being able to perform pattern exposure through a temporary support, the temporary support preferably has high transparency, and the transmittance at a wavelength of 313 nm, a wavelength of 365 nm, a wavelength of 405 nm, and a wavelength of 436 nm is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 90% or more.

[0724] Preferred values ​​of the transmittance include 87%, 92%, 98%, and the like.

[0725] The transmittance was calculated as the ratio of the light emitted from the temporary support to the light amount of light of each wavelength incident (= amount of emitted light / amount of incident light×100; %).

[0726] From the viewpoint of pattern formation during pattern exposure through the temporary support and transparency of the temporary support, the temporary support preferably has a small haze. Specifically, the temporary support preferably has a haze value of 2% or less, more preferably 0.5% or less, and further preferably 0.1% or less.

[0727] From the viewpoint of pattern formability when pattern exposure is performed through the temporary support and transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably small.

[0728] The total number of particles, foreign matter and defects with a diameter of 1 μm or more contained in the temporary support is preferably 50 pieces / 10 mm. 2 Below, more preferably 10 / 10mm 2 Below, below is more preferably 3 / 10mm 2 , particularly preferably 0 / 10mm 2 .

[0729] In order to improve the adhesion between the temporary support and the photosensitive composition layer, the surface of the temporary support in contact with the photosensitive composition layer may be surface-modified by ultraviolet (UV) irradiation, corona discharge, plasma or the like.

[0730] When the surface modification is performed by ultraviolet irradiation, the exposure amount of ultraviolet rays is not particularly limited, but is preferably 10 mJ / cm 2 ~2000mJ / cm 2 , more preferably 50 mJ / cm 2 ~1000mJ / cm 2 .

[0731] As the light source for ultraviolet irradiation, for example, there can be mentioned a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, a light emitting diode (LED), etc. that emits light in a wavelength band of 150 nm to 450 nm. The lamp output and illumination are not particularly limited and can be appropriately set, for example, according to the desired exposure amount.

[0732] In order to provide handleability, a layer containing fine particles (also referred to as a "lubricant layer") may be provided on the surface of the temporary support.

[0733] The lubricant layer may be provided on one surface or on both surfaces of the temporary support.

[0734] The diameter of the particles contained in the lubricant layer is not particularly limited, but is preferably, for example, 0.05 μm to 0.8 μm. The film thickness of the lubricant layer is not particularly limited, but is preferably, for example, 0.05 μm to 1.0 μm.

[0735] The thickness of the temporary support is not particularly limited, but is, for example, preferably 5 μm to 200 μm, more preferably 5 μm to 150 μm, further preferably 5 μm to 50 μm, and particularly preferably 5 μm to 25 μm from the viewpoint of handleability and versatility.

[0736] The thickness of the temporary support was calculated as an average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM: Scanning Flectron Microscope).

[0737] As the temporary support, a commercially available product can be used.

[0738] Examples of commercially available temporary supports include Lumirror (registered trademark) 16KS40, Lumirror (registered trademark) 16FB40, Lumirror (registered trademark) #38-U48, Lumirror (registered trademark) #75-U34 and Lumirror (registered trademark) #25T60 [all manufactured by TORAY INDUSTRIES, INC.], and Cosmo shine (registered trademark) A4100, Cosmo shine (registered trademark) A4160, Cosmo shine (registered trademark) A4300, Cosmoshine (registered trademark) A4360 and Cosmo shine (registered trademark) A8300 [all manufactured by TOYOBO CO., LTD.].

[0739] The temporary support may be a recycled product. As a recycled product, a product obtained by washing and making fragments of used films etc. as a material and making the fragments into films may be cited. As a specific example of a recycled product, the Ecouse series manufactured by TORAY INDUSTRIES, INC. may be cited.

[0740] Examples of the temporary support include a biaxially stretched polyethylene terephthalate film having a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film having a thickness of 9 μm.

[0741] Preferred forms of temporary supports are described, for example, in paragraphs

[0017] to

[0018] of Japanese Patent Publication No. 2014-085643, paragraphs

[0019] to

[0026] of Japanese Patent Publication No. 2016-027363, paragraphs

[0041] to

[0057] of International Publication No. 2012 / 081680, and paragraphs

[0029] to

[0040] of International Publication No. 2018 / 179370, and the contents of these publications are incorporated into this specification.

[0742] <Photosensitive Composition Layer>

[0743] The transfer film of the present invention has a photosensitive composition layer containing the photosensitive composition of the present invention. According to the transfer film of the present invention, a pattern can be formed on a transfer object by transferring the photosensitive composition layer to a transfer object and then exposing and developing the transferred object.

[0744] The photosensitive composition layer may be any layer as long as it contains the photosensitive composition according to the present invention, and is preferably a layer composed of the photosensitive composition according to the present invention or a layer composed of the solid content of the photosensitive composition according to the present invention.

[0745] The photosensitive composition layer may be a positive photosensitive composition layer or a negative photosensitive composition layer, but is preferably a negative photosensitive composition layer.

[0746] The negative photosensitive composition layer refers to a photosensitive composition layer in which the solubility of the exposed portion in the developer is reduced by exposure. When the photosensitive composition layer is a negative photosensitive composition layer, the formed pattern corresponds to a cured layer.

[0747] The photosensitive composition layer may contain a predetermined amount of impurities.

[0748] As specific examples of impurities, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen and their ions can be cited. Among them, halide ions (for example, chloride ions, bromide ions and iodide ions), sodium ions and potassium ions are easily mixed as impurities, so it is preferably set to the following content.

[0749] The content of impurities in the photosensitive composition layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less, based on mass. Furthermore, the content of impurities in the photosensitive composition layer may be 1 ppb or more, or 0.1 ppm or more, based on mass.

[0750] As a specific example of the content of impurities in the photosensitive composition layer, there can be mentioned an embodiment in which all the above-mentioned impurities are 0.6 ppm on a mass basis.

[0751] As a method for setting the content of impurities in the photosensitive composition layer within the above range, for example, there can be mentioned: a method of selecting a raw material with a small content of impurities as a raw material of the photosensitive composition; a method of preventing the mixing of impurities when forming the photosensitive composition layer; and a method of washing and removing the photosensitive composition layer. By this method, the content of impurities in the photosensitive composition layer can be set within the above range.

[0752] Impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

[0753] The photosensitive composition layer may contain residual monomers of each structural unit of the above-mentioned alkali-soluble resin (hereinafter, also simply referred to as "residual monomers").

[0754] From the viewpoint of patterning and reliability, the content of residual monomers in the photosensitive resin layer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and further preferably 500 mass ppm or less relative to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but may be, for example, 1 mass ppm or more, or 10 mass ppm or more.

[0755] From the viewpoint of patterning and reliability, the content of residual monomers in the photosensitive composition layer is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and further preferably 100 mass ppm or less relative to the total solid content of the photosensitive composition. The lower limit is not particularly limited, but may be, for example, 0.1 mass ppm or more, or 1 mass ppm or more.

[0756] The residual monomer amount of monomers when synthesizing an alkali-soluble resin by polymer reaction is also preferably within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.

[0757] The amount of residual monomers in the photosensitive composition layer can be measured by a known method such as liquid chromatography and gas chromatography.

[0758] The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition layer is preferably as low as possible.

[0759] The content of these compounds in the photosensitive composition layer is preferably 100 ppm or less, more preferably 20 ppm or less, and further preferably 4 ppm or less, based on mass. The lower limit can be 10 ppb or more, or 100 ppb or more, based on mass.

[0760] The content of these compounds can be reduced by, for example, selecting compounds with a small content of these compounds as raw materials of the photosensitive composition and preventing the inclusion of these compounds when forming the photosensitive composition layer.

[0761] The contents of these compounds can be quantified by known measurement methods.

[0762] From the viewpoint of improving reliability and lamination properties, the content of water in the photosensitive composition layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass.

[0763] <<Thickness of Photosensitive Composition Layer>>

[0764] The thickness of the photosensitive composition layer (also referred to as "film thickness") is not particularly limited.

[0765] For example, when used as a partition wall of a micro LED display, the thickness of the photosensitive composition layer is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of further suppressing color mixing of light between adjacent pixels.

[0766] Furthermore, for example, from the viewpoint of workability, the film thickness of the photosensitive composition layer is preferably 20 μm or less, and more preferably 15 μm or less.

[0767] The film thickness of the photosensitive composition layer was calculated as an average value of five arbitrary points measured by cross-sectional observation using a scanning electron microscope (SEM: Scanning Electron Microscope).

[0768] <<Refractive Index of Photosensitive Composition Layer>>

[0769] The refractive index of the photosensitive composition layer is not particularly limited, but is, for example, preferably 1.41 to 1.59, more preferably 1.47 to 1.56.

[0770] The refractive index of the photosensitive composition layer is a value at a wavelength of 550 nm measured using an ellipsometer in an environment at an atmospheric temperature of 25°C.

[0771] <<Color of Photosensitive Composition Layer>>

[0772] The photosensitive composition layer is preferably colorless.

[0773] Specifically, total reflection 1 incident angle: 8°, light source: D-65 (2° field of view)] In the CIE1976 (L*, a*, b*) color space, the L* value is preferably 10 to 90, the a* value is preferably -1.0 to 1.0, and the b* value is preferably -1.0 to 1.0.

[0774] <<Dissolution Rate of Photosensitive Composition Layer>>

[0775] From the viewpoint of suppressing residues during development, the dissolution rate of the photosensitive composition layer in a 1.0 mass % sodium carbonate aqueous solution is preferably 0.01 μm / sec or more, more preferably 0.10 μm / sec or more, and even more preferably 0.20 μm / sec or more.

[0776] Furthermore, from the viewpoint of the edge shape of the pattern, the dissolution rate of the photosensitive composition layer in a 1.0 mass % sodium carbonate aqueous solution is preferably 5.0 μm / sec or less, more preferably 4.0 μm / sec or less, and even more preferably 3.0 μm / sec or less.

[0777] Specific preferred numerical values ​​include 1.8 μm / sec, 1.0 μm / sec, and 0.7 μm / sec.

[0778] The dissolution rate per unit time of the photosensitive composition layer in a 1.0 mass % sodium carbonate aqueous solution was measured as follows.

[0779] A 1.0 mass % sodium carbonate aqueous solution at a liquid temperature of 25° C. is used to spray develop a photosensitive composition layer (with a film thickness of 1.0 μm to 10 μm) formed on a glass substrate from which the solvent has been fully removed until the photosensitive composition layer is completely dissolved (up to 2 minutes). The dissolution rate of the photosensitive composition layer is calculated by dividing the film thickness of the photosensitive composition layer by the time required for the photosensitive composition layer to be completely dissolved. In addition, if it is not completely dissolved within 2 minutes, the calculation is performed in the same manner based on the change in film thickness until that point. For development, a spray nozzle (model: 1 / 4MINJJX030PP) manufactured by H.IKEUCHI Co., Ltd. is used, and the spray pressure of the spray is set to 0.08 MPa. Under the above conditions, the spray flow rate per unit time is set to 1,800 mL / min.

