Photocurable composition, method for producing cured film, film, solid-state imaging element, image display device, and radical polymerization initiator

Abstract

The present invention provides a photocurable composition comprising a colorant, a radical polymerization initiator represented by formula (1), and a radical polymerizable compound, a method for producing a cured film using the photocurable composition, a film, a solid-state imaging element or an image display device, or a novel radical polymerization initiator. In formula (1), Ar1 represents a (k + m + 1)-valent aromatic group or a (k + m + 1)-valent heteroaromatic group, Ar2 represents a (k + 2)-valent aromatic group or a (k + 2)-valent heteroaromatic group, R6 each independently represents a halogen atom or a monovalent organic group, L represents a single bond or CR11R12, R11 and R12 each independently represent a hydrogen atom, an alkyl group or an aryl group, and Y1 represents a group represented by formula (2). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a photocurable composition, a method for producing a cured film, a film, a solid-state imaging element, an image display device, and a radical polymerization initiator. Background Art

[0002] An optical filter such as a color filter is produced using a photocurable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound.

[0003] As conventional photopolymerization initiators, photopolymerization initiators described in JP-A-2012-519191 or JP-A-2016-531926 are known.

[0004] Japanese Patent Application Publication No. 2012-519191 describes a carbazole oxime ester photoinitiator.

[0005] The 2016-531926 Gazette describes an oxime ester photoinitiator having an indole ring or the like. Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] An object of the embodiments of the present invention is to provide a highly sensitive photocurable composition.

[0008] Furthermore, another embodiment of the present invention is to provide a method for producing a cured film using the photocurable composition, a film, a solid-state imaging element, or an image display device.

[0009] Furthermore, another embodiment of the present invention is to provide a novel radical polymerization initiator.

[0010] Means for solving technical problems

[0011] Means for solving the above-mentioned problems include the following.

[0012] <1> A photocurable composition comprising:

[0013] Colorants;

[0014] A radical polymerization initiator represented by formula (1); and

[0015] Free radical polymerizable compounds.

[0016] [Chemical formula 1]

[0017]

[0018] In formula (1), Ar1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group, Ar2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group, R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, k represents 0 or 1, R6 each independently represents a halogen atom or a monovalent organic group, and one or more R 6 Can be used with Ar 1 Together they form a ring structure; Y1 represents a group represented by the following formula (2); m represents an integer of 0 to 4; and n represents 0 or 1.

[0019] [Chemical formula 2]

[0020]

[0021] In formula (2), R2 represents an alkyl group, wherein when L2 is CHR, R2 may be a hydrogen atom, R3 represents a hydrogen atom or an alkyl group, R4 represents an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, R each independently represents a hydrogen atom or an alkyl group, two or more of R2, R3, R4 and R may be linked to each other to form a ring structure, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to the oxime group.

[0022] <2> The photocurable composition according to <1>, wherein

[0023] The above Y1 is a group represented by the following formula (3).

[0024] [Chemical formula 3]

[0025]

[0026] In formula (3), L3 and L4 each independently represent CHR, O, S or NR, at least one of L3 and L4 is CHR, R represents a hydrogen atom or an alkyl group, R5 each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 6, and * represents a linking portion to the oxime group.

[0027] <3> The photocurable composition according to <1> or <2>, wherein

[0028] The above R6 is a halogen atom, a nitro group, a cyano group or a group represented by the following formula (4).

[0029] [Chemical formula 4]

[0030]

[0031] In formula (4), Ar3 represents an aryl group or a heteroaryl group, and * represents a linking portion with Ar1.

[0032] <4> The photocurable composition according to any one of <1> to <3>, wherein

[0033] The radical polymerization initiator represented by the above formula (1) is a compound represented by the following formula (5).

[0034] [Chemical formula 5]

[0035]

[0036] In formula (5), Ar3 represents an aryl group or a heteroaryl group, R7 represents an alkyl group or an aryl group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, Z represents an alkylene group having 1 to 3 carbon atoms, k represents 0 or 1, n represents 0 or 1, and p represents an integer of 1 to 6.

[0037] <5> The photocurable composition according to any one of <1> to <4>, wherein

[0038] The content of the colorant is 60% by mass or more based on the total solid content of the composition.

[0039] <6> The photocurable composition according to any one of <1> to <5>, further comprising a resin.

[0040] <7> The photocurable composition according to <6>, wherein

[0041] The resin includes a resin that is a graft polymer having a graft chain, wherein the graft chain includes at least one selected from the group consisting of a polyether chain, a polyester chain, and a polyacrylic acid chain, and the graft chain has a weight average molecular weight of 1,000 or more.

[0042] <8> The photocurable composition according to <6>, wherein

[0043] The above-mentioned resin includes a resin having a (meth)acryloyl group, an epoxy group or an oxetane group.

[0044] <9> The photocurable composition according to any one of <1> to <8>, further comprising a pigment derivative.

[0045] <10> The photocurable composition according to any one of <1> to <9>, further comprising a chain transfer agent.

[0046] <11> The photocurable composition according to any one of <1> to <10>, further comprising a sensitizer.

[0047] <12> The photocurable composition according to any one of <1> to <11>, which is used for excimer laser exposure having a wavelength of 150 nm to 300 nm.

[0048] <13> A method for producing a cured film, comprising the step of irradiating the photocurable composition according to any one of <1> to <12> with an excimer laser having a wavelength of 150 nm to 300 nm.

[0049] <14> A film which is a cured product of the photocurable composition according to any one of <1> to <12>.

[0050] <15> A solid-state imaging element including the film according to <14>.

[0051] <16> An image display device comprising the film according to <14>.

[0052] <17> A radical polymerization initiator represented by formula (1).

[0053] [Chemical formula 6]

[0054]

[0055] In formula (1), Ar1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group, Ar2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group, R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, k represents 0 or 1, R6 each independently represents a halogen atom or a monovalent organic group, and one or more R 6 Can be used with Ar 1 Together they form a ring structure; Y1 represents a group represented by the following formula (2-1); m represents an integer of 0 to 4; and n represents 0 or 1.

[0056] [Chemical formula 7]

[0057]

[0058] In formula (2-1), R3 represents a hydrogen atom or an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, L Arepresents an alkylene group having 1 to 6 carbon atoms, R each independently represents a hydrogen atom or an alkyl group, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to an oxime group.

[0059] Effects of the Invention

[0060] According to an embodiment of the present invention, a highly sensitive photocurable composition is provided.

[0061] Furthermore, according to another embodiment of the present invention, there is provided a method for producing a cured film using the photocurable composition, a film, a solid-state imaging element, or an image display device.

[0062] Furthermore, according to another embodiment of the present invention, a novel radical polymerization initiator is provided. DETAILED DESCRIPTION

[0063] The following is a detailed description of the present invention. The description of the components described below is based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0064] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0065] In the marking of groups (atomic groups) in this specification, the marking not indicating substituted or unsubstituted includes groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0066] In this specification, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, examples of light used in exposure include active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light [EUV (Extreme Ultraviolet) light], X-rays, and electron beams.

[0067] In the present specification, “(meth)acrylate” means both or either acrylate and methacrylate, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0068] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0069] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene conversion values ​​measured by GPC (gel permeation chromatography) method.

[0070] In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.

[0071] In this specification, a pigment refers to a colorant that is not easily dissolved in a solvent.

[0072] In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the expected effect of the step is achieved.

[0073] In the present specification, an oxime compound having E-isomer and Z-isomer may be either the E-isomer or the Z-isomer unless otherwise specified.

[0074] Hereinafter, the present invention will be described in detail.

[0075] (Photocurable composition)

[0076] The photocurable composition according to the present invention contains a colorant, a radical polymerization initiator represented by formula (1), and a radical polymerizable compound.

[0077] [Chemical formula 8]

[0078]

[0079] In formula (1), Ar1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group, Ar2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group, R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, k represents 0 or 1, R6 each independently represents a halogen atom or a monovalent organic group, and one or more R 6 Can be used with Ar 1 Together they form a ring structure; Y1 represents a group represented by the following formula (2); m represents an integer of 0 to 4; and n represents 0 or 1.

[0080] [Chemical formula 9]

[0081]

[0082] In formula (2), R2 represents an alkyl group, wherein when L2 is CHR, R2 may be a hydrogen atom, R3 represents a hydrogen atom or an alkyl group, R4 represents an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, R each independently represents a hydrogen atom or an alkyl group, two or more of R2, R3, R4 and R may be linked to each other to form a ring structure, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to the oxime group.

[0083] Furthermore, the photocurable composition of the present invention can be preferably used as a photocurable composition for exposure with light having a wavelength of 150 nm to 300 nm, and can be particularly preferably used as a photocurable composition for exposure with an excimer laser having a wavelength of 150 nm to 300 nm.

[0084] As a result of intensive studies, the present inventors have found that a highly sensitive photocurable composition can be obtained by adopting the above-mentioned structure.

[0085] It is speculated that the radical polymerization initiator represented by the above formula (1) has a structure in which two aromatic rings are linked by an ether bond, so the light absorption peak becomes sharper and the absorption efficiency is improved. Moreover, since the group represented by the above formula (2) promotes the generation of free radicals from the oxime ester structure, a highly sensitive photocurable composition can be obtained.

[0086] The photocurable composition of the present invention can be preferably used as a photocurable composition for an optical filter. As an optical filter, a color filter and an infrared transmission filter can be mentioned, preferably a color filter. That is, the photocurable composition of the present invention can be preferably used as a photocurable composition for a color filter. More specifically, it can be preferably used as a photocurable composition for forming pixels of a color filter. As the type of pixel, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be mentioned.

[0087] As the infrared transmission filter, preferably, there can be mentioned a filter satisfying the following spectral characteristics, that is, the maximum value of the transmittance in the wavelength range of 400nm to 640nm is 20% or less, preferably 15% or less, more preferably 10% or less, and the minimum value of the transmittance in the wavelength range of 1,100nm to 1,300nm is 70% or more, preferably 75% or more, more preferably 80% or more. The infrared transmission filter is preferably a filter satisfying any one of the following spectral characteristics (1) to (5).

[0088] (1): A filter having a maximum transmittance of 20% or less, preferably 15% or less, more preferably 10% or less in the wavelength range of 400 nm to 640 nm, and a minimum transmittance of 70% or more, preferably 75% or more, more preferably 80% or more in the wavelength range of 800 nm to 1,500 nm.

[0089] (2) A filter having a maximum transmittance of 20% or less, preferably 15% or less, more preferably 10% or less in the wavelength range of 400 nm to 750 nm, and a minimum transmittance of 70% or more, preferably 75% or more, more preferably 80% or more in the wavelength range of 900 nm to 1,500 nm.

[0090] (3): A filter having a maximum transmittance of 20% or less, preferably 15% or less, more preferably 10% or less in the wavelength range of 400 nm to 830 nm, and a minimum transmittance of 70% or more, preferably 75% or more, more preferably 80% or more in the wavelength range of 1,000 nm to 1,500 nm.

[0091] (4): A filter whose maximum transmittance in the wavelength range of 400 nm to 950 nm is 20% or less, preferably 15% or less, more preferably 10% or less, and whose minimum transmittance in the wavelength range of 1,100 nm to 1,500 nm is 70% or more, preferably 75% or more, more preferably 80% or more.

[0092] (5): A filter having a maximum transmittance of 20% or less, preferably 15% or less, more preferably 10% or less in the wavelength range of 400 nm to 1,050 nm, and a minimum transmittance of 70% or more, preferably 75% or more, more preferably 80% or more in the wavelength range of 1,200 nm to 1,500 nm.

[0093] Furthermore, the photocurable composition of the present invention can be preferably used for solid-state imaging elements. More specifically, it can be preferably used as a photocurable composition for an optical filter for a solid-state imaging element, and more preferably as a photocurable composition for a color filter for a solid-state imaging element.

[0094] The solid content concentration of the photocurable composition of the present invention is preferably 5% to 40% by mass. The lower limit is more preferably 7.5% by mass or more, and further preferably 10% by mass or more. The upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.

[0095] <Radical polymerization initiator represented by formula (1)>

[0096] The photocurable composition according to the present invention contains a radical polymerization initiator represented by the above formula (1).

[0097] Furthermore, the radical polymerization initiator represented by the above formula (1) is preferably a photoradical polymerization initiator, and more preferably a photoradical polymerization initiator that generates radicals by light having a wavelength of 150 nm to 300 nm.

[0098] The exposure wavelength at which the radical polymerization initiator represented by the above formula (1) generates radicals is preferably 150 nm to 460 nm, more preferably 150 nm to 420 nm, further preferably 150 nm to 380 nm, and particularly preferably 150 nm to 300 nm.

[0099] From the viewpoints of sensitivity, adhesion and undercut suppression, Ar1 in formula (1) is preferably an aromatic group with a valence of (k+m+1), more preferably a group obtained by removing (k+m+1) hydrogen atoms from benzene which may be substituted or a group obtained by removing (k+m+1) hydrogen atoms from naphthalene which may be substituted, further preferably a group obtained by removing (k+m+1) hydrogen atoms from benzene which may be substituted, and particularly preferably a group obtained by removing (k+m+1) hydrogen atoms from unsubstituted benzene.

[0100] From the viewpoints of sensitivity, adhesion and undercut suppression, Ar2 in formula (1) is preferably an aromatic group with a valence of (k+2), more preferably a group obtained by removing (k+2) hydrogen atoms from benzene which may be substituted or a group obtained by removing (k+2) hydrogen atoms from naphthalene which may be substituted, further preferably a group obtained by removing (k+2) hydrogen atoms from benzene which may be substituted, and particularly preferably a group obtained by removing (k+2) hydrogen atoms from unsubstituted benzene.

[0101] Furthermore, from the viewpoints of sensitivity, adhesion, and undercut suppression, Ar1 and Ar2 in formula (1) are preferably line-symmetrical with respect to the oxygen atom bonded to Ar1 and Ar2.

[0102] The aromatic group and heteroaromatic group in Ar1 and Ar2 in formula (1) may further have a substituent. As the substituent, there is no particular limitation, and preferably a substituent having 0 to 100 carbon atoms can be cited, and more preferably a substituent having 0 to 50 carbon atoms can be cited. As the above-mentioned substituent, for example, a halogen atom, a hydroxyl group, an amino group, an alkyl group, a cycloalkyl group, an alkenyl group, a heterocyclic group, an aryl group, a heteroaryl group, an acyl group, a nitro group, a cyano group, a sulfo group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a morpholino group, an alkoxyalkyl group, a carboxyl group, a carboxyl-substituted alkyl group, etc. can be cited. In addition, these substituents may further have a substituent, and the substituents may be bonded to each other to form a ring structure.

[0103] Among them, as the substituent of the aromatic group and the heteroaromatic group in Ar1 and Ar2 in formula (1), a halogen atom is preferred, and a bromine atom is more preferred.

[0104] From the viewpoints of sensitivity, adhesion and undercut suppression, R in formula (1) 11 and R 12 Each independently is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms.

[0105] And, R 11 and R 12 The alkyl group and aryl group in the formula (A) may have a substituent. As the substituent, the above-mentioned substituents may be mentioned. Among them, as the substituent, an alkoxy group may be preferably mentioned.

[0106] From the viewpoints of sensitivity, adhesion, and undercut suppression, L in formula (1) is preferably a single bond.

[0107] From the viewpoint of sensitivity, adhesion, and undercut suppression, k in formula (1) is preferably 1.

[0108] When the structure including Ar1, Ar2, oxygen atom, L and k in formula (1) is shown below as X, preferred specific examples of X are shown below. In addition, * represents the bonding position to R6 and the carbonyl group in formula (1).

[0109] [Chemical formula 10]

[0110]

[0111] [Chemical formula 11]

[0112]

[0113] Among them, from the viewpoint of sensitivity, X is preferably at least one group selected from the group consisting of X-3, X-8, X-11, and X-12, and more preferably X-3.

[0114] From the viewpoints of sensitivity, adhesion and undercut suppression, R6 in formula (1) is preferably a halogen atom, a nitro group, a cyano group, a group having at least an aromatic ring or a heteroaromatic ring, more preferably a bromine atom, an aromatic acyl group or a heteroaromatic acyl group, further preferably a bromine atom or an aromatic acyl group, and particularly preferably an aromatic acyl group.

[0115] The aromatic ring, heteroaromatic ring, aromatic acyl group or heteroaromatic acyl group in R6 may have a substituent. As the substituent, the above-mentioned substituents can be mentioned. Among them, as the substituent, a halogen atom, a nitro group, a cyano group, an alkoxy group, an alkylthio group, a trifluoromethyl group, a dimethylamino group or a morpholinyl group can be preferably mentioned, and a bromine atom can be more preferably mentioned.

[0116] From the viewpoint of sensitivity, adhesion, and undercut suppression, m in formula (1) is preferably 1 or 2, and more preferably 1.

[0117] Furthermore, from the viewpoint of sensitivity, R6 in formula (1) is preferably a halogen atom, a nitro group, a cyano group or a group represented by the following formula (4), more preferably a bromine atom or a group represented by the following formula (4), and further preferably a group represented by the following formula (4).

[0118] [Chemical formula 12]

[0119]

[0120] In formula (4), Ar3 represents an aryl group or a heteroaryl group, and * represents a linking portion with Ar1.

[0121] From the viewpoint of sensitivity, Ar3 in formula (4) is preferably an aryl group which may have a substituent, more preferably an aryl group having 6 to 14 carbon atoms which may have a substituent, further preferably an aryl group having 6 to 10 carbon atoms which may have a substituent, and particularly preferably a naphthyl group which may have a substituent.

[0122] Examples of the aryl group in Ar3 include phenyl, naphthyl, and anthracenyl.

[0123] Examples of the heteroaryl group in Ar3 include furyl, thienyl, and pyrrolyl.

[0124] The aryl or heteroaryl group in Ar3 may have a substituent. As the substituent, the above-mentioned substituents may be mentioned. Among them, as the substituent, preferably a halogen atom, a nitro group, a cyano group, an alkoxy group, an alkylthio group, a trifluoromethyl group, a dimethylamino group or a morpholinyl group may be mentioned, and more preferably a bromine atom may be mentioned.

[0125] Preferred specific examples of R6 in formula (1) are shown below: In addition, * represents a bonding position with Ar1.

[0126] Furthermore, as preferred specific examples of R6, a halogen atom, a nitro group, and a cyano group are also preferably mentioned.

[0127] [Chemical formula 13]

[0128]

[0129] Among them, from the viewpoint of sensitivity, R6 is preferably at least one group selected from the group consisting of a bromine atom, R6-1, R6-12, R6-13, R6-14, R6-15, R6-16, R6-19 and R6-20, more preferably at least one group selected from the group consisting of a bromine atom, R6-12, R6-13, R6-14, R6-15, R6-19 and R6-20, and particularly preferably at least one group selected from the group consisting of R6-12, R6-13, R6-14, R6-15, R6-19 and R6-20.