[0780] <<Dissolution Rate of Cured Film of Photosensitive Composition Layer>>

[0781] The dissolution rate of the cured film of the photosensitive composition layer (with a film thickness of 1.0 μm to 10 μm) in a 1.0 mass % sodium carbonate aqueous solution is preferably 3.0 μm / second or less, more preferably 2.0 μm / second or less, further preferably 1.0 μm / second or less, and particularly preferably 0.2 μm / second or less. The cured film of the photosensitive composition layer is exposed to light using i-rays (wavelength 365 nm) at an exposure amount of 300 mJ / cm 2 A film obtained by exposing a photosensitive composition layer.

[0782] Specific preferred numerical values ​​include 0.8 μm / sec, 0.2 μm / sec, and 0.001 μm / sec.

[0783] The dissolution rate of the cured film (film thickness range 1.0 μm to 10 μm) of the photosensitive composition layer in 1.0 mass % sodium carbonate aqueous solution is measured by the same method as the dissolution rate per unit time of the photosensitive composition layer in 1.0 mass % sodium carbonate aqueous solution.

[0784] <<Swelling Rate of Photosensitive Composition Layer>>

[0785] From the viewpoint of improving pattern forming properties, the swelling ratio of the photosensitive composition layer after exposure in a 1.0 mass % sodium carbonate aqueous solution is preferably 100% or less, more preferably 50% or less, and even more preferably 30% or less.

[0786] The swelling ratio of the photosensitive composition layer after exposure in a 1.0 mass % sodium carbonate aqueous solution was measured as follows.

[0787] An ultra-high pressure mercury lamp was used, and the exposure amount was 500 mJ / cm 2 , a photosensitive composition layer (film thickness 1.0 μm to 10 μm) formed on a glass substrate from which the solvent was fully removed was exposed. Each glass substrate was immersed in a 1.0 mass % sodium carbonate aqueous solution at a liquid temperature of 25°C, and the film thickness at the time point after 30 seconds was measured. Then, the ratio of the increase in film thickness after immersion relative to the film thickness before immersion was calculated.

[0788] Specific preferred numerical values ​​include 4%, 13%, and 25%.

[0789] <<Foreign Matter in Photosensitive Composition Layer>>

[0790] From the viewpoint of pattern formation, the number of foreign particles having a diameter of 1.0 μm or more in the photosensitive composition layer is preferably 10 particles / mm. 2 Below, more preferably 5 / mm 2 the following.

[0791] The amount of foreign matter in the photosensitive composition layer is measured as follows.

[0792] Five random regions (1 mm x 1 mm) on the surface of the photosensitive composition layer were observed with the naked eye using an optical microscope from the normal direction of the surface of the photosensitive composition layer. The number of foreign matter with a diameter of 1.0 μm or more in each region was measured and the number of foreign matter was calculated by taking the arithmetic average.

[0793] As a specific preferred value, 0 / mm can be cited. 2 , 1 piece / mm 2 , 4 pieces / mm 2 , 8 pieces / mm 2 wait.

[0794] <<Haze of dissolved matter in photosensitive composition layer>>

[0795] From the viewpoint of suppressing the generation of aggregates during development, 1.0 cm 3 The haze of the solution obtained by forming a photosensitive composition layer is preferably 60% or less, more preferably 30% or less, further preferably 10% or less, and particularly preferably 1% or less.

[0796] The above-mentioned haze is measured as follows.

[0797] First, a 1.0 mass % sodium carbonate aqueous solution was prepared and the liquid temperature was adjusted to 30° C. Next, 1.0 cm 3 The photosensitive composition layer was formed. The mixture was stirred at 30°C for 4 hours while being careful not to mix in bubbles. After stirring, the haze of the solution after the photosensitive composition layer was dissolved was measured. The haze was measured using a haze meter as a measuring device, a liquid measuring unit and a liquid measuring cell with an optical path length of 20 mm.

[0798] As the haze meter, for example, a haze meter (model: NDH4000) manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD. can be preferably used. However, the haze meter is not limited to the above.

[0799] Specific preferred numerical values ​​include 0.4%, 1.0%, 9%, and 24%.

[0800] <Protective film>

[0801] The transfer film according to the present invention may have a protective film.

[0802] As the protective film, for example, a resin film having heat resistance and solvent resistance can be cited.

[0803] Examples of the protective film include polyolefin films such as polypropylene films and polyethylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, and polystyrene films.

[0804] Furthermore, as the protective film, a resin film made of the same material as that of the temporary support may be used.

[0805] As the protective film, a polyolefin film is preferred, a polypropylene film or a polyethylene film is more preferred, and a polyethylene film is further preferred.

[0806] The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, further preferably 5 μm to 40 μm, and particularly preferably 15 μm to 30 μm.

[0807] The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and is preferably 100 μm or less from the viewpoint of relatively low cost.

[0808] The number of fish eyes with a diameter of 80 μm or more contained in the protective film is preferably 5 / 1 m 2 the following.

[0809] Fisheyes are formed when foreign matter, undissolved matter, oxidative degradation products, etc. of the material enter the film when the film is manufactured by methods such as hot melting, kneading, extrusion, biaxial stretching, and casting.

[0810] The number of particles with a diameter of 3 μm or more contained in the protective film is preferably 30 particles / mm. 2 Below, more preferably 10 / mm 2 Below, more preferably 5 / mm 2 Thereby, it is possible to suppress defects caused by the transfer of the unevenness due to the particles contained in the protective film to the photosensitive composition layer.

[0811] From the viewpoint of providing windability, the arithmetic mean roughness Ra of the surface on the opposite side of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. On the other hand, the arithmetic mean roughness Ra of the surface on the opposite side of the surface of the protective film in contact with the photosensitive composition layer is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

[0812] From the viewpoint of suppressing defects during transfer, the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.03 μm or more. On the other hand, the surface roughness Ra of the surface of the protective film in contact with the photosensitive composition layer is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.30 μm or less.

[0813] The protective film may be a recycled product. As a recycled product, a product made of a film made of a product obtained by washing and making fragments of used films etc. As a specific example of a recycled product, the Ecouse series manufactured by TORAY INDUSTRIES, INC. may be cited.

[0814] <<Relationship between temporary support, photosensitive composition layer and protective film>>

[0815] In the transfer film involved in the present invention, it is preferred that the cured film obtained by curing the photosensitive composition layer has an elongation at break of 15% or more at 120°C, the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the temporary support is 50 nm or less, and the arithmetic mean roughness Ra of the surface on the photosensitive composition layer side of the protective film is 150 nm or less.

[0816] The transfer film according to the present invention preferably satisfies the following formula (T1).

[0817] X×Y<1500……Formula (T1)

[0818] In formula (T1), X represents the elongation at break of a cured film obtained by curing the photosensitive composition layer at 120°C (%), and Y represents the arithmetic mean roughness Ra (nm) of the surface of the temporary support on the photosensitive composition layer side.

[0819] More preferably, X×Y is 750 or less.

[0820] Specific numerical values ​​of X include 18%, 25%, 30%, 35% and the like.

[0821] Specific numerical values ​​of Y include 4 nm, 8 nm, 15 nm, and 30 nm.

[0822] Specific numerical values ​​of X×Y include 150, 200, 300, 360, 900, and the like.

[0823] In the transfer film of the present invention, the elongation at break of a cured film obtained by curing the photosensitive composition layer at 120° C. is preferably more than twice the elongation at break of a cured film obtained by curing the photosensitive composition layer at 23° C.

[0824] Regarding the elongation at break, an ultra-high pressure mercury lamp was used with an exposure dose of 120 mJ / cm 2 After the photosensitive composition layer with a thickness of 20 μm was exposed to light and cured, a high pressure mercury lamp was used at an exposure dose of 400 mJ / cm 2 The cured film was further exposed and heated at 145° C. for 30 minutes, and used as a test sample, and was measured by a tensile test.

[0825] The transfer film according to the present invention preferably satisfies the following formula (T2).

[0826] Y≤Z……Formula (T2)

[0827] In formula (T2), Y represents the arithmetic mean roughness Ra value (nm) of the surface on the photosensitive composition layer side of the temporary support, and Z represents the arithmetic mean roughness Ra value (nm) of the surface on the photosensitive composition layer side of the protective film.

[0828] <<Application of transfer film>>

[0829] The transfer film according to the present invention can be used in various applications.

[0830] The transfer film according to the present invention can be used for, for example, a black matrix (so-called black barrier ribs) or the like.

[0831] <Method for producing transfer film>

[0832] The method for producing the transfer film according to the present invention is not particularly limited, and a known method can be used.

[0833] As a method for producing the transfer film involved in the present invention, for example, from the viewpoint of excellent productivity, there can be cited a method comprising the following steps: a step of coating a photosensitive composition on the surface of a temporary support to form a coating film; and a step of drying the formed coating film to form a photosensitive composition layer.

[0834] Examples of a method for coating the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (ie, a slit coating method).

[0835] Examples of the method for drying the coating film include natural drying, heating drying, and reduced-pressure drying. These drying methods can be used alone or in combination of two or more.

[0836] As a method for drying the coating film, heating drying and / or reduced pressure drying are preferred.

[0837] In the present invention, "drying" means removing at least a part of the solvent contained in the composition.

[0838] The drying temperature is preferably 80° C. or higher, more preferably 90° C. or higher. The upper limit of the drying temperature is preferably 130° C. or lower, more preferably 120° C. or lower. Drying may be performed while continuously changing the temperature.

[0839] The drying time is preferably 20 seconds or longer, more preferably 40 seconds or longer, and further preferably 60 seconds or longer. The upper limit of the drying time is not particularly limited, but is, for example, preferably 600 seconds or shorter, and more preferably 300 seconds or shorter.

[0840] In the transfer film involved in the present invention, when there is a protective film on the surface of the photosensitive composition layer on the opposite side of the temporary support, for example, by pressing the protective film on the photosensitive composition layer formed as described above and bonding it, a transfer film having a structure of temporary support / photosensitive composition layer / protective film can be manufactured.

[0841] The method for laminating the protective film and the photosensitive composition layer is not particularly limited, and a known method can be used.

[0842] When the protective film and the photosensitive composition layer are bonded together, for example, a known laminator such as a vacuum laminator and an automatic laminator can be used.

[0843] The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0844] The transfer film produced as described above can be wound up to produce and store a roll-shaped transfer film. The roll-shaped transfer film can be directly provided in this form to a step of laminating the film with a substrate in a roll-to-roll method.