[0130] From the viewpoint of sensitivity, R1 in formula (1) is preferably an alkyl group, an aryl group, an alkoxy group or an aryloxy group, more preferably an alkyl group or an aryl group, further preferably an alkyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

[0131] The alkyl group, aryl group, alkoxy group, aryloxy group or the like in R1 may have a substituent. Examples of the substituent include the substituents listed above.

[0132] Y1 in the formula (1) is a group represented by the following formula (2).

[0133] [Chemical formula 14]

[0134]

[0135] In formula (2), R2 represents an alkyl group, wherein when L2 is CHR, R2 may be a hydrogen atom, R3 represents a hydrogen atom or an alkyl group, R4 represents an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, R each independently represents a hydrogen atom or an alkyl group, two or more of R2, R3, R4 and R may be linked to each other to form a ring structure, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to the oxime group.

[0136] From the viewpoint of sensitivity, R2 in formula (2) is preferably an alkyl group.

[0137] From the viewpoint of sensitivity, R3 in formula (2) is preferably a hydrogen atom.

[0138] From the viewpoint of sensitivity, R4 in formula (2) is preferably an alkyl group.

[0139] Among them, from the viewpoint of compatibility with a radical polymerizable compound and sensitivity, it is preferred that R2 and R4 are bonded to each other to form a ring structure, and it is more preferred that R2 and R4 are bonded to each other to form an aliphatic hydrocarbon ring structure.

[0140] From the viewpoint of sensitivity, L1 in formula (2) is preferably O, S or NR, and more preferably O or NR.

[0141] From the viewpoint of sensitivity, L2 in formula (2) is preferably CHR.

[0142] From the viewpoint of sensitivity, R in the above NR is preferably an alkyl group, more preferably a methyl group or a cycloalkyl group, and particularly preferably a methyl group, a cyclopentyl group or a cyclohexyl group.

[0143] From the viewpoint of sensitivity, R in the above CHR is preferably a hydrogen atom.

[0144] From the viewpoint of sensitivity, Z in formula (2) is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and particularly preferably a single bond.

[0145] Furthermore, from the viewpoint of sensitivity, Y1 in formula (1) is more preferably a group represented by the following formula (2-1).

[0146] [Chemical formula 15]

[0147]

[0148] In formula (2-1), R3 represents a hydrogen atom or an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, L A represents an alkylene group having 1 to 6 carbon atoms, R each independently represents a hydrogen atom or an alkyl group, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to an oxime group.

[0149] Preferred embodiments of R3, L1, L2, R and Z in formula (2-1) are respectively the same as preferred embodiments of R3, L1, L2, R and Z in formula (2).

[0150] From the perspective of sensitivity, L in formula (2-1) A It is preferably an alkylene group having 3 or 4 carbon atoms, and more preferably a 1,3-propylene group.

[0151] Furthermore, from the viewpoint of sensitivity, Y1 in formula (1) is more preferably a group represented by the following formula (3).

[0152] [Chemical formula 16]

[0153]

[0154] In formula (3), L3 and L4 each independently represent CHR, O, S or NR, at least one of L3 and L4 is CHR, R represents a hydrogen atom or an alkyl group, R5 each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 6, and * represents a linking portion to the oxime group.

[0155] From the viewpoint of sensitivity, L3 in formula (3) is preferably O, S or NR.

[0156] From the viewpoint of sensitivity, L4 in formula (3) is preferably CHR.

[0157] Preferred aspects of R in formula (3) are the same as preferred aspects of R in formula (2).

[0158] From the viewpoint of sensitivity, R5 in formula (3) is preferably a hydrogen atom.

[0159] From the viewpoint of sensitivity, p in formula (3) is preferably an integer of 3 to 5, more preferably 3 or 4, and particularly preferably 3.

[0160] Preferred specific examples of Y1 in formula (1) are shown below. In addition, * represents the bonding position to the oxime group.

[0161] [Chemical formula 17]

[0162]

[0163] Among them, from the viewpoint of sensitivity, Y1 is preferably at least one group selected from the group consisting of Y-1, Y-2, Y-3, Y-12, Y-13, Y-14, Y-15, Y-16, Y-17 and Y-18, and more preferably at least one group selected from the group consisting of Y-2, Y-13, Y-14, Y-15, Y-16, Y-17 and Y-18.

[0164] The above R1~R5, R, L A Each group such as the alkyl group, aryl group, alkylene group, and alkyl group in alkoxy group in Z may further have a substituent. As the substituent, preferably, the substituent described above in Ar1 can be mentioned.

[0165] From the viewpoint of sensitivity, n in formula (1) is preferably 0.

[0166] From the viewpoints of sensitivity, adhesion, and undercut suppression, the radical polymerization initiator represented by the above formula (1) is preferably a compound represented by the following formula (5).

[0167] [Chemical formula 18]

[0168]

[0169] In formula (5), Ar3 represents an aryl group or a heteroaryl group, R7 represents an alkyl group or an aryl group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, Z represents an alkylene group having 1 to 3 carbon atoms, k represents 0 or 1, n represents 0 or 1, and p represents an integer of 1 to 6.

[0170] Ar3, L, R in formula (5) 11 , R 12 The preferred forms of Z, k, n and p are respectively the same as those of Ar3, L, R 11 , R 12 The preferred embodiments of , Z, k, n and p are the same.

[0171] From the viewpoint of sensitivity, R7 in formula (5) is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

[0172] The alkyl group or aryl group in R7 may have a substituent. Examples of the substituent include the substituents listed above.

[0173] The free radical polymerization initiator represented by the above formula (1) preferably has absorption in any one of the ArF absorption region, i.e., a wavelength of 193 nm, the KrF absorption region, i.e., a wavelength of 248 nm, and the i-ray absorption region, i.e., a wavelength of 365 nm, and more preferably has absorption in any one of the ArF absorption region, i.e., a wavelength of 193 nm, and the KrF absorption region, i.e., a wavelength of 248 nm.

[0174] From the viewpoint of sensitivity, the gram extinction coefficient of the radical polymerization initiator represented by the above formula (1) at either a wavelength of 248 nm or 365 nm is preferably 1,000 L·g -1 cm -1 More preferably, 10,000 L·g -1 cm -1 More preferably, 20,000 L·g -1 cm -1 above.

[0175] The gram absorption coefficient of the radical polymerization initiator represented by the formula (1) is measured by the following method.

[0176] Accurately weigh 12.5 mg of the polymerization initiator and place it in a 100 mL volumetric flask. Add acetonitrile to it and dissolve it completely. Take out 2 mL of the polymerization initiator solution with a quantitative pipette and make it up to volume in a 25 mL volumetric flask. Use this as the measurement sample.

[0177] A sample was added to a 1 cm square 5 mL quartz glass cuvette, and absorbance was measured in air to calculate the gram absorption coefficient. The measuring instrument used was (UH4150 ultraviolet-visible-near-infrared spectrophotometer (manufactured by Hitachi High-Tech Science Corporation)).

[0178] From the viewpoint of sensitivity, the molecular weight of the radical polymerization initiator represented by the formula (1) is preferably 150 or more, more preferably 200 or more, and particularly preferably 250 or more. The upper limit is preferably less than 1,000, more preferably less than 900, and even more preferably less than 800.

[0179] As specific examples of the free radical polymerization initiator represented by the above formula (1), preferably A-1 to A-190 can be cited, but it is not limited to these. In addition, X represents X as a structure including the above-mentioned Ar1, Ar2, oxygen atom, L and k, and R6-1 to R6-28, X-1 to X-14 and Y-1 to Y-25 are respectively the same groups as the above-mentioned R6-1 to R6-28, X-1 to X-14 and Y-1 to Y-25. In addition, tBu represents a tert-butyl group, and Ph represents a phenyl group.

[0180] [Table 1]

[0181]

[0182] [Table 2]

[0183]

[0184] [Table 3]

[0185]

[0186] [Table 4]

[0187]

[0188] [Table 5]

[0189]

[0190] The photocurable composition according to the present invention may contain one radical polymerization initiator represented by the above formula (1) alone, or two or more radical polymerization initiators. When two or more radical polymerization initiators are used, the total amount thereof is preferably within the following range.

[0191] From the viewpoint of sensitivity and coating film uniformity, the content of the free radical polymerization initiator represented by the above formula (1) is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 25% by mass, further preferably 0.1% by mass to 20% by mass, and particularly preferably 1% by mass to 15% by mass, relative to the total solid content of the photocurable composition.

[0192] Furthermore, the free radical polymerization initiator represented by the above formula (1) preferably has no absorption at a wavelength of 450 nm or more, more preferably has no absorption at a wavelength of 420 nm or more, and particularly preferably has no absorption in a wavelength range longer than 400 nm. In addition, in the present invention, "no absorption" means that the gram absorption coefficient at this wavelength is 100 L·g -1 cm -1 The radical polymerization initiator represented by the above formula (1) is preferably white to light yellow. The above colors are preferred because they have little influence on the spectral distribution of the color filter.

[0193] The method for producing the radical polymerization initiator represented by the above formula (1) is not particularly limited, and the radical polymerization initiator may be produced by a known method or by referring to a known method.

[0194] Furthermore, as a method for producing the radical polymerization initiator represented by the above formula (1), for example, the same method as described in JP-A-2016-531926 can be used. Instead of carbazole or diphenyl sulfide in the method described in the above publication, an ether-linked aromatic compound can be used to synthesize it by a similar synthesis method.