[0845] [Method for producing laminate]

[0846] The method for manufacturing a laminate involved in the present invention (hereinafter, also referred to as the "manufacturing method involved in the present invention") is a method for manufacturing a laminate having a black pattern, which comprises, in sequence: a process of forming a photosensitive composition layer containing the above-mentioned photosensitive composition involved in the present invention on a substrate (hereinafter, also referred to as the "forming process"); a process of pattern-exposing the above-mentioned photosensitive composition layer (hereinafter, also referred to as the "exposure process"); and a process of developing the above-mentioned photosensitive composition layer (hereinafter, also referred to as the "developing process"). The method for manufacturing a laminate includes a process of coloring a specific color material precursor to black after the above-mentioned pattern exposure process (hereinafter, also referred to as the "developing process").

[0847] Hereinafter, the sequence of the above steps will be described in detail.

[0848] <Formation process>

[0849] The forming step is a step of forming a photosensitive composition layer containing the photosensitive composition according to the present invention on a substrate.

[0850] The forming step may be a step of forming a photosensitive composition layer containing the photosensitive composition involved in the present invention on a substrate. For example, it may be a step of forming a photosensitive composition layer by forming a coating film of the photosensitive composition involved in the present invention on a substrate and drying the formed coating film. Alternatively, it may be a step of forming a photosensitive composition layer on a substrate by using the transfer film involved in the present invention and bringing the surface of the photosensitive composition layer on the side opposite to the temporary support into contact with the substrate and bonding them together (hereinafter also referred to as a "bonding step"), but preferably it is a bonding step.

[0851] In the laminating step, the surface of the photosensitive composition layer of the transfer film of the present invention on the side opposite to the temporary support is brought into contact with the substrate and laminated, thereby forming a photosensitive composition layer on the substrate. In addition, in the transfer film of the present invention, when a protective film is provided on the surface of the photosensitive composition layer on the side opposite to the temporary support, the laminating step is performed after the protective film is peeled off.

[0852] The method for bonding the photosensitive composition layer and the substrate is not particularly limited, and a known method can be used.

[0853] For bonding the photosensitive composition layer and the substrate, for example, a known laminator such as a vacuum laminator and an automatic laminator can be used.

[0854] The laminator preferably includes any heatable roller such as a rubber roller and is capable of applying pressure and heat.

[0855] The lamination temperature is preferably, for example, 70°C to 130°C.

[0856] As the substrate, a glass substrate or a resin substrate is preferred.

[0857] The substrate is preferably a transparent substrate, more preferably a transparent resin substrate.

[0858] The refractive index of the substrate is preferably 1.50 to 1.52.

[0859] Examples of the glass substrate include tempered glass such as Gorilla Glass (registered trademark) manufactured by Corning Incorporated Co., Ltd.

[0860] The thickness of the glass substrate is preferably 0.01 mm to 1.1 mm, more preferably 0.1 mm to 0.7 mm.

[0861] Examples of the resin substrate include substrates made of resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), triacetyl cellulose (TAC), polyimide (PI), polybenzoxazole (PBO), and cycloolefin polymer (COP).

[0862] The thickness of the resin substrate is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm.

[0863] As the material of the substrate, for example, materials described in Japanese Patent Application Laid-Open Nos. 2010-86684, 2010-152809, and 2010-257492 can be preferably used.

[0864] <Exposure Process>

[0865] The exposure step is a step of pattern-exposing the photosensitive composition layer.

[0866] “Pattern exposure” refers to exposure in a patterned manner, that is, exposure with exposed areas and unexposed areas. The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited and can be adjusted appropriately.

[0867] For example, when the photosensitive composition layer is a negative type, the exposed portion of the photosensitive composition layer on the substrate under pattern exposure is cured to eventually form a cured film. On the other hand, the non-exposed portion of the photosensitive composition layer on the substrate under pattern exposure is not cured, but is dissolved and removed by the developer in the development step described later. The non-exposed portion can form an opening of the cured film after the development step.

[0868] As the light source for pattern exposure, any light of a wavelength region (e.g., 365 nm or 405 nm) that can irradiate the photosensitive composition layer can be appropriately selected and used. Among them, the dominant wavelength of the exposure light for pattern exposure is preferably 365 nm. In addition, the dominant wavelength refers to the wavelength with the highest intensity.

[0869] Examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.

[0870] The exposure dose is preferably 5 mJ / cm 2 ~200mJ / cm 2 , more preferably 10 mJ / cm 2 ~200mJ / cm 2 .

[0871] When a photosensitive composition layer is formed on a substrate using a transfer film, pattern exposure may be performed after peeling off the temporary support, or pattern exposure may be performed through the temporary support before peeling off the temporary support and then peeling off the temporary support.

[0872] From the viewpoint of preventing contamination of the mask due to contact with the photosensitive composition layer and avoiding the influence of foreign matter attached to the mask on exposure, it is preferred to perform pattern exposure without peeling the temporary support.

[0873] From the viewpoint of improving resolution by suppressing scattering of exposure light due to the temporary support and suppressing diffraction of light that has passed through the mask, it is preferred to perform pattern exposure after peeling off the temporary support.

[0874] The pattern exposure may be exposure through a mask or digital exposure using laser or the like.

[0875] Examples of a base material of a mask when performing exposure through a mask include a quartz mask, a soda-lime glass mask, and a film mask.

[0876] Among these, a quartz mask is preferably excellent in dimensional accuracy, and a thin film mask is easily enlarged, so it is preferred.

[0877] As the substrate of the film mask, a polyester film is preferred, and a polyethylene terephthalate film is more preferred.

[0878] A specific example of the substrate of the thin film mask is XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.).

[0879] Preferred aspects of the light source, exposure amount, and exposure method used for exposure are described, for example, in paragraphs

[0146] to

[0147] of International Publication No. 2018 / 155193, and these contents are incorporated into this specification.

[0880] <Development Process>

[0881] The development step is a step of developing the photosensitive composition layer after pattern exposure.

[0882] The pattern is formed by developing the photosensitive composition layer after pattern exposure.

[0883] The development of the photosensitive composition layer after the pattern exposure can be performed using a developer.

[0884] As the developer, an alkaline aqueous solution is preferred.

[0885] Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

[0886] The pH of the alkaline aqueous solution at 25°C is preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12.

[0887] The content of the basic compound in the basic aqueous solution is preferably 0.1% by mass to 5% by mass, and more preferably 0.1% by mass to 3% by mass, relative to the total mass of the basic aqueous solution.

[0888] In the present invention, as a developer preferably used, for example, there can be mentioned the developer described in paragraph

[0194] of International Publication No. 2015 / 093271.

[0889] Examples of the method of development include spin immersion development, shower development, shower development, spin development, and immersion development.

[0890] In the present invention, as a development method preferably used, for example, there can be mentioned the development method described in paragraph

[0195] of International Publication No. 2015 / 093271.

[0891] The development process may include: a stage of performing the development described above; and a stage of performing a heat treatment (also referred to as “post-baking”) on the pattern obtained by the development described above.

[0892] The temperature of the post-baking is preferably 80° C. to 260° C., and more preferably 90° C. to 160° C. The time of the post-baking is preferably 1 minute to 180 minutes, and more preferably 10 minutes to 60 minutes.

[0893] <Color Development Process>

[0894] The production method according to the present invention includes a step of developing a specific color material precursor contained in the photosensitive composition layer into black color (ie, a color development step) after the pattern exposure step (ie, an exposure step).

[0895] The color development step may be performed after the exposure step, for example, during the development step or after the development step. In addition, "after the exposure step" means "after exposure for curing the photosensitive composition layer".

[0896] In the color development step, a stimulus is applied to the photosensitive composition layer and / or the specific color material precursor contained in the photosensitive composition layer, thereby causing the specific color material precursor to develop black color.

[0897] The method of causing the specific color material precursor to develop black color varies depending on the stimulus for causing the specific color material precursor to develop black color.

[0898] For example, when the stimulus is heat, there may be mentioned a method of heating the photosensitive composition layer after the exposure step, etc. The method of heating the photosensitive composition layer after the exposure step is not particularly limited, and a known heating method may be employed.

[0899] Examples of the heating means include an oven, a hot plate, and a heating roller.

[0900] The heating temperature is not particularly limited as long as it is a temperature at which the specific color material precursor develops black, and can be appropriately set according to the black color development temperature of the specific color material precursor. For example, when the specific color material precursor is a compound represented by formula (1), the heating temperature is preferably 80°C to 260°C.

[0901] The heating time is not particularly limited and can be appropriately set according to the degree of color development. When the photosensitive composition layer contains a thermoplastic resin, the heating time is preferably appropriately adjusted, for example, shortened, in consideration of maintaining the pattern shape.

[0902] As a method for making a specific color material precursor develop black by heat, it is preferred to perform post-baking in a development process so that the specific color material precursor contained in the photosensitive composition layer develops black. For example, when the specific color material precursor is a compound represented by formula (1), a pattern containing the specific color material precursor obtained by development is heated during post-baking, so that the compound represented by formula (1) reacts with oxygen in the air to become an oxidized body, thereby developing black.

[0903] For example, when the stimulus is an acid, there may be mentioned a method in which an acid generator or the like is used to generate an acid in the photosensitive composition layer after the exposure step.

[0904] As a method for generating an acid in the photosensitive composition layer after the exposure step using an acid generator, for example, there can be mentioned a method utilizing the difference in reaction rate between a curing reaction by photoradical polymerization of a polymerizable monomer and a color development reaction of a specific color material precursor caused by an acid generated by a photoacid generator.

[0905] For example, when the specific color material precursor is a leuco dye, the curing reaction by photoradical polymerization of the polymerizable monomer or the like precedes the color development reaction of the leuco dye caused by the acid generated by the photoacid generator, and thus the curing reaction is not easily affected by the color development reaction.

[0906] In addition, there is no clear distinction between the curing step of performing a curing reaction and the coloring step of performing a coloring reaction, but since the coloring step is not a step of exposing the photosensitive composition to cure, it is not included in the exposure step in the manufacturing method involved in the present invention.

[0907] Furthermore, as a method of generating an acid in the photosensitive composition layer after the exposure step by an acid generator, for example, there can be mentioned a method of utilizing the difference between the absorption spectrum of the photoradical polymerization initiator and the absorption spectrum of the photoacid generator.

[0908] For example, when a polymerizable monomer is subjected to a curing reaction by photoradical polymerization, light having a wavelength absorbed by a photoradical polymerization initiator and not absorbed by a photoacid generator is irradiated, and when a specific color material precursor is colored, light having a wavelength not absorbed by a photoacid generator is irradiated, thereby making the curing reaction less susceptible to the coloring reaction.