[0195] <Other radical polymerization initiators>

[0196] The photocurable composition according to the present invention may contain a radical polymerization initiator other than the radical polymerization initiator represented by the above formula (1).

[0197] Examples of other radical polymerization initiators include oxime compounds, α-aminoacetophenone compounds, α-hydroxyketone compounds, and acylphosphine compounds.

[0198] Among them, oxime compounds are preferred.

[0199] By using the radical polymerization initiator represented by the above formula 1 and other radical polymerization initiators simultaneously, a pattern having a better balance and good rectangularity can be obtained.

[0200] As oxime compounds, compounds described in paragraph 0142 of International Publication No. 2022 / 085485, polymers described in Japanese Patent Publication No. 2020-172619, compounds represented by Formula 1 described in International Publication No. 2020 / 152120, oxime ester compounds described in International Publication No. 2021 / 023144, etc. can be cited. As specific examples and commercially available products of oxime compounds, compounds described in paragraph 0142 of International Publication No. 2022 / 085485 can be used. And, as a commercially available product, TR-PBG-327 (TRONLY Corporation) can be cited.

[0201] Furthermore, it is also preferable to use a non-coloring compound or a highly transparent compound that is not easily discolored as the oxime compound. Commercially available products include ADEKA ARKLS (registered trademark: the same below), NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0202] In addition, as other free radical polymerization initiators, fluorenylaminoketone-based photoinitiators described in JP-A-2020-507664, photopolymerization initiators represented by the general formula (1) in JP-A-2021-173858, photopolymerization initiators described in paragraphs 0022 to 0024 of JP-A-2021-173858, photopolymerization initiators represented by the general formula (1) in JP-A-2021-170089, photopolymerization initiators described in paragraphs 0117 to 0120 of JP-A-2021-170089, Compounds described in Japanese Patent Publication No. 2021-181406, photopolymerization initiators described in Japanese Patent Publication No. 2022-013379, compounds represented by formula (1) described in Japanese Patent Publication No. 2022-015747, fluorine-containing fluorene oxime ester photoinitiators described in Japanese Patent Table No. 2021-507058, initiators described in the specification of Chinese Patent Application Publication No. 110764367, initiators described in Japanese Patent Table No. 2022-518535, initiators described in International Publication No. 2021 / 175855, etc.

[0203] Furthermore, as the oxime compound, the compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 can be used.

[0204] Specific examples of the oxime compound include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

[0205] Furthermore, as the oxime compound, the following compounds can be particularly preferably exemplified.

[0206] [Chemical formula 19]

[0207]

[0208] [Chemical formula 20]

[0209]

[0210] [Chemical formula 21]

[0211]

[0212] The mass ratio when the free radical polymerization initiator represented by the above formula (1) and other free radical polymerization initiators are used simultaneously is not particularly limited. From the viewpoint of sensitivity, the content of the free radical polymerization initiator represented by the above formula (1) relative to the total mass of the polymerization initiator is preferably 10 mass % or more, more preferably 50 mass % or more, further preferably 80 mass % or more, and particularly preferably 90 mass % or more.

[0213] <Coloring agent>

[0214] The photocurable composition according to the present invention contains a colorant.

[0215] As the colorant, there can be mentioned a color colorant and a black colorant, etc. As the color colorant, there can be mentioned a colorant having a maximum absorption wavelength in the range of 400nm to 700nm. For example, there can be mentioned a green colorant, a red colorant, a yellow colorant, a purple colorant, a blue colorant, an orange colorant, etc.

[0216] The colorant can be a pigment or a dye.

[0217] Furthermore, as the colorant, from the viewpoint of colorability and dispersibility, it is preferably at least one pigment selected from the group consisting of diketopyrrolopyrrole pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments, quinoline yellow pigments, azo pigments, azomethine pigments and dioxazine pigments, and more preferably at least one pigment selected from the group consisting of diketopyrrolopyrrole pigments, phthalocyanine pigments and isoindoline pigments.

[0218] Furthermore, a black pigment can be used. As the black pigment, carbon black, or a pigment containing a titanium atom or a zirconium atom can be used.

[0219] The average primary particle size of the pigment is preferably 1 nm to 200 nm. The lower limit is more preferably 5 nm or more, and further preferably 10 nm or more. The upper limit is more preferably 180 nm or less, further preferably 150 nm or less, and particularly preferably 100 nm or less. In addition, in the present specification, the primary particle size of the pigment can be obtained by observing the primary particles of the pigment through a transmission electron microscope and based on the image photographs obtained. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding thereto is calculated as the primary particle size of the pigment. In addition, the average primary particle size in the present specification is set to the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

[0220] The crystallite size determined from the half width of a peak originating from any crystal plane in an X-ray diffraction spectrum when CuKα rays of the pigment are used as the X-ray source is preferably 0.1 nm to 100 nm, more preferably 0.5 nm to 50 nm, further preferably 1 nm to 30 nm, and particularly preferably 5 nm to 25 nm.

[0221] As green colorants, phthalocyanine compounds and phthalocyanine compounds can be mentioned, preferably phthalocyanine compounds. In addition, the green colorant is preferably a pigment. As specific examples of green colorants, green pigments such as CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66 can be mentioned. In addition, as green colorants, compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used.

[0222] The green colorant is preferably CI Pigment Green 7, 36, 58, 59, 62, or 63, and more preferably CI Pigment Green 7, 36, 58, or 59.

[0223] Examples of the red colorant include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds, preferably diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds, and more preferably diketopyrrolopyrrole compounds. The red colorant is preferably a pigment. Specific examples of red colorants include CI (color index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 1 As the red colorant, the compounds described in paragraph 0034 of International Publication No. 2022 / 085485 can also be used. As the red colorant, Lumogen FOrange 240 (manufactured by BASF, red pigment, perylene pigment) can also be used.

[0224] The red colorant is preferably CI Pigment Red 122, 177, 179, 254, 255, 264, 269, 272, 291, and more preferably CI Pigment Red 254, 264, 272.

[0225] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinoline yellow compounds, and perylene compounds. The yellow colorant is preferably a pigment, more preferably an azo pigment, an azomethine pigment, an isoindoline pigment, a pteridine pigment, a quinoline yellow pigment, or a perylene pigment, and still more preferably an azo pigment or an azomethine pigment. Specific examples of yellow colorants include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120 0, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and other yellow pigments.

[0226] Furthermore, as a yellow colorant, an azobarbituric acid nickel complex having the following structure can also be used.

[0227] [Chemical formula 22]

[0228]

[0229] Furthermore, as the yellow colorant, the compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485 can also be used.

[0230] The yellow colorant is preferably CI Pigment Yellow 117, 129, 138, 139, 150, 185.

[0231] Examples of the orange colorant include CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.

[0232] Examples of the violet colorant include violet pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0233] As blue coloring agents, CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. can be mentioned. In addition, aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue coloring agents. As specific examples, compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Application Publication No. 2011-157478 can be mentioned.

[0234] Color colorants can also use dyes. There are no particular restrictions on the dyes, and known dyes can be used. For example, dyes such as pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyrromethene can be cited.

[0235] Color colorants can also use pigment polymers. The pigment polymer is preferably a dye used by dissolving in an organic solvent. In addition, the pigment polymer can form particles. When the pigment polymer is a particle, it is usually used in a state dispersed in a solvent. The pigment polymer in a particle state can be obtained, for example, by emulsion polymerization, and the compounds and manufacturing methods described in Japanese Patent Gazette No. 2015-214682 can be cited as specific examples. The pigment polymer can also use the compounds described in paragraph 0048 of International Publication No. 2022 / 085485.

[0236] The color colorant can use a diarylmethane compound described in Japanese Unexamined Patent Publication No. 2020-504758, a triarylmethane dye polymer described in Korean Unexamined Patent Publication No. 10-2020-0028160, a xanthene compound described in Japanese Unexamined Patent Publication No. 2020-117638, a phthalocyanine compound described in International Publication No. 2020 / 174991, an indoline compound described in Japanese Unexamined Patent Publication No. 2020-160279, or Salts thereof, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069069 The compound represented by formula 1 described in Japanese Patent No. 10-2020-0069062, the zinc phthalocyanine halogenide pigment described in Japanese Patent No. 6809649, the isoindoline compound described in Japanese Patent Publication No. 2020-180176, the phenothiazine compound described in Japanese Patent Publication No. 2021-187913, the quinoline yellow compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0030759, the The polymer dye described in Patent Publication No. 10-2020-0061793, the colorant described in Japanese Patent Publication No. 2022-029701, the isoindoline compound described in International Publication No. 2022 / 014635, the aluminum phthalocyanine compound described in International Publication No. 2022 / 024926, the compound described in Japanese Patent Publication No. 2022-045895, and the compound described in International Publication No. 2022 / 050051. The color colorant can be a rotaxane, and the pigment skeleton can be used for the cyclic structure of the rotaxane, can also be used for the rod-shaped structure, or can be used for both structures.

[0237] Two or more chromatic colorants may be used in combination. Furthermore, when two or more chromatic colorants are used in combination, black can be formed by the combination of two or more chromatic colorants.