[0909] Furthermore, for example, when the stimulus is an acid, a method of bringing the photosensitive composition layer after the exposure step into contact with an acidic solution may also be mentioned.

[0910] Examples of a method for bringing the photosensitive composition layer after the exposure step into contact with the acidic solution include immersing in the acidic solution, spraying the acidic solution, and applying the acidic solution.

[0911] Examples of the acidic solution include a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, and a nitric acid aqueous solution.

[0912] Among these, as the acidic solution, an aqueous hydrochloric acid solution is preferable.

[0913] The concentration of the aqueous hydrochloric acid solution is preferably, for example, 5% by mass to 15% by mass.

[0914] Furthermore, in the method of making the specific color material precursor develop black, when the stimulus for making the specific color material precursor develop black is, for example, light, a method of irradiating the photosensitive composition layer after the exposure process with light, etc., when it is, for example, a base, a method of generating a base in the photosensitive composition layer after the exposure process by a base generator, etc., etc., and when it is, for example, a free radical, a method of generating free radicals in the photosensitive composition layer after the exposure process by a free radical generator, etc., etc., etc., can be mentioned. Any method is preferably performed by appropriately adjusting within a range that does not interfere with the exposure process.

[0915] The thickness of the black pattern of the laminate produced by the production method of the present invention is preferably 5 μm or more, more preferably 10 μm or more. For example, from the viewpoint of workability, the upper limit is preferably 20 μm or less, more preferably 15 μm or less.

[0916] If the exposed film is black, the exposure light is absorbed, so the polymerization and curing are insufficient, and it is difficult to form a thick film pattern. In contrast, in the manufacturing method of the present invention, by exposing the photosensitive composition layer before the specific color material precursor is colored black, that is, the photosensitive composition layer that does not appear black, the exposure light is difficult to be absorbed, and sufficient polymerization and curing can be performed, so that the formation of a black pattern with a thickness of 5 μm or more can be achieved.

[0917] [Laminate produced by the production method of the present invention]

[0918] The laminated body produced by the production method according to the present invention has a black pattern.

[0919] The black pattern of the laminated body produced by the production method according to the present invention has excellent light shielding properties and exhibits a high aspect ratio.

[0920] The film thickness of the black pattern of the laminated body produced by the production method according to the present invention is preferably 5 μm or more, more preferably 10 μm or more.

[0921] When the film thickness of the black pattern is 5 μm or more, for example, when the black pattern is used as a partition wall, there is a tendency that color mixing between pixels is further suppressed.

[0922] From the viewpoint of workability, the upper limit of the film thickness of the black pattern is preferably 20 μm or less, and more preferably 15 μm or less.

[0923] The absorbance of the black pattern of the laminate produced by the production method of the present invention at a wavelength of 365 nm is preferably 2.0 or more, more preferably 3.0 or more. The upper limit is not particularly limited, and for example, it may be 5.0 or less.

[0924] The average absorbance of the black pattern of the laminate produced by the production method of the present invention at a wavelength of 400 nm to 700 nm is preferably 2.0 or more, more preferably 3.0 or more. The upper limit is not particularly limited, and may be, for example, 5.0 or less.

[0925] The aspect ratio of the film thickness of the black pattern to the line width of the bottom of the laminate produced by the production method of the present invention is preferably 1.0 or more, more preferably 2.0 or more. The upper limit is not particularly limited, and for example, 10.0 or less and 5.0 or less can be mentioned.

[0926] In the present invention, the aspect ratio, which is the ratio of the film thickness to the bottom line width, is determined by observing the cross section of the black pattern using a SEM (scanning electron microscope) and measuring the film thickness and bottom line width of the black pattern, and by the following formula.

[0927] "Aspect ratio" = "Film thickness" / "Line width at bottom"

[0928] [Laminated body]

[0929] The laminated body involved in the present invention has a substrate and a black pattern, the film thickness of the above-mentioned black pattern is 5μm or more, the ratio of the film thickness to the line width at the bottom, that is, the aspect ratio is 1.0 or more, and the average absorbance at a wavelength of 400nm to 700nm is 2.0 or more.

[0930] The laminated body according to the present invention has excellent light shielding properties and a thick film with a high aspect ratio pattern.

[0931] <Base Material>

[0932] The laminated body according to the present invention has a substrate.

[0933] The substrate of the laminate according to the present invention has the same meaning as the substrate in the production method according to the present invention, and preferred embodiments thereof are also the same, so description thereof is omitted here.

[0934] <Black pattern>

[0935] The laminated body according to the present invention has a black pattern.

[0936] The thickness of the black pattern of the laminated body according to the present invention is 5 μm or more, preferably 10 μm or more. The upper limit is not particularly limited, but is, for example, preferably 20 μm or less, more preferably 15 μm or less.

[0937] The aspect ratio of the film thickness of the black pattern of the laminated body according to the present invention to the line width of the bottom is 1.0 or more, preferably 2.0 or more. The upper limit is not particularly limited, and for example, 10.0 or less and 5.0 or less may be mentioned.

[0938] The average absorbance of the black pattern of the laminated body according to the present invention at a wavelength of 400 nm to 700 nm is 2.0 or more, preferably 3.0 or more. The upper limit is not particularly limited, and for example, is 5.0 or less.

[0939] The ratio of the top line width to the bottom line width of the black pattern of the laminated body of the present invention (top line width / bottom line width) is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. The ratio of the top line width to the bottom line width of 0.8 to 1.2 indicates that the black pattern has excellent rectangularity.

[0940] In the present invention, a cross-section of the black pattern is observed using a SEM (scanning electron microscope), and the bottom line width and the top line width of the black pattern are measured to obtain the ratio of the top line width to the bottom line width (top line width / bottom line width).

[0941] The black pattern of the laminated body according to the present invention preferably contains a color material represented by the following formula (I).

[0942] The color material represented by formula (I) is an oxidized product of the compound represented by formula (1) above, and is a compound formed when the compound represented by formula (1) is subjected to thermal stimulation and reacts with oxygen in the air.

[0943] In addition, when tautomers and / or geometric isomers exist in the compound represented by formula (I), the existing tautomers and / or geometric isomers are included in the compound represented by formula (I).

[0944] [Chemical formula 41]

[0945]

[0946] In formula (I), X 1a , X 2a , X 3a , X 4a , Y 1a and Y 2a Each independently represents an oxygen atom, a sulfur atom or NL 1a .L1a represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group. A', B' and C' each independently represent an aromatic ring.

[0947] X in formula (I) 1a , X 2a , X 3a , X 4a , Y 1a and Y 2a The meaning of is the same as X in the above formula (1) 1 , X 2 , X 3 , X 4 , Y 1 and Y 2 The meanings are the same and the preferred embodiments are also the same, so the description is omitted here.

[0948] A', B' and C' in formula (I) have the same meanings as A, B and C in formula (1) above, and preferred embodiments thereof are also the same, so their description is omitted here.

[0949] When the black pattern of the laminated body according to the present invention contains a color material represented by formula (I), it may contain only one color material represented by formula (I) or may contain two or more color materials represented by formula (I).

[0950] When the black pattern possessed by the laminate involved in the present invention contains a colorant represented by formula (I), the content of the colorant represented by formula (I) in the black pattern is not particularly limited, but for example, it is preferably 5% by mass to 25% by mass, and more preferably 10% by mass to 20% by mass, relative to the total mass of the black pattern.

[0951] [Micro LED Display]

[0952] The micro LED display according to the present invention includes the laminated body according to the present invention.

[0953] The micro LED display of the present invention comprises the laminate of the present invention, i.e., a substrate and a black pattern having a thickness of 5 μm or more, an aspect ratio of the bottom thickness to the line width of 1.0 or more, and an average absorbance of 2.0 or more at a wavelength of 400 nm to 700 nm. The black pattern can function as a partition wall.

[0954] As a mode of the micro LED display involved in the present invention, for example, the following mode can be cited: a micro LED array substrate having a plurality of micro LEDs, a partition provided between the plurality of micro LEDs, and a substrate opposite to the micro LED array substrate, wherein the partition is a black pattern in the laminated body involved in the present invention, and the substrate opposite to the micro LED array substrate is a base material in the laminated body involved in the present invention. In the micro LED display of this mode, by having a partition with excellent light shielding properties and a high aspect ratio, light leakage from the micro LEDs and the light-emitting parts of each pixel and color mixing between each pixel can be suppressed, thereby improving the contrast.

[0955] In the micro LED display of the present invention, the width of the black pattern that can function as a partition wall is preferably greater than 3 μm from the viewpoint of pattern processability, and is preferably less than 100 μm from the viewpoint of ensuring more micro LED light emitting areas and further improving brightness.

[0956] Example

[0957] Below, the present invention is further described in detail by examples. The materials, usage, ratio, processing content, processing sequence etc. shown in the following examples can be appropriately changed as long as they do not depart from the purpose of the present invention. Therefore, the scope of the present invention should not be interpreted in a limited manner by the examples shown below.

[0958] In addition, unless otherwise specified, "part" and "%" are based on mass.

[0959] In the following examples, the weight average molecular weight of a resin is a weight average molecular weight determined by polystyrene conversion using gel permeation chromatography (GPC).

[0960] [Synthesis of Binder Polymer P-1]

[0961] Into a 1000 mL flask, 82.4 g of propylene glycol monomethyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation) was placed, and the mixture was heated to 90° C. under a nitrogen stream. To the heated propylene glycol monomethyl ether, a solution prepared by dissolving 38.4 g of styrene [manufactured by FUJIFILM Wako Pure Chemical Corporation], 30.1 g of dicyclopentanyl methacrylate [trade name: FANCRYL (registered trademark) FA-513M, manufactured by Hitachi Chemical Co., Ltd.] and 34.0 g of methacrylic acid [manufactured by FUJIFILM Wako Pure Chemical Corporation] in 20 g of propylene glycol monomethyl ether, and a solution prepared by dissolving 5.4 g of dimethyl 2,2'-azobis(2-methylpropionate) [trade name: V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation] as a polymerization initiator in 43.6 g of propylene glycol monomethyl ether acetate [manufactured by FUJIFILM Wako Pure Chemical Corporation] were simultaneously added dropwise over 3 hours.

[0962] After the dropwise addition was completed, 0.75 g of a polymerization initiator (V-601) was added three times every 1 hour to the solution after the dropwise addition was completed, and the solution after the addition was further reacted for 3 hours.

[0963] Next, the obtained solution was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether.

[0964] Next, the diluted solution was heated to 100° C. under air flow.

[0965] Next, 0.53 g of tetraethylammonium bromide [manufactured by FUJIFILM Wako Pure Chemical Corporation] and 0.26 g of p-methoxyphenol [manufactured by FUJIFILM Wako Pure Chemical Corporation] were added to the heated solution.

[0966] Next, 25.5 g of glycidyl methacrylate [trade name: BLEMMER (registered trademark) GH, manufactured by NOF CORPORATION] was added dropwise to the obtained solution over 20 minutes.

[0967] Next, the obtained solution was reacted at 100° C. for 7 hours to obtain 350.6 g of a solution of the binder polymer P-1.

[0968] The solid content concentration of the obtained solution was 36.3% by mass.

[0969] The obtained binder polymer P-1 contained the constituent units shown in Table 1, had a weight average molecular weight (Mw) of 17,000, a degree of dispersion (Mw / Mn) of 2.4, and an acid value of 94.5 mgKOH / g.

[0970] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by standard polystyrene conversion by gel permeation chromatography (GPC), and were also determined by the same method for the binder polymer P-2 described later.

[0971] The acid value was measured according to the method described in JIS K 0070: 1992. The acid value was also measured by the same method in the binder polymer P-2 described below.

[0972] The amount of residual monomers measured by gas chromatography (GC) was less than 0.1% by mass based on the solid content of the binder polymer P-1 for all monomers.

[0973] The “solid content” refers to all components in the solution of the binder polymer P-1 excluding the solvent, and even if the components are in a liquid state, they are included in the solid content. The same applies to the binder polymer P-2 described below.

[0974] [Synthesis of Binder Polymer P-2]

[0975] A 2000 mL flask was charged with 60 g of propylene glycol monomethyl ether acetate [trade name: PGM-Ac, manufactured by Sanwa Chemical Industry Co., Ltd.] and 240 g of propylene glycol monomethyl ether [trade name: PGM, manufactured by Sanwa Chemical Industry Co., Ltd.] Then, the liquid in the flask was heated to 90° C. while being stirred at 250 rpm (revolution per minute).

[0976] Next, 107.1 g of methacrylic acid [trade name: Acryester (registered trademark) M, manufactured by Mitsubishi Chemical Corporation], 5.46 g of methyl methacrylate [trade name: MMA, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.] and 231.42 g of cyclohexyl methacrylate [trade name: CHMA, manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.] were mixed and diluted with 60 g of propylene glycol monomethyl ether acetate to prepare a dropping solution (1).

[0977] Next, 9.637 g of dimethyl 2,2′-azobis(2-methylpropionate) [trade name: V-601, manufactured by FUJIFILM Wako Pure Chemical Corporation] as a polymerization initiator was dissolved in 136.56 g of propylene glycol monomethyl ether acetate to prepare a dropping solution (2).

[0978] The dropwise addition liquid (1) and the dropwise addition liquid (2) prepared in the above are simultaneously dropped into a 2000 mL flask containing a liquid heated to the above 90°C over 3 hours. Next, the container containing the dropwise addition liquid (1) is cleaned with 12 g of propylene glycol monomethyl ether acetate, and the obtained cleaning liquid is dropped into the above 2000 mL flask. Next, the container containing the dropwise addition liquid (2) is cleaned with 6 g of propylene glycol monomethyl ether acetate, and the obtained cleaning liquid is dropped into the above 2000 mL flask. During the dropping of these cleaning liquids, the reaction liquid in the above 2000 mL flask was maintained at a liquid temperature of 90°C and stirred at a stirring speed of 250 rpm. After the dropping, as a post-reaction, the reaction liquid in the flask was maintained at a liquid temperature of 90°C and stirred for further 1 hour at a stirring speed of 250 rpm.

[0979] Next, as the first additional addition of the polymerization initiator, 2.401 g of V-601 was added to the reaction solution after the post-reaction. Next, the container containing V-601 was rinsed with 6 g of propylene glycol monomethyl ether acetate, and the obtained rinsed solution was further added to the reaction solution, followed by stirring at 90° C. for 1 hour.

[0980] Next, 2.401 g of V-601 was added to the obtained reaction solution as the second additional addition of the polymerization initiator. Next, the container containing V-601 was washed with 6 g of propylene glycol monomethyl ether acetate, and the obtained washing solution was further added to the reaction solution, followed by stirring at 90° C. for 1 hour.

[0981] Next, 2.401 g of V-601 was added to the obtained reaction solution as the third additional addition of the polymerization initiator. Next, the container containing V-601 was washed with 6 g of propylene glycol monomethyl ether acetate, and the obtained washing solution was further added to the reaction solution, followed by stirring at 90° C. for 3 hours.

[0982] Next, 178.66 g of propylene glycol monomethyl ether acetate was added to the obtained reaction solution. Next, 1.8 g of tetraethylammonium bromide [manufactured by FUJIFILM Wako Pure Chemical Corporation] and 0.8 g of hydroquinone monomethyl ether [manufactured by FUJIFILM Wako Pure Chemical Corporation] were added to the obtained reaction solution. Next, 6 g of propylene glycol monomethyl ether acetate was used to wash the container containing tetraethylammonium bromide and the container containing hydroquinone monomethyl ether, respectively, and the obtained washing liquid was further added to the reaction solution.

[0983] Next, the temperature of the obtained reaction solution was raised to 100°C.

[0984] Next, 76.03 g of glycidyl methacrylate [trade name: BLEMMER (registered trademark) G, manufactured by NOF CORPORATION] was added dropwise to the heated reaction solution over 1 hour. Next, the container containing BLEMMER G was rinsed with 6 g of propylene glycol monomethyl ether acetate, and the obtained rinsed solution was further added to the reaction solution, followed by stirring at 100° C. for 6 hours for addition reaction.

[0985] Next, the obtained reaction liquid was cooled and then filtered using a dust removal mesh filter (mesh size: 100 mesh) to obtain 1158 g of a solution of the binder polymer P-2.

[0986] The solid content concentration of the obtained solution was 36.3% by mass.

[0987] The obtained binder polymer P-2 contained the constituent units shown in Table 1, had a weight average molecular weight (Mw) of 27,000, a degree of dispersion (Mw / Mn) of 1.8, and an acid value of 95.0 mgKOH / g.

[0988] The amount of residual monomers measured by gas chromatography (GC) was less than 0.1% by mass based on the solid content of the binder polymer P-2 for all monomers.

[0989] [Table 1]

[0990]

[0991] In Table 1, structural units other than the structural unit having a (meth)acryloyl group are represented by the abbreviations of the monomers used to form each structural unit.

[0992] The structural unit having a (meth)acryloyl group is represented as an addition structure of monomers. For example, MAA-GMA means a structural unit obtained by adding glycidyl methacrylate (GMA) to a structural unit derived from methacrylic acid (MAA).

[0993] The following abbreviations represent the following monomers, respectively.

[0994] "St": Styrene

[0995] "CHMA": Cyclohexyl methacrylate

[0996] “MAA”: methacrylic acid

[0997] "MMA": methyl methacrylate

[0998] "GMA": Glycidyl methacrylate

[0999] "DCPMA": dicyclopentyl methacrylate

[1000] [Synthesis of a color material precursor that develops black color upon stimulation]

[1001] According to the following scheme, the following compounds (1) and (3) were synthesized. 2 correspond.

[1002] [Chemical formula 42]

[1003]

[1004] [Chemical formula 43]

[1005]

[1006] [Chemical formula 44]

[1007]

[1008] [Synthesis of Compound (1)]

[1009] Referring to J.Am.Chem.Soc.2015,137,15947-15956, a compound corresponding to the black compound in the above scheme was synthesized using isatin as a starting material [the following compound (100)]. After adding 150 mL of tetrahydrofuran (THF) [containing a stabilizer, Wako first grade, manufactured by FUJIFILM Wako Pure Chemical Corporation] to a 300 mL three-necked flask, 10.0 g of the synthesized compound (100) and 4.9 g of zinc powder [Wako special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation] were added. The three-necked flask was immersed in ice water, the internal temperature was maintained at 5°C or less, and 15 mL of trifluoroacetic acid [Wako special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation] was added dropwise. After the addition was completed, the external equipment was removed and the reaction was allowed to proceed in a water bath for 2 hours so that the internal temperature would not exceed 40°C. The reaction solution was filtered through diatomaceous earth, and 10 mL of ultrapure water was added to the filtrate, and THF was removed by distillation at 40°C under reduced pressure. The precipitated gray solid was filtered and rinsed with 300 mL of ultrapure water. It was dried for 12 hours using a blower dryer set at 50°C to obtain 4.5 g of compound (1) (yield 46%).

[1010] [Chemical formula 45]

[1011]

[1012] pass 1 H-NMR confirmed that the structure of the obtained compound (1) was the structure of the above-mentioned compound (1). The NMR data of the obtained compound (1) are shown below.

[1013] <NMR data of compound (1)>

[1014] 1 H-NMR(CDCl3-d)δ=0.80-1.90(m, 30H), 3.30-3.70(m, 4H), 4.20-4.50(s×3, 4H), 6.20-6.50(m, 2H), 6.80-7.20(m, 6H), 7.30-7.40(m, 2H)

[1015] [Synthesis of Compound (3)]

[1016] With reference to Journal of Medicinal Chemistry, 2008, 51, 4932-4947, isatin was reacted with 1-bromohexane to synthesize an isatin derivative. Using the synthesized isatin derivative, compound (3) was synthesized by the same method as compound (1) above.

[1017] pass 1 H-NMR confirmed that the structure of the obtained compound (3) was the structure of the above-mentioned compound (3). The NMR data of the obtained compound (3) are shown below.

[1018] <NMR data of compound (3)>

[1019] 1 H-NMR (CDCl3-d) δ = 0.69-0.71 (t, 6H), 3.35-3.76 (m, 12H), 4.20-4.50 (s×3, 4H), 6.20-6.50 (m, 2H), 6.80-7.20 (m, 6H), 7.30-7.40 (m, 2H)

[1020] [Synthesis of compound (2)]

[1021] In the above scheme, a black compound [compound (101) having the following structure] is synthesized directly from isatin without passing through an isatin derivative. After adding 100 mL of N,N-dimethylformamide (DMF) [Wako special grade, manufactured by FUJIFILM Wako Pure Chemical Corporation] to a 300 mL three-necked flask, 10.0 g of compound (101) and 1.0 g of Palladium 10% on Carbon [trade name, manufactured by Tokyo Chemical Industry Co., Ltd.] are further added. A balloon filled with nitrogen is installed on the flask, and the inside of the flask is degassed and then replaced with nitrogen. The reaction is allowed to react for 2 hours at room temperature under a nitrogen atmosphere. The reaction solution is filtered with diatomaceous earth, and the diatomaceous earth is rinsed with ethyl acetate. The filtrate is placed in an evaporator in a hot water bath at 40°C, and the ethyl acetate is distilled off to obtain a DMF solution containing the target compound. The DMF solution was purified by silica gel column chromatography, and the fraction containing the target product was put into the evaporator again to obtain 10 mg (yield 0.22%) of the precipitated gray compound (2).