[0238] As a black colorant, there is no particular limitation, and known black colorants can be used. For example, as an inorganic black colorant, carbon black, titanium black, zirconium oxynitride, graphite, etc. can be cited, preferably carbon black, titanium black or zirconium oxynitride, more preferably titanium black or zirconium oxynitride. Titanium black refers to black particles containing titanium atoms, preferably low-order titanium oxide and titanium oxynitride. Titanium black can use the titanium black described in paragraph 0044 of International Publication No. 2022 / 085485. As an organic black colorant, bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, etc. can be cited, preferably bisbenzofuranone compounds and perylene compounds. Organic black pigments can use the compounds described in paragraph 0166 of International Publication No. 2022 / 065215. Furthermore, as an organic black colorant, perylene black (Lumogen Black FK4280, etc.) and Paliogen Black S0084 described in paragraphs 0016 to 0020 of JP-A-2017-226821 may also be used.

[0239] The photocurable composition according to the present invention may contain a single colorant or two or more colorants. When two or more colorants are used, the total amount thereof is preferably within the following range.

[0240] From the viewpoint of further exerting the effect of the present invention, the content of the colorant is preferably 10% to 75% by mass relative to the total solid content of the photocurable composition. The upper limit is more preferably 70% by mass or less, and more preferably 65% ​​by mass or less. The lower limit is more preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 60% by mass or more.

[0241] <Radical polymerizable compounds>

[0242] The photocurable composition according to the present invention contains a radical polymerizable compound.

[0243] Examples of the radical polymerizable compound include compounds having an ethylenically unsaturated group.

[0244] As the resin type free radical polymerizable compound, there can be mentioned a resin containing a repeating unit having a free radical polymerizable group. The weight average molecular weight (Mw) of the resin type polymerizable compound is preferably 2,000 to 2,000,000. The upper limit of the weight average molecular weight is more preferably 1,000,000 or less, and further preferably 500,000 or less. The lower limit of the weight average molecular weight is more preferably 3,000 or more, and further preferably 5,000 or more.

[0245] The molecular weight of the monomer type radical polymerizable compound (polymerizable monomer) is preferably less than 2,000, more preferably 1,500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.

[0246] The compound having an ethylenically unsaturated group as a polymerizable monomer is preferably a 3-15-functional (meth)acrylate compound, and more preferably a 3-6-functional (meth)acrylate compound. Specific examples include the compounds described in paragraph 0128 of International Publication No. 2022 / 085485 and the compounds described in Japanese Patent Application Publication No. 2017-194662, and the contents thereof are incorporated into this specification.

[0247] As the compound having an ethylenically unsaturated group, the compounds described in paragraphs 0129 to 0137 of International Publication No. 2022 / 085485 can also be used. The compound having an ethylenically unsaturated group may be a compound having an acid group such as a carboxyl group, a sulfone group, or a phosphoric acid group, a compound having a caprolactone structure, a compound having an alkyleneoxy group, or a compound having a fluorene skeleton.

[0248] As the compound having an ethylenically unsaturated group, UA-7200 (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by KYOEISHA CHEMICAL Co., Ltd.), 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), and the like are also preferably used.

[0249] The content of the radical polymerizable compound is preferably 0.1% to 50% by mass relative to the total solid content of the photocurable composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and further preferably 40% by mass or less.

[0250] In the photocurable composition according to the present invention, the radical polymerizable compound may be used alone or in combination of two or more. When two or more radical polymerizable compounds are used, the total amount thereof is preferably within the above range.

[0251] <Resin>

[0252] The photocurable composition according to the present invention preferably further contains a resin.

[0253] The photocurable composition of the present invention can use a resin as a free radical polymerizable compound. The free radical polymerizable compound is preferably a compound containing at least a resin. For example, the resin is formulated for the purpose of dispersing a pigment or the like in the photocurable composition or for the purpose of an adhesive. In addition, the resin mainly used to disperse the pigment or the like in the photocurable composition is also referred to as a dispersant. However, such a use of the resin is an example, and the resin can also be used for purposes other than such a use.

[0254] In addition, resins having radical polymerizable groups also belong to radical polymerizable compounds.

[0255] Furthermore, the photocurable composition according to the present invention more preferably further contains a resin other than the radical polymerizable compound.

[0256] The weight average molecular weight of the resin is preferably 3000 to 2000000. The upper limit is preferably 1000000 or less, more preferably 500000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

[0257] As resin, (meth) acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide resin, polyamideimide resin, polyolefin resin, cycloolefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, polyurea resin etc. can be mentioned. Among these resins, one kind can be used alone, or two or more kinds can be mixed and used. As cycloolefin resin, from the viewpoint of improving heat resistance, it is preferably norbornene resin. As commercial products of norbornene resin, for example, ARTON series (for example, ARTON F4520) made by JSR Corporation etc. can be mentioned. Furthermore, as a resin, a resin described in paragraphs 0091 to 0099 of International Publication No. 2022 / 065215, a blocked polyisocyanate resin described in Japanese Patent Publication No. 2016-222891, a resin described in Japanese Patent Publication No. 2020-122052, a resin described in Japanese Patent Publication No. 2020-111656, a resin described in Japanese Patent Publication No. 2020-139021, and a resin described in Japanese Patent Publication No. 2017-138503 containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain can also be used. Furthermore, as a resin, a resin having a fluorene skeleton can also be preferably used. Regarding a resin having a fluorene skeleton, reference can be made to the description of U.S. Patent Application Publication No. 2017 / 0102610, which is incorporated into this specification. In addition, as the resin, the resin described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Application Publication No. 2020-186325, the resin represented by Formula 1 described in Korean Patent Application Publication No. 10-2020-0078339, and the copolymer containing an epoxy group and an acid group described in International Publication No. 2022 / 030445 can also be used.

[0258] As the resin, it is preferred to use a resin having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic group, and a phenolic hydroxyl group. These acid groups may be only one type or may be two or more types. For example, a resin having an acid group can be used as an alkali-soluble resin. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, further preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

[0259] As the resin, the compounds described in paragraphs 0056 to 0059 of International Publication No. 2022 / 085485 can also be used.

[0260] As the resin, it is also preferable to use a resin having a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated group and a cyclic ether group. Among them, from the viewpoint of outgassing inhibition, it is preferable to have a (meth)acryloyl group, an epoxy group or an oxetanyl group.

[0261] Furthermore, as a resin, a resin (hereinafter also referred to as resin Ep) having at least one repeating unit selected from the repeating unit represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2) (hereinafter also referred to as repeating unit Ep) can also be used. The above-mentioned resin Ep may contain only one of the repeating units represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2), or may contain the repeating unit represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2) separately. When containing these two repeating units, the ratio of the repeating unit represented by the formula (Ep-1) to the repeating unit represented by the formula (Ep-2) is preferably a repeating unit represented by the formula (Ep-1): the repeating unit represented by the formula (Ep-2) = 5:95 to 95:5, more preferably 10:90 to 90:10, and further preferably 20:80 to 80:20 in terms of molar ratio.

[0262] [Chemical formula 23]

[0263]

[0264] In formula (Ep-1) and (Ep-2), L 1 represents a single bond or a divalent linking group, R 1 represents a hydrogen atom or a substituent. 1 The substituent represented by may be an alkyl group or an aryl group, and an alkyl group is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 1 Preferably, L is a hydrogen atom or a methyl group. 1 The divalent linking group represented by the invention includes alkylene (preferably an alkylene having 1 to 12 carbon atoms), arylene (preferably an arylene having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, and a group formed by combining two or more of these. The alkylene may be any of a straight chain, a branched chain, and a cyclic chain, preferably a straight chain or a branched chain. Furthermore, the alkylene may have a substituent or may be unsubstituted. As the substituent, a hydroxyl group, an alkoxy group, etc. may be mentioned.

[0265] The content of the repeating unit Ep in the resin Ep is preferably 1 mol% to 100 mol% in all repeating units of the resin Ep. The upper limit is more preferably 90 mol% or less, and further preferably 80 mol% or less. The lower limit is more preferably 2 mol% or more, and further preferably 3 mol% or more.

[0266] The resin Ep may have other repeating units other than the above-mentioned repeating unit Ep. Examples of other repeating units include repeating units having an acid group and repeating units having an ethylenically unsaturated group.

[0267] Examples of the acid group include a phenolic hydroxyl group, a carboxyl group, a sulfone group, and a phosphoric acid group. A phenolic hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0268] Examples of the ethylenically unsaturated group include a vinyl group, a styryl group, a (meth)allyl group, and a (meth)acryloyl group.

[0269] When the resin Ep contains repeating units having an acid group, the content of the repeating units having an acid group in the resin Ep is preferably 5 mol% to 85 mol% in all repeating units of the resin Ep. The upper limit is more preferably 60 mol% or less, and further preferably 40 mol% or less. The lower limit is more preferably 8 mol% or more, and further preferably 10 mol% or more.

[0270] When the resin Ep contains a repeating unit having an ethylenically unsaturated group, the content of the repeating unit having an ethylenically unsaturated group in the resin Ep is preferably 1 mol% to 65 mol% in all the repeating units of the resin Ep. The upper limit is more preferably 45 mol% or less, and further preferably 30 mol% or less. The lower limit is more preferably 2 mol% or more, and further preferably 3 mol% or more.

[0271] Resin Ep preferably further comprises repeating units having aromatic hydrocarbon rings. As aromatic hydrocarbon rings, benzene rings or naphthalene rings are preferred, preferably benzene rings. Aromatic hydrocarbon rings may have substituents. As substituents, alkyl groups and the like can be cited. When the resin having a cyclic ether group comprises repeating units having aromatic hydrocarbon rings, the content of repeating units having aromatic hydrocarbon rings is preferably 1 mol% to 65 mol% in all repeating units of the resin having a cyclic ether group. The upper limit is more preferably 45 mol% or less, and more preferably 30 mol% or less. The lower limit is more preferably 2 mol% or more, and more preferably 3 mol% or more. As repeating units having aromatic hydrocarbon rings, repeating units of monofunctional polymerizable compounds having aromatic hydrocarbon rings such as vinyl toluene and benzyl (meth) acrylate can be cited.