[1022] [Chemical formula 46]

[1023]

[1024] pass 1H-NMR confirmed that the structure of the obtained compound (2) was the structure of the above-mentioned compound (2). The NMR data of the obtained compound (2) are shown below.

[1025] <NMR data of compound (2)>

[1026] 1 H-NMR (DMSO-d6) δ = 4.25-4.40 (m, 2H), 4.75-4.84 (m, 2H), 6.47-6.55 (m, 1H), 6.70-7.00 (m, 7H), 7.10-7.32 (m, 2H)

[1027] [Synthesis of Compound (65)]

[1028] Compound (65) was obtained in the same manner as in the synthesis of compound (1), except that "5-(bromomethyl)undecane" was used instead of "2-ethylhexyl bromide".

[1029] pass 1 H-NMR confirmed that the structure of the obtained compound (65) was the structure of the above-mentioned compound (65). The NMR data of the obtained compound (65) is shown below.

[1030] <NMR data of compound (65)>

[1031] 1 H-NMR (CDCl3) δ = 0.83-0.89 (m, 12H), 0.90-1.50 (m, 32H), 1.60-1.78 (brs×2, 2H), 3.38- 3.60(m, 4H), 4.25-4.48(m, 4H), 6.23-6.50(m, 2H), 6.82-7.07(m, 6H), 7.33-7.40(m, 2H)

[1032] [Color evaluation of color material precursor]

[1033] 1.1 mg of compound (1) was dissolved in 50 mL of tetrahydrofuran (THF) [containing a stabilizer, Wako grade 1, manufactured by FUJIFILM WakoPure Chemical Corporation] to prepare a THF solution of compound (1). Next, the prepared THF solution of compound (1) was added to a 1 cm colorimetric cell, and the absorption spectrum was measured using a spectrophotometer [model: UV-1800, manufactured by Shimadzu Corporation] as a measuring device, and the molar absorption coefficient at each wavelength was calculated for every 1 nm. Then, the average molar absorption coefficient of any continuous 100 nm range within the wavelength range of 400 nm to 700 nm was calculated, and the color of the color material precursor was evaluated according to the following evaluation criteria.

[1034] Regarding compound (3), compound (2), compound (65), 2'-anilino-6'-(dibutylamino)-3'-methylfluoran [manufactured by Tokyo Kagaku Kogyo Co., Ltd.] and BLACK 305 [manufactured by Fukui Yamada Chemical Co., Ltd.], the average molar absorption coefficient was calculated by the same procedure as in the above-mentioned compound (1), and the color of the color material precursor was evaluated according to the following evaluation criteria.

[1035] Table 2 shows the color evaluation results of the color material precursors.

[1036] The evaluation result is preferably "A", "B" or "C".

[1037] -Evaluation Criteria-

[1038] A: The average molar absorption coefficient is 100 L / (mol·cm) or less.

[1039] B: The average molar absorption coefficient is within the range of more than 100 L / (mol·cm) and 200 L / (mol·cm) or less.

[1040] C: The average molar absorption coefficient is within the range of more than 200 L / (mol·cm) and 400 L / (mol·cm).

[1041] D: The average molar absorption coefficient exceeds 400 L / (mol·cm).

[1042] [Evaluation of black color development of color material precursor]

[1043] 1.1 mg of compound (1) was heated for 60 minutes in an environment with an atmospheric temperature of 230° C. to develop a black color. The obtained black color-developed body of compound (1) was dissolved in 50 mL of tetrahydrofuran (THF) (containing a stabilizer, Wako grade 1, manufactured by FUJIFILM Wako Pure Chemical Corporation) to prepare a THF solution of the black color-developed body of compound (1). Next, the THF solution of the prepared black color-developed body of compound (1) was placed in a 1 cm colorimetric cell, and a spectrophotometer (model: UV-1800, manufactured by SHIMADZU CORPORATION) was used as a measuring device to measure the absorption spectrum, and the maximum absorption wavelength and the molar absorption coefficient at the maximum absorption wavelength were calculated (wherein, when there are two or more maximum absorption wavelengths, the molar absorption coefficient at the wavelength with the maximum absorption was calculated). In addition, the molar absorption coefficient at each wavelength was calculated for every 1 nm, and the average molar absorption coefficient of any continuous 100 nm range within the wavelength range of 400 nm to 700 nm was calculated, and evaluation was performed according to the following evaluation criteria.

[1044] For compound (3), compound (2), and compound (65), absorption spectra were measured in the same order as in compound (1) above, and the maximum absorption wavelength and the molar absorption coefficient at the maximum absorption wavelength were determined (wherein, when there are two or more maximum absorption wavelengths, the molar absorption coefficient at the wavelength with the maximum absorption was determined). Furthermore, the average molar absorption coefficient of any continuous 100 nm range within the wavelength range of 400 nm to 700 nm was calculated and evaluated according to the following evaluation criteria.

[1045] In an environment of an atmospheric temperature of 25°C, 2 ml of a 10% by mass aqueous solution of hydrochloric acid was added dropwise to 1.1 mg of 2'-anilino-6'-(dibutylamino)-3'-methylfluoran (manufactured by Tokyo Kagaku Kogyo Co., Ltd.) and mixed, and then allowed to stand for 10 minutes to develop a black color. The obtained black color-developing body was heated to 150°C in a far infrared heating furnace (so-called IR oven) for 15 minutes to separate a black color-developing body powder. The separated black color-developing body powder was dissolved in 50 mL of tetrahydrofuran (THF) to prepare a THF solution of a black color-developing body of 2'-anilino-6'-(dibutylamino)-3'-methylfluoran. Using the THF solution of the prepared 2'-anilino-6'-(dibutylamino)-3'-methylfluorane black color-developing body, the absorption spectrum was measured in the same order as in the above-mentioned compound (1), and the maximum absorption wavelength and the molar absorptivity at the maximum absorption wavelength were obtained (wherein, when there are two or more maximum absorption wavelengths, the molar absorptivity at the wavelength with the maximum absorption was obtained). In addition, the average molar absorptivity of any continuous 100 nm range within the wavelength range of 400 nm to 700 nm was calculated and evaluated according to the following evaluation criteria.

[1046] Regarding BLACK 305 [manufactured by Fukui Yamada Chemical Co., Ltd.], the absorption spectrum was measured in the same procedure as that in the above-mentioned 2'-anilino-6'-(dibutylamino)-3'-methylfluoran [manufactured by Tokyo Kagaku Kogyo Co., Ltd.], and the maximum absorption wavelength and the molar absorption coefficient at the maximum absorption wavelength were determined (wherein, when there are two or more maximum absorption wavelengths, the molar absorption coefficient at the wavelength with the maximum absorption was calculated). In addition, the average molar absorption coefficient of any continuous 100 nm range within the wavelength range of 400 nm to 700 nm was calculated and evaluated according to the following evaluation criteria.

[1047] Table 2 shows the results of the black color development evaluation of the color material precursor.

[1048] A higher value of the average molar absorption coefficient indicates better light-shielding properties.

[1049] The evaluation result is preferably "A" or "B".

[1050] -Evaluation Criteria-

[1051] A: The average molar absorption coefficient is 3000 L / (mol·cm) or more.

[1052] B: The average molar absorption coefficient is within the range of 2000 L / (mol·cm) or more and less than 3000 L / (mol·cm).

[1053] C: The average molar absorption coefficient is less than 2000 L / (mol·cm).

[1054] [Table 2]

[1055]

[1056] [Preparation of photosensitive composition]

[1057] [Examples 1A to 4A]

[1058] The components were mixed to obtain the composition shown in Table 3. After adding zirconia beads (bead diameter: 0.1 mm) in an amount three times the mass of the above-mentioned mixture to the obtained mixture, dispersion was performed for 90 minutes using an MSE (Multi-Stacked Elements) mixer at a peripheral speed of 9 m / sec. After dispersion, the zirconia beads were separated using a filter with a nominal filtration particle size of 73 μm to obtain photosensitive compositions X-1 to X-4 of Examples 1A to 4A.

[1059] [Examples 5A to 8A and Comparative Example 1A]

[1060] The components were mixed to obtain the composition shown in Table 4. After adding zirconia beads (bead diameter: 0.1 mm) in an amount three times the mass of the above-mentioned mixture to the obtained mixture, the mixture was dispersed for 90 minutes using an MSE (Multi-Stacked Elements) mixer at a peripheral speed of 9 m / sec. After dispersion, the zirconia beads were separated using a filter with a nominal filtration particle size of 73 μm, and photosensitive compositions X-5 to X-8 and Y-1 of Examples 5A to 8A and Comparative Example 1A were obtained.

[1061] [Example 9A]

[1062] The components were mixed to obtain the composition shown in Table 5. To the obtained mixture, zirconia beads (bead diameter: 0.1 mm) were added in an amount three times the mass of the above-mentioned mixture. Then, after dispersion was performed for 70 minutes using an MSE (Multi-Stacked Elements) mixer at a peripheral speed of 9 m / sec, the peripheral speed was changed to 6 m / m, and dispersion was further performed for 40 minutes. After dispersion, the above-mentioned zirconia beads were separated using a filter with a nominal filtration particle size of 73 μm, and the photosensitive composition X-9 of Example 9A was obtained.

[1063] [Example 10A]

[1064] After mixing the components to have the composition shown in Table 5, the mixture was stirred for 20 minutes to obtain a photosensitive composition X-10 of Example 10A.

[1065] [Table 3]

[1066]

[1067] [Table 4]

[1068]

[1069] [Table 5]

[1070]

[1071] [Production of transfer film]

[1072] [Example 1B]

[1073] The photosensitive composition X-1 of Example 1A was applied on a temporary support [trade name: Lumirror (registered trademark) 16KS40, biaxially stretched polyethylene terephthalate (PET) film, thickness: 16 μm, manufactured by TORAY INDUSTRIES, INC.] using a slit nozzle in an amount of coating so that the film thickness after drying was 15 μm, thereby forming a coating film. Next, the solvent in the formed coating film was volatilized in a drying zone at 100° C. to form a photosensitive composition layer. Next, a protective film [trade name: Lumirror (registered trademark) 16KS40, biaxially stretched polyethylene terephthalate (PET) film, thickness: 16 μm, manufactured by TORAY INDUSTRIES, INC.] was crimped onto the formed photosensitive composition layer to produce a transfer film of Example 1B.

[1074] [Example 2B to Example 16B]

[1075] Except having set the kind of photosensitive composition and the film thickness of the photosensitive composition layer as shown in Table 6, the same operation as in Example 1B was carried out to produce transfer films of Examples 2B to 16B.

[1076] [Comparative Examples 1B and 2B]

[1077] Except that the kind of the photosensitive composition and the film thickness of the photosensitive composition layer were set as shown in Table 6, the same operation as in Example 1B was carried out to prepare transfer films of Comparative Examples 1B and 2B.

[1078] [Measurement and evaluation]

[1079] <Measurement of Absorption Coefficient Before and After Color Development Due to Stimulation>

[1080] 1. Absorbance and Absorption Coefficient before Color Development

[1081] After peeling off the protective film from each transfer film of Examples 1B to 16B and Comparative Examples 1B and 2B, the exposed surface of the photosensitive composition layer was laminated on Gorilla Glass (registered trademark) [thickness: 700 μm, manufactured by Corning Incorporated Co., Ltd.], thereby obtaining a laminate having a laminate structure of temporary support body / photosensitive composition layer / Gorilla Glass. In the lamination conditions, the roller temperature was set to 110°C, the linear pressure was set to 0.6 MPa, and the linear speed (so-called lamination speed) was set to 2.0 m / min. The temporary support body was peeled off from each laminated body produced to produce a laminate X1.

[1082] The absorbance of the laminate X1 produced at a wavelength of 365 nm was measured using an ultraviolet-visible spectrophotometer [Model: UV-1800, manufactured by SHIMADZU CORPORATION] (denoted as "abs." in the table; the same applies hereinafter). The absorbance value obtained by the measurement was divided by the film thickness to obtain the absorbance per 1 μm film thickness (so-called absorption coefficient). The results are shown in Table 6.

[1083] 2. Absorbance and Absorption Coefficient after Color Development

[1084] (1) Examples 1B to 6B and 9B to 16B and Comparative Examples 1B and 2B

[1085] After peeling off the protective film from the transfer film, the exposed surface of the photosensitive composition layer is laminated on Gorilla Glass (registered trademark) [thickness: 700 μm, manufactured by Corning Incorporated Co., Ltd.], thereby obtaining a laminate having a laminate structure of temporary support / photosensitive composition layer / Gorilla Glass. In the lamination conditions, the roller temperature is set to 110°C, the line pressure is set to 0.6 MPa, and the line speed (so-called lamination speed) is set to 2.0 m / min. Next, using a proximity exposure machine with an ultra-high pressure mercury lamp [manufactured by Hitachi High-Tech Corporation.], without peeling off the temporary support, i-rays (wavelength 365 nm) are used with an exposure amount of 150 mJ / cm 2 The laminate was exposed. After exposure, the laminate was left standing for 1 hour, and then the temporary support of the laminate was peeled off. Then, i-ray (wavelength 365nm) was used at an exposure dose of 1000mJ / cm 2After the temporary support was peeled off, the laminate was further exposed and then left to stand for 1 hour. Next, the laminate was heated for 5 minutes using convection with the internal temperature set at 210° C., thereby producing a laminate Y1.

[1086] (2) Examples 7B and 8B

[1087] After peeling off the protective film from the transfer film, the exposed surface of the photosensitive composition layer is laminated on Gorilla Glass (registered trademark) [thickness: 700 μm, manufactured by Corning Incorporated Co., Ltd.], thereby obtaining a laminate having a laminate structure of temporary support / photosensitive composition layer / Gorilla Glass. In the lamination conditions, the roller temperature is set to 110°C, the line pressure is set to 0.6 MPa, and the line speed (so-called lamination speed) is set to 2.0 m / min. Next, using a proximity exposure machine with an ultra-high pressure mercury lamp [manufactured by Hitachi High-Tech Corporation.], without peeling off the temporary support, i-rays (wavelength 365 nm) are used with an exposure amount of 150 mJ / cm 2 The laminate was exposed. After exposure, the laminate was left standing for 1 hour, and then the temporary support of the laminate was peeled off. Then, i-ray (wavelength 365nm) was used at an exposure dose of 1000mJ / cm 2 After the temporary support was peeled off, the laminate was further exposed and then left for 1 hour. Then, the laminate was immersed in a 10 mass % hydrochloric acid aqueous solution at an ambient temperature of 25° C. for 20 minutes. Then, the laminate was heated for 5 minutes using convection with the internal temperature set at 210° C., thereby producing a laminate Y1.

[1088] (3) Observation and measurement

[1089] The produced laminated bodies Y1 were observed with naked eyes. As a result, it was confirmed that all the laminated bodies Y1 were black.

[1090] Furthermore, the absorbance of the laminate Y1 produced at a wavelength of 365 nm and the average absorbance at a wavelength of 400 nm to 700 nm (represented as "average abs." in the table; the same applies hereinafter) were measured using an ultraviolet-visible spectrophotometer [model: UV-1800, manufactured by SHIMADZU CORPORATION]. Furthermore, the absorbance value of the laminate Y1 at a wavelength of 365 nm and the average absorbance value at a wavelength of 400 nm to 700 nm obtained by the measurement were divided by the film thickness, respectively, thereby obtaining the absorbance and average absorbance per 1 μm film thickness. The results are shown in Table 6.

[1091] 3. Aspect Ratio

[1092] (1) Examples 1B to 6B and 9B to 16B and Comparative Examples 1B and 2B

[1093] After peeling off the protective film from the transfer film, the exposed surface of the photosensitive composition layer is laminated on a PET film with a thickness of 50 μm [trade name: Cosmo shine (registered trademark) A4360, manufactured by TOYOBO C0., LTD.], thereby obtaining a laminate having a laminate structure of temporary support body / photosensitive composition layer / PET film. In the lamination conditions, the roller temperature is set to 110°C, the line pressure is set to 0.6 MPa, and the line speed (so-called lamination speed) is set to 2 m / min. Next, using a proximity exposure machine with an ultra-high pressure mercury lamp [manufactured by Hitachi High-Tech Corporation.] and a photomask, without peeling off the temporary support body, use i-rays (wavelength 365 nm) with an exposure amount of 150 mJ / cm 2 , the prepared laminate was exposed. In addition, the photomask has an L (line) / S (space) pattern in the range of 1 μm to 100 μm in which the line width changes every 1 μm. After exposure, the temporary support of the laminate was peeled off. Next, it was developed for 30 seconds using a 1 mass % concentration of potassium carbonate aqueous solution (liquid temperature: 30°C), and after rinsing with a pure water spray, it was dried at 75°C for 13 seconds, and the photosensitive composition layer in the non-exposed part was removed by development. Furthermore, i-rays (wavelength 365nm) were used with an exposure amount of 1000mJ / cm 2 The photosensitive composition layer was cured by exposure. Next, the laminated body obtained by curing the photosensitive composition layer was subjected to heat treatment for 10 minutes using convection with the internal temperature set at 210° C., thereby producing a laminated body Z1 having a pattern.

[1094] (2) Examples 7B and 8B

[1095] After peeling off the protective film from the transfer film, the exposed surface of the photosensitive composition layer is laminated on a PET film 1 with a thickness of 50 μm [Trade name: Cosmo shine (registered trademark) A4360, manufactured by TOYOBO C0., LTD.], thereby obtaining a laminate having a laminate structure of a temporary support body / photosensitive composition layer / PET film. In the lamination conditions, the roller temperature is set to 110°C, the line pressure is set to 0.6 MPa, and the line speed (the so-called lamination speed) is set to 2 m / min. Next, using a proximity exposure machine with an ultra-high pressure mercury lamp [manufactured by Hitachi High-Tech Corporation.] and a photomask, without peeling off the temporary support body, use i-rays (wavelength 365 nm) with an exposure amount of 150 mJ / cm2 , the produced laminate was exposed. In addition, the photomask has an L (line) / S (space) pattern in the range of 1 μm to 100 μm in which the line width changes every 1 μm. After exposure, the temporary support of the laminate was peeled off. Next, it was developed for 30 seconds using a 1% by mass concentration of potassium carbonate aqueous solution (liquid temperature: 30°C), and after rinsing with a pure water spray, it was dried at 75°C for 13 seconds, and the photosensitive composition layer in the non-exposed part was removed by development.

[1096] Furthermore, the i-ray (wavelength 365 nm) was used with an exposure dose of 1000 mJ / cm 2 The photosensitive composition layer was exposed to light to cure. Next, the laminate formed by curing the photosensitive composition layer was immersed in a 10 mass % hydrochloric acid aqueous solution at an ambient temperature of 25° C. for 20 minutes. Next, the laminate after immersion was heated for 10 minutes using convection with the internal temperature set at 210° C., thereby producing a laminate Z1 having a pattern.

[1097] (3) Observation and measurement

[1098] The produced laminated body Z1 was observed with naked eyes. As a result, it was confirmed that all the laminated bodies Z1 were black.

[1099] In addition, the cross-section of the laminate Z1 was observed using a SEM (scanning electron microscope), and the film thickness of the pattern and the minimum line width of the image dissection were measured, and the aspect ratio was calculated by the following formula. In addition, the "minimum line width of the image dissection" refers to the line width of the bottom of the pattern with the smallest line width in the pattern in which no residue is confirmed when the space portion is observed using an optical microscope. The results are shown in Table 6.

[1100] "Aspect ratio" = "Film thickness" / "Minimum line width for resolution"

[1101] 4. Top line width / Bottom line width

[1102] The same operation as in “3. Aspect Ratio” was performed to produce a laminated body Z1.

[1103] The cross-section of the laminate Z1 was observed using a SEM (scanning electron microscope), and the line width at the bottom and the line width at the top of the pattern with the smallest line width in the resolution were measured to obtain the ratio of the line width at the top to the line width at the bottom (line width at the top / line width at the bottom). The results are shown in Table 6.

[1104] The closer the ratio of the line width at the top to the line width at the bottom is to 1, the more excellent the rectangular property of the pattern is.

[1105] 5. Thermal stability

[1106] The absorbance of the laminate Y1 produced in "2. Absorbance and Absorption Coefficient after Color Development" at a wavelength of 550 nm was measured using an ultraviolet-visible spectrophotometer (model: UV-1800, manufactured by SHIMADZU CORPORATION), and the values ​​obtained were divided by the film thickness to obtain the absorbance per 1 μm film thickness (so-called absorption coefficient). The obtained absorption coefficient is referred to as the "absorption coefficient before heat treatment".

[1107] Next, the laminate Y1 was subjected to a heat treatment for 60 minutes using convection with the internal temperature set at 230°C. Then, the absorbance of the laminate B after the heat treatment at a wavelength of 550nm was measured using an ultraviolet-visible spectrophotometer (model: UV-1800, manufactured by SHIMADZU CORPORATION), and the obtained values ​​were divided by the film thickness to obtain the absorbance per 1 μm film thickness (so-called absorption coefficient). The obtained absorption coefficient is referred to as the "absorption coefficient after heat treatment".