[0272] As the resin, it is also preferred to use a resin having an aromatic carboxyl group (hereinafter also referred to as resin Ac). In resin Ac, the aromatic carboxyl group may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. The aromatic carboxyl group is preferably contained in the main chain of the repeating unit. In addition, in this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. Among the aromatic carboxyl groups, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.

[0273] The resin Ac is preferably a resin containing at least one repeating unit selected from the repeating unit represented by the formula (Ac-1) and the repeating unit represented by the formula (Ac-2).

[0274] [Chemical formula 24]

[0275]

[0276] In formula (Ac-1), Ar 1 represents a group containing an aromatic carboxyl group, L 1 Indicates -COO- or CONH-, L 2 It represents a divalent linking group.

[0277] In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxyl group, L 11 Indicates -COO- or CONH-, L 12 represents a trivalent linking group, P 10 Represents a polymer chain.

[0278] In the formula (Ac-1), Ar 1 Examples of the group containing an aromatic carboxyl group include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, etc. Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds of the following structures.

[0279] [Chemical formula 25]

[0280]

[0281] In the above formula, Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).

[0282] [Chemical formula 26]

[0283]

[0284] Ar 1The group containing an aromatic carboxyl group represented by may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated group or a cyclic ether group, and more preferably an ethylenically unsaturated group.

[0285] As Ar 1 Specific examples of the group containing an aromatic carboxyl group represented by include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), a group represented by the formula (Ar-13), and the like.

[0286] [Chemical formula 27]

[0287]

[0288] In the formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

[0289] In the formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and further preferably 2.

[0290] In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and further preferably 1. However, at least one of n3 and n4 is an integer of 1 or more.

[0291] In the formula (Ar-13), Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the above formula (Q-1) or a group represented by the above formula (Q-2).

[0292] In the formulas (Ar-11) to (Ar-13), *1 represents 1 bonding position.

[0293] In formula (Ac-1), L 1 It represents -COO- or CONH-, and preferably represents -COO-.

[0294] As L in formula (Ac-1) 2 The divalent linking group represented by may include alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and a group formed by combining two or more of these. The number of carbon atoms of the alkylene is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The alkylene may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The alkylene and arylene groups may have substituents. As substituents, hydroxyl groups and the like may be mentioned. L 2The divalent linking group represented by is preferably -L 2a -O- represented group. 2a Examples include alkylene groups; arylene groups; groups formed by combining alkylene groups and arylene groups; groups formed by combining at least one selected from alkylene groups and arylene groups with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and S-, etc., and alkylene groups are preferred. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The alkylene group may be any of a linear, branched, or cyclic group. The alkylene group and the arylene group may have a substituent. As the substituent, a hydroxyl group and the like may be mentioned.

[0295] As Ar in formula (Ac-2) 10 The group containing an aromatic carboxyl group represented by 1 The meanings are the same and the preferred aspects are also the same.

[0296] In formula (Ac-2), L 11 It represents -COO- or CONH-, and preferably represents -COO-.

[0297] As L in formula (Ac-2) 12 The trivalent linking group represented by may include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups formed by combining two or more of these. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be any of straight chain, branched chain, and cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group and the like. L 12 The trivalent linking group represented is preferably a group represented by the formula (L12-1), and more preferably a group represented by the formula (L12-2).

[0298] [Chemical formula 28]

[0299]

[0300] In formula (L12-1), L 12b represents a trivalent linking group, X 1 represents S, and *1 represents L in formula (Ac-2) 11 The bonding position of *2 indicates the bonding position with P of formula (Ac-2). 10 The bonding position of L 12bExamples of the trivalent linking group represented by include a hydrocarbon group; a group consisting of a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-, etc., preferably a hydrocarbon group or a group consisting of a hydrocarbon group and -O-.

[0301] In formula (L12-2), L 12c represents a trivalent linking group, X 1 represents S, and *1 represents L in formula (Ac-2) 11 The bonding position of *2 indicates the bonding position with P of formula (Ac-2). 10 The bonding position of L 12c Examples of the trivalent linking group represented by include a hydrocarbon group; a group consisting of a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-, and the like, and a hydrocarbon group is preferred.

[0302] In formula (Ac-2), P 10 Represents a polymer chain. 10 The polymer chain represented preferably has at least one repeating unit selected from the group consisting of a poly(meth)acrylic acid repeating unit, a polyether repeating unit, a polyester repeating unit, and a polyol repeating unit. 10 The weight average molecular weight is preferably 500 to 20,000. The lower limit is more preferably 1,000 or more. The upper limit is more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. 10 When the weight average molecular weight of the pigment is within the above range, the dispersibility of the pigment in the composition is good. When the resin having an aromatic carboxyl group is a resin having a repeating unit represented by formula (Ac-2), the resin can be preferably used as a dispersant.

[0303] P 10 The polymer chain represented may contain a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated groups.

[0304] The photocurable composition according to the present invention preferably contains a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).

[0305] Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. When the total amount of the amount of acid groups and the amount of basic groups is set to 100 mol %, the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more.

[0306] The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 mgKOH / g to 105 mgKOH / g.

[0307] The alkaline dispersant (alkaline resin) refers to a resin having a larger amount of basic groups than acid groups. When the total amount of the acid groups and the basic groups is set to 100 mol %, the alkaline dispersant (alkaline resin) is preferably a resin having a basic group amount exceeding 50 mol %.

[0308] The basic group contained in the basic dispersant is preferably an amino group.

[0309] The resin used as the dispersant is also preferably a graft polymer. For details of the graft polymer, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

[0310] Furthermore, from the viewpoint of dispersion stability, the resin preferably includes a graft polymer having a graft chain, wherein the graft chain includes at least one selected from the group consisting of a polyether chain, a polyester chain, and a polyacrylic acid chain, and the weight average molecular weight of the graft chain is 1,000 or more.

[0311] The resin used as a dispersant is also preferably a polyimine dispersant containing nitrogen atoms on at least one of the main chain and the side chain. As a polyimine dispersant, it is preferably a resin having a main chain and a side chain and having a basic nitrogen atom on at least one of the main chain and the side chain, wherein the main chain contains a partial structure having a functional group with a pKa of less than 14, and the number of atoms of the side chain is 40 to 10,000. There is no particular limitation on the basic nitrogen atom as long as it is a basic nitrogen atom. The polyimine dispersant can refer to the records of paragraphs 0102 to 0166 of Japanese Patent Publication No. 2012-255128, and the content is incorporated into this specification.

[0312] The resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Examples of such resins include dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0313] The resin used as a dispersant is also preferably a resin containing repeating units having ethylenically unsaturated groups in the side chains. The content of repeating units having ethylenically unsaturated groups in the side chains of all repeating units of the resin is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, and further preferably 20 mol% to 70 mol%.

[0314] As the resin having an oxetane group, for example, a resin described in International Publication No. 2021 / 182268 or International Publication No. 2021 / 187257 can be used.

[0315] Furthermore, the resin used as the dispersant is preferably a resin containing an oxetane group in a side chain, and more preferably a resin containing a repeating unit having an oxetane group in a side chain.

[0316] Furthermore, the resin containing an oxetane group in the side chain is preferably a graft polymer.

[0317] As the resin containing an oxetane group in the side chain, the resin described in the examples described below can be preferably cited. The content of the repeating unit having an oxetane group in the side chain of the above resin in all the repeating units of the resin is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, and further preferably 20 mol% to 70 mol%.

[0318] In addition, as a dispersant, a resin described in Japanese Patent Application Publication No. 2018-087939, a block copolymer (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Application No. 6432077, a polyethyleneimine having a polyester side chain described in International Publication No. 2016 / 104803, a block copolymer described in International Publication No. 2019 / 125940, a block polymer having an acrylamide structural unit described in Japanese Patent Application Publication No. 2020-066687, a block polymer having an acrylamide structural unit described in Japanese Patent Application Publication No. 2020-066688, a dispersant described in International Publication No. 2016 / 104803, and the like can also be used.

[0319] As the dispersant, a polyamic acid type dispersion resin or a polyimide type dispersion resin can also be used. As such resins, dispersants described in International Publication No. 2022 / 019253, International Publication No. 2022 / 019254, and International Publication No. 2022 / 019255 can also be used.

[0320] The dispersant can be obtained as a commercial product, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie GmbH (e.g., Disperbyk-111, 161, 2001, etc.), SOLSPERSE series manufactured by Japan Lubrizol Corporation (e.g., SOLSPERSE 20000, 76500, etc.), and Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc., etc. In addition, the product described in paragraph 0129 of Japanese Unexamined Patent Publication No. 2012-137564 and the product described in paragraph 0235 of Japanese Unexamined Patent Publication No. 2017-194662 can also be used as the dispersant.

[0321] When the photocurable composition of the present invention contains a resin as a free radical polymerizable compound, the content of the resin is preferably 1% to 70% by mass relative to the total solid content of the photocurable composition. The lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65% ​​by mass or less, and further preferably 60% by mass or less.

[0322] Furthermore, the content of the resin having an acid group is preferably 1% to 70% by mass relative to the total solid content of the photocurable composition. The lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65% ​​by mass or less, further preferably 60% by mass or less.

[0323] Furthermore, the content of the alkali-soluble resin is preferably 1% to 70% by mass relative to the total solid content of the photocurable composition. The lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65% ​​by mass or less, further preferably 60% by mass or less.

[0324] When the photocurable composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1% by mass to 30% by mass relative to the total solid content of the photocurable composition. The upper limit is more preferably 25% by mass or less, and more preferably 20% by mass or less. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. In addition, the content of the resin as a dispersant is preferably 1 to 100 parts by mass relative to 100 parts by mass of the colorant. The upper limit is more preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and particularly preferably 60 parts by mass or less. The lower limit is more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more.

[0325] The photocurable composition according to the present invention may contain only one resin or two or more resins. When two or more resins are contained, the total amount of these resins is preferably within the above range.

[0326] <Solvent>

[0327] The photocurable composition of the present invention preferably contains a solvent. As the solvent, an organic solvent can be mentioned. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coating property of the composition. As organic solvents, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, etc. can be mentioned. For details of these, reference can be made to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated into this specification. In addition, ester solvents substituted with cyclic alkyl groups and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, cyclopentane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropanol, etc. However, it is sometimes preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents for reasons such as environmental aspects (for example, it can be set to 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less relative to the total amount of the organic solvent).

[0328] In the present invention, it is preferred to use an organic solvent with a low metal content. The metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion: parts per billion) or less. Organic solvents of mass ppt (parts pertrillion: parts per trillion) level can be used as needed, such organic solvents are provided, for example, by Toyo Gosei Co., Ltd (Chemical Industry Daily, November 13, 2015).

[0329] As a method for removing impurities such as metals from an organic solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter can be cited. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

[0330] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). Furthermore, the isomers may contain only one type or multiple types.

[0331] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0332] The content of the solvent in the photocurable composition is preferably 10% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and further preferably 30% by mass to 90% by mass.

[0333] Moreover, from the viewpoint of environmental control, the photocurable composition of the present invention is preferably substantially free of environmental control substances. In addition, in the present invention, substantially free of environmental control substances means that the content of environmental control substances in the photocurable composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These are registered as environmental control substances based on REACH (Registration Evaluation Authorization and Restriction of Chemicals: Registration, Evaluation, Permit and Restriction of Chemicals) Act, PRTR (Pollutant Release and Transfer Register: Pollutant Release and Transfer Report) Act, VOC (Volatile Organic Compounds: Volatile Organic Compounds) control, etc., and the amount of use and operation methods are strictly controlled. These compounds are sometimes used as solvents when manufacturing the various components used in the photocurable composition, and sometimes mixed into the photocurable composition as residual solvents. From the viewpoint of human safety and environmental protection, it is preferred to reduce these substances as much as possible. As a method for reducing environmentally controlled substances, there can be cited a method of heating and reducing the system interior to set the boiling point above the environmentally controlled substances, thereby distilling and removing the environmentally controlled substances from the system interior and reducing the environmentally controlled substances. In addition, when distilling and removing a small amount of environmentally controlled substances, in order to improve efficiency, it is also useful to make it azeotropic with a solvent having the same boiling point as the solvent. In addition, when containing a compound with free radical polymerizability, a polymerization inhibitor can be added and removed by reduced pressure distillation to inhibit free radical polymerization during the reduced pressure distillation and removal, resulting in crosslinking between molecules. These distillation removal methods can be implemented at any stage, such as the stage of raw materials, the stage of products that react the raw materials (such as resin solutions after polymerization, multifunctional monomer solutions), or the stage of photocurable compositions prepared by mixing these compounds.

[0334] <Pigment derivatives>

[0335] The photocurable composition of the present invention preferably further comprises a pigment derivative. The pigment derivative can be used as a dispersing aid, for example. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.

[0336] Examples of the pigment skeleton constituting the pigment derivative include a quinoline pigment skeleton, a benzimidazolone pigment skeleton, a benzindole pigment skeleton, a benzothiazole pigment skeleton, an imine pigment skeleton, a squarylium pigment skeleton, a crotonium pigment skeleton, an oxonol pigment skeleton, a pyrrolopyrrole pigment skeleton, a diketopyrrolopyrrole pigment skeleton, an azo pigment skeleton, an azomethine pigment skeleton, a phthalocyanine pigment skeleton, a naphthalocyanine pigment skeleton, an anthraquinone pigment skeleton, a quinacridone pigment skeleton, a dioxazine pigment skeleton, a perindole pigment skeleton, a perylene pigment skeleton, a thioindigo pigment skeleton, an isoindoline pigment skeleton, an isoindolinone pigment skeleton, a quinoline yellow pigment skeleton, an imine pigment skeleton, a dithiol pigment skeleton, a triarylmethane pigment skeleton, and a pyrromethene pigment skeleton.

[0337] Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boric acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group, and salts thereof. Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li + 、Na + , K + etc.), alkaline earth metal ions (Ca 2+ Mg 2+ As the carboxylic acid amide group, preferably -NHCOR X1 As the sulfonic acid amide group, preferably -NHSO2R X2 As the imidic acid group, preferably -SO2NHSO2R X3 、-CONHSO2R X4 、-CONHCOR X5 SO2NHCOR X6 The group represented by is more preferably -SO2NHSO2R X3 . R X1 ~R X6 R each independently represents an alkyl group or an aryl group. X1 ~R X6 The alkyl group and aryl group represented by the above-mentioned may have a substituent, and the substituent is preferably a halogen atom, and more preferably a fluorine atom.

[0338] Examples of the basic group include amino, pyridyl and salts thereof, ammonium salts and phthalimidomethyl groups. Examples of the atom or atomic group constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, and phenolate ions.

[0339] The pigment derivative may have excellent visible transparency (hereinafter referred to as a transparent pigment derivative). The maximum value (εmax) of the molar absorption coefficient of the transparent pigment derivative in the wavelength region of 400 nm to 700 nm is preferably 3,000 L·mol-1 cm -1 Below, more preferably 1,000 L·mol -1 cm -1 Below, more preferably 100 L·mol -1 cm -1 The lower limit of εmax is, for example, 1 L·mol -1 cm -1 Above, it can also be 10L·mol -1 cm -1 above.

[0340] Specific examples of pigment derivatives include compounds described in paragraph 0124 of International Publication No. 2022 / 085485, benzimidazolone compounds or salts thereof described in Japanese Patent Application Publication No. 2018-168244, and compounds having an isoindoline skeleton described in general formula (1) in Japanese Patent No. 6996282.

[0341] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the colorant. Furthermore, the total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, and particularly preferably 50% by mass or more, relative to the total solid content of the photocurable composition. The upper limit is preferably 70% by mass or less, more preferably 65% ​​by mass or less. One type of the pigment derivative may be used alone, or two or more types may be used simultaneously.

[0342] <Chain transfer agent>

[0343] From the viewpoint of adhesion, the photocurable composition according to the present invention preferably further contains a chain transfer agent.

[0344] Examples of the chain transfer agent include thiol compounds, thiocarbonylthio compounds, and dimers of aromatic α-methylalkenyl groups, and thiol compounds are preferred because the line width of the pattern can be easily adjusted even with a small amount of the compound. Furthermore, the chain transfer agent is preferably a compound with little coloration.

[0345] -Mercaptan compounds-

[0346] The thiol compound is a compound having one or more thiol groups, preferably a compound having two or more thiol groups. The upper limit of the number of thiol groups contained in the thiol compound is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, particularly preferably 8 or less, and most preferably 6 or less. The lower limit of the number of thiol groups contained in the thiol compound is preferably 3 or more. From the viewpoint of adhesion, the thiol compound is particularly preferably a compound having 4 thiol groups.

[0347] Furthermore, the thiol compound is also preferably a compound derived from a polyfunctional alcohol.

[0348] The thiol compound is preferably a compound represented by the following formula (SH-1).

[0349] L 1 -(SH) n Formula (SH-1)

[0350] In the formula, SH represents a thiol group, L 1 It represents an n-valent group, where n represents an integer of 1 or greater.

[0351] In formula (SH-1), L 1 The n-valent group represented by may include hydrocarbon groups, heterocyclic groups, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, -SO2- or groups consisting of combinations thereof. R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Furthermore, the aliphatic hydrocarbon group may be cyclic or non-cyclic. Furthermore, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may not have a substituent. Furthermore, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a condensed ring. The heterocyclic group may be a monocyclic ring or a condensed ring. As the heterocyclic group, a 5-membered ring or a 6-membered ring is preferred. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Furthermore, as heteroatoms constituting the heterocyclic group, nitrogen atoms, oxygen atoms, sulfur atoms, etc. may be mentioned. 1 The number of carbon atoms in is preferably 3-100, more preferably 6-50.

[0352] In formula (SH-1), n ​​represents an integer greater than 1. The upper limit of n is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, particularly preferably 8 or less, and most preferably 6 or less. The lower limit of n is preferably 2 or more, more preferably 3 or more. n is particularly preferably 4.

[0353] Specific examples of thiol compounds include compounds of the following structures: Commercially available products of thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd.), Sanceler M (manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.), and Karenz MT BD1 (manufactured by SHOWA DENKOK.K.).

[0354] [Chemical formula 29]

[0355]

[0356] [Chemical formula 30]

[0357]

[0358] [Chemical formula 31]

[0359]

[0360] [Chemical formula 32]

[0361]

[0362] -Thiocarbonylthio compounds-

[0363] The thiocarbonylthio compound is a compound having a thiocarbonylthio group (-SC(=S)-) in the molecule, and examples thereof include bis(thiocarbonyl) disulfide compounds (compounds represented by the following formula (SC-1)), dithioester compounds (compounds represented by the following formula (SC-2)), trithiocarbonate compounds (compounds represented by the following formula (SC-3)), dithiocarbamate compounds (compounds represented by the following formula (SC-4)), and xanthate compounds (compounds represented by the following formula (SC-5)).