[1108] The difference in the extinction coefficient before and after the heat treatment was calculated from the following formula, and the thermal stability after coloration or coloring was evaluated according to the following evaluation criteria.

[1109] "Difference in absorption coefficient before and after heat treatment" = "Absorption coefficient before heat treatment" - "Absorption coefficient after heat treatment"

[1110] -Evaluation Criteria-

[1111] A: The difference in the absorption coefficient before and after the heat treatment is less than 0.01.

[1112] B: The difference in the extinction coefficient before and after the heat treatment is in the range of 0.01 or more and less than 0.1.

[1113] C: The difference in the extinction coefficient before and after the heat treatment is within the range of 0.1 or more and less than 0.5.

[1114] D: The difference in extinction coefficient before and after the heat treatment is 0.5 or more.

[1115] The evaluation result is preferably "A", "B" or "C".

[1116] The smaller the difference in the absorption coefficient before and after the heat treatment, the less likely the color-developed or colored film is to fade due to heat, indicating excellent thermal stability.

[1117] [Table 6]

[1118]

[1119] From the results shown in Table 6, it was confirmed that the photosensitive compositions X-1 to X-10 according to the present invention can form a film having excellent light-shielding properties and have excellent patterning properties.

[1120] Furthermore, it was confirmed that the photosensitive compositions X-1 to X-10 according to the present invention can form a pattern having excellent light-shielding properties and rectangular properties.

[1121] It was confirmed that the photosensitive compositions X-1 to X-6, X-9, and X-10 according to the present invention containing a color material precursor that develops black color by heat are less likely to fade by heat after color development and can form a film having better thermal stability.

[1122] 1 Example 1C)

[1123] On a glass substrate 1 (trade name: Eagle (registered trademark) XG, thickness: 700 μm, manufactured by Corning Incorporated Co., Ltd.), a photosensitive composition X-1 was applied using a slit nozzle in an amount such that the film thickness after drying was 15 μm, thereby forming a coating film. Next, the solvent in the formed coating film was volatilized in a drying zone at 100° C. to form a photosensitive composition layer, thereby preparing a laminate X2 having a laminate structure of a glass substrate / photosensitive composition layer.

[1124] In addition, similarly to the laminate X1 in Example 1B, the absorbance of the produced laminate X2 at a wavelength of 365 nm was measured using an ultraviolet visible spectrophotometer (Model: UV-1800, manufactured by SHIMADZU CORPORATION). As a result, the same value as that of the laminate X1 in Example 1B was obtained.

[1125] Then, a proximity exposure machine (manufactured by Hitachi High-Tech Corporation) equipped with an ultra-high pressure mercury lamp was used to expose the sample with an i-ray (wavelength 365 nm) at an exposure dose of 150 mJ / cm 2 After the laminate X2 prepared in the above was exposed, it was left to stand for 1 hour. Then, i-ray (wavelength 365nm) was further used at an exposure dose of 1000mJ / cm 2 After the laminate X2 was exposed, it was left to stand for 1 hour. Then, the laminate X2 was heated for 5 minutes using convection with the internal temperature set at 210° C., thereby manufacturing a laminate Y2.

[1126] The produced laminated body Y2 was observed with the naked eye, and it was confirmed that it was black.

[1127] In addition, similarly to the laminate Y1 in Example 1B, the absorbance of the produced laminate Y2 at a wavelength of 365 nm and the average absorbance at a wavelength of 400 nm to 700 nm were measured using an ultraviolet-visible spectrophotometer [Model: UV-1800, manufactured by SHIMADZU CORPORATION], and the absorbance and average absorbance per 1 μm film thickness were calculated, yielding the same values ​​as those for the laminate Y1 in Example 1B.

[1128] Then, a proximity exposure machine (manufactured by Hitachi High-Tech Corporation.) with an ultra-high pressure mercury lamp and a photomask was used to expose the film with i-rays (wavelength 365 nm) at an exposure dose of 150 mJ / cm 2 , the laminate X2 produced as described above was exposed. In addition, the photomask has an L (line) / S (space) pattern in which the line width changes every 1 μm in the range of 1 μm to 100 μm. After exposure, the temporary support of the laminate was peeled off. Next, it was developed for 30 seconds using a 1 mass % concentration of potassium carbonate aqueous solution (liquid temperature: 30°C), and after rinsing with a pure water spray, it was dried at 75°C for 13 seconds, and the photosensitive composition layer in the non-exposed part was removed by development. Furthermore, i-rays (wavelength 365nm) were used with an exposure amount of 1000mJ / cm 2 The photosensitive composition layer was cured by exposure. Next, the laminated body obtained by curing the photosensitive composition layer was subjected to heat treatment for 10 minutes using convection with the internal temperature set at 210° C., thereby producing a laminated body Z2 having a pattern.

[1129] The produced laminate Z2 was observed with the naked eye, and it was confirmed that it was black.

[1130] Furthermore, similarly to the laminate Z1 in Example 1B, the aspect ratio of the pattern and the ratio of the top line width to the bottom line width of the produced laminate Z2 were calculated, and the same values ​​as those of the pattern of the laminate Z1 in Example 1B were obtained.

[1131] Furthermore, the laminate Y2 produced in the above was subjected to a thermal stability evaluation test in the same manner as the laminate Y1 in Example 1B. As a result, the same result as that of the laminate Y1 in Example 1B was obtained.

[1132] The entire contents of the invention of Japanese Patent Application No. 2022-106690 filed on June 30, 2022 and the invention of Japanese Patent Application No. 2023-015691 filed on February 3, 2023 are incorporated into this specification by reference.

[1133] All documents, patent applications, and technical specifications described in this specification are incorporated herein by reference to the same extent as if each document, patent application, and technical specification was specifically and individually described as being incorporated by reference.

Claims

1. A photosensitive composition comprising a color material precursor that develops black color when stimulated.

2. The photosensitive composition according to claim 1, wherein The stimulus is at least one selected from the group consisting of heat, light, acid, alkali and free radicals.

3. The photosensitive composition according to claim 1, wherein The stimulus is heat. 4 . The photosensitive composition according to claim 1 , further comprising an alkali-soluble resin, a polymerizable monomer and a photopolymerization initiator.

5. The photosensitive composition according to claim 1, wherein When a film having a film thickness of 1 μm is formed using the photosensitive composition, the absorbance of the film at a wavelength of 365 nm is 0.1 or less.

6. The photosensitive composition according to claim 1, wherein When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the absorbance of the film at a wavelength of 365 nm is 0.2 or more.

7. The photosensitive composition according to claim 1, wherein When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the average absorbance of the film at a wavelength of 400 nm to 700 nm is 0.2 or more.

8. The photosensitive composition according to claim 1, wherein The color material precursor is a compound represented by the following formula (1): In formula (1), X 1 , X 2 , X 3 , X 4 , Y 1 and Y 2 Each independently represents an oxygen atom, a sulfur atom or NL 1 , L 1 represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group, R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom, -OL 2 、-OCO-L 3 , -SL 2 or-OSO-L 3 , L 2 represents a hydrogen atom or an alkyl group, L 3 represents an alkyl group or an amino group, wherein R 1 and R 2 At least one of represents a hydrogen atom, R 3 and R 4 At least one of represents a hydrogen atom, and A, B and C each independently represent an aromatic ring.

9. A photosensitive composition comprising: The color material precursor develops black color by at least one stimulus selected from the group consisting of heat, light, acid, alkali and free radicals; Alkali soluble resin; polymerizable monomers; and Photopolymerization initiator, The photosensitive composition satisfies all of the following (1) to (3), (1) When a film having a thickness of 1 μm is formed using the photosensitive composition, the absorbance of the film at a wavelength of 365 nm is 0.1 or less, (2) when the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the absorbance of the film at a wavelength of 365 nm is 0.2 or more, (3) When the photosensitive composition is used and the color material precursor is colored black by the stimulation to form a black film having a film thickness of 1 μm, the average absorbance of the film at a wavelength of 400 nm to 700 nm is 0.2 or more.

10. The photosensitive composition according to claim 9, wherein The color material precursor is a compound represented by the following formula (1): In formula (1), X 1 , X 2 , X 3 , X 4 , Y 1 and Y 2 Each independently represents an oxygen atom, a sulfur atom or NL 1 , L 1 represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group, R 1 , R 2 , R 3 and R 4 Each independently represents a hydrogen atom, -OL 2 、-OCO-L 3 , -SL 2 or-OSO-L 3 , L 2 represents a hydrogen atom or an alkyl group, L 3 represents an alkyl group or an amino group, wherein R 1 and R 2 At least one of represents a hydrogen atom, R 3 and R 4 At least one of represents a hydrogen atom, and A, B and C each independently represent an aromatic ring.

11. A transfer film, comprising: Temporary supports; and A photosensitive composition layer comprising the photosensitive composition according to any one of claims 1 to 10.

12. The transfer film according to claim 11, wherein The photosensitive composition layer has a film thickness of 5 μm or more.

13. A method for manufacturing a laminate having a black pattern, comprising: A step of forming a photosensitive composition layer containing the photosensitive composition according to any one of claims 1 to 10 on a substrate; A step of pattern-exposing the photosensitive composition layer; and a step of developing the photosensitive composition layer, The method for producing a laminate includes, after the pattern exposure step, a step of developing the color material precursor into black.

14. The method for producing a laminate according to claim 13, wherein: The black pattern has a thickness of 5 μm or more. 15 . A laminate having a black pattern and produced by the production method according to claim 13 .

16. The laminate according to claim 15, wherein The black pattern has a thickness of 5 μm or more.

17. The laminate according to claim 15, wherein The black pattern has an absorbance of 2.0 or more at a wavelength of 365 nm.

18. The laminate according to claim 15, wherein The black pattern has an average absorbance of 2.0 or more at a wavelength of 400 nm to 700 nm.

19. The laminate according to claim 15, wherein The aspect ratio, which is a ratio of the film thickness of the black pattern to the line width of the bottom, is 1.0 or more.

20. A laminate comprising a substrate and a black pattern, The black pattern has a film thickness of 5 μm or more, an aspect ratio of the film thickness to the line width at the bottom of the pattern is 1.0 or more, and an average absorbance at a wavelength of 400 nm to 700 nm is 2.0 or more.

21. The laminate according to claim 20, wherein The ratio of the line width of the uppermost portion of the black pattern to the line width of the bottom portion is 0.8 to 1.

2.

22. The laminate according to claim 20, wherein The black pattern includes a color material represented by the following formula (I), In formula (I), X 1a , X 2a , X 3a , X 4a , Y 1a and Y 2a Each independently represents an oxygen atom, a sulfur atom or NL 1a , L 1a represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an aminocarbonyl group, and A', B' and C' each independently represent an aromatic ring.

23. A micro LED display comprising the laminate according to claim 20 or 21.

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