[0364] [Chemical formula 33]

[0365]

[0366] In formula (SC-1) to formula (SC-5), Z 1 ~Z 11 Each independently represents a substituent.

[0367] As Z 1 ~Z 11 The substituent represented by may be alkyl, aryl, heteroaryl, -SR Z1 、-NR Z1 R Z2 、-NR Z1 -NR Z2 R Z3 、-COOR Z1 、-OCOR Z1 、-CONR Z1 R Z2 、-P(=O)(OR Z1 )2 or -OP(=O)R Z1 R Z2 (Among them, R Z1 , R Z2 and R Z3Each of them is independently an alkyl group, an aryl group or a heteroaryl group. ) etc. Furthermore, in the above groups, one or more hydrogen atoms bonded to a carbon atom may be substituted by a cyano group, a carboxyl group or the like.

[0368] The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0369] The aryl group has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms.

[0370] The heteroaryl group is preferably a monocyclic heteroaryl group or a fused-ring heteroaryl group having 2 to 8 fused rings, and more preferably a monocyclic heteroaryl group or a fused-ring heteroaryl group having 2 to 4 fused rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the heteroaryl group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.

[0371] Specific examples of the bis(thiocarbonyl) disulfide compounds include tetraethylthiuram disulfide, tetramethylthiuram disulfide, bis(n-octylmercapto-thiocarbonyl) disulfide, bis(n-dodecylmercapto-thiocarbonyl) disulfide, bis(benzylmercapto-thiocarbonyl) disulfide, bis(n-butylmercapto-thiocarbonyl) disulfide, bis(tert-butylmercapto-thiocarbonyl) disulfide, bis(n-heptylmercapto-thiocarbonyl) disulfide, bis(n-hexylmercapto-thiocarbonyl) disulfide, bis(n-pentylmercapto-thiocarbonyl) disulfide, bis(n-nonylmercapto-thiocarbonyl) disulfide, bis(n-decylmercapto-thiocarbonyl) disulfide, bis(tert-dodecylmercapto-thiocarbonyl) disulfide, bis(n-tetradecylmercapto-thiocarbonyl) disulfide, bis(n-hexadecylmercapto-thiocarbonyl) disulfide, and bis(n-octadecylmercapto-thiocarbonyl) disulfide.

[0372] Specific examples of the dithioester compound include 2-phenyl-2-propylbenzodisulfate, 4-cyano-4-(phenylthiocarbonylthio)pentanoic acid, and 2-cyano-2-propylbenzodisulfate.

[0373] Specific examples of the trithiocarbonate compound include S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonate, 4-cyano-4-[(dodecylthio-thiocarbonyl)thio]pentanoic acid, cyanomethyldodecyl trithiocarbonate, and 2-(dodecylthiocarbonylthiothio)-2-methylpropionic acid.

[0374] Specific examples of the dithiocarbamate compound include cyanomethylmethyl(phenyl)carbamoyl disulfate and cyanomethyldiphenylcarbamoyl disulfate.

[0375] Specific examples of the xanthate compound include xanthate esters and the like.

[0376] -Dimer of aromatic α-methylalkenyl group-

[0377] Examples of the dimer of the aromatic α-methylalkenyl group include 2,4-diphenyl-4-methyl-1-pentene and the like.

[0378] Furthermore, as the chain transfer agent, a trithiocarbonate compound which is used as a RAFT agent in RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization which is one type of living polymerization can also be preferably used.

[0379] The molecular weight of the chain transfer agent is preferably 200 or more because it can suppress contamination of the device due to sublimation, etc. The upper limit is preferably 1,000 or less, more preferably 800 or less, and further preferably 600 or less because it can increase the SH valence per unit mass.

[0380] From the viewpoint of adhesion, the content of the chain transfer agent is preferably 0.01% to 10% by mass, more preferably 0.01% to 5% by mass, and further preferably 0.05% to 1% by mass relative to the total solid content of the photocurable composition. The chain transfer agent may be used alone or in combination of two or more.

[0381] <Sensitizer>

[0382] The photocurable composition of the present invention preferably further contains a sensitizer. By containing a sensitizer, not only the exposure sensitivity to i-rays (wavelength 365 nm) but also the exposure sensitivity to KrF excimer laser (wavelength 248 nm) can be improved.

[0383] Furthermore, from the viewpoint of sensitivity, the sensitizer preferably includes a sensitizer having absorption at a wavelength of 365 nm.

[0384] Examples of the sensitizer include aromatic compounds such as benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, coumarin, phenothiazine and its derivatives, 3-(aroylmethylene)thiazoline, rhodanine, camphorquinone, and the like.

[0385] Also, preferred examples of the sensitizer include eosin, rose bengal, erythrosine, xanthene, thioxanthone, acridine such as 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl)pentane, cyanine pigments, and merocyanine pigments.

[0386] Specific examples of the sensitizer include the following sensitizers.

[0387] 1. Thioxanthones

[0388] Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxy-thioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano -3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-sulfonylphenylthioxanthone, 3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 1,3-dimethyl-2-hydroxy-9H-thioxanthone-9-one 2-ethylhexyl ether, 1- Ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboxylic imide, N-octylthioxanthone-3,4-dicarboxylic imide, N-(1 ,1,3,3-tetramethylbutyl)thioxanthone-3,4-dicarboxylic imide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylic acid polyethylene glycol ester, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propane ammonium chloride;

[0389] 2. Benzophenone

[0390] Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(methylethylamino)benzophenone, 4,4'-bis(p-isopropylphenoxy)benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2-benzoylbenzoic acid methyl ester, 4-(2- 1-[4-(4-benzoyl-phenylthio)phenyl]-2-methyl-2-(toluene-4-sulfonyl)propan-1-one, 4-benzoyl-N,N,N-trimethylbenzylamine chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-chloropropylamine monohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxytridecyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethyl-benzylamine chloride;

[0391] 3. Coumarin

[0392] Coumarin 1, Coumarin 2, Coumarin 6, Coumarin 7, Coumarin 30, Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337, Coumarin 500, 3-Benzoyl-7-methoxy-coumarin, 3-Benzoyl-5,7-dimethoxy-coumarin, 3-Benzoyl-5,7-dipropoxy-coumarin, 3-Benzoyl-6,8-dichlorocoumarin, 3-Benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis[5,7-di(propyloxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-diethylamino-coumarin), 3-isobutyrylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3- Benzoyl-5,7-di(methoxyethoxy)coumarin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyryl-7-dimethylaminocoumarin, 5,7-dimethoxy-3-(1-naphthoyl)coumarin, 5,7-diethoxy-3-(1-naphthoyl)coumarin, 3-benzoylbenzo[f]coumarin, 7-diethylamino-3 -thiopheneylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, 3-(4-cyanobenzoyl)-5,7-dipropoxycoumarin, 7-dimethylamino-3-phenylcoumarin, 7-diethylamino-3-phenylcoumarin, coumarin derivatives disclosed in JP09-179299-A and JP09-325209-A, such as 7-[{4-chloro-6-(diethylamino)-S-triazine-2-yl}amino]-3-phenylcoumarin;

[0393] 4.3-(Aroylmethylene)thiazolines

[0394] 3-Methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline;

[0395] 5. Rhodanine

[0396] 4-dimethylaminobenzylidene rhodanine, 4-diethylaminobenzylidene rhodanine, 3-ethyl-5-(3-octyl-2-benzothiazolylidene)rhodanine, and rhodanine derivatives represented by formula [1], [2] or [7] disclosed in Japanese Patent Application Laid-Open No. 8-305019;

[0397] 6. Other compounds

[0398] Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, diphenyl ketone, 4,4'-bis(dimethylamino)diphenyl ketone, 2-acetylnaphthalene, 2-naphthaldehyde, dansyl acid derivatives, 9,10-anthraquinone, anthracene, pyrene, aminopyrene, perylene, phenanthrene, phenanthrenequinone, 9-fluorenone, dibenzosuberone, curcumin, xanthone, thiomichler's ketone, α-(4-dimethylaminobenzylidene) ketone such as 2,5-bis(4-diethylaminobenzylidene)cyclopentanone, 2-(4-dimethylaminobenzylidene)indene-1-one, 3-(4-dimethylaminophenyl)-1 -inden-5-yl-propenone, 3-phenylthiophthalimide, N-methyl-3,5-bis(ethylthio)phthalimide, N-methyl-3,5-bis(ethylthio)phthalimide, phenothiazine, methylphenothiazine, amines such as N-phenylglycine, ethyl 4-dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, triethanolamine, methyldiethanolamine, dimethylaminoethanol, ethyl 2-(dimethylamino)benzoate, poly(propylene glycol)-4-(dimethylamino)benzoate.

[0399] The sensitizer is preferably at least one compound selected from the group consisting of benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, and coumarin and its derivatives from the viewpoint of sensitivity.

[0400] Furthermore, as a sensitizer, in order to promote photopolymerization, an amine compound can be added, for example, triethanolamine, N-methyldiethanolamine, ethyl p-dimethylaminobenzoate, ethyl 2-(dimethylamino)benzoate, 2-ethylhexyl-p-dimethylaminobenzoate, octyl p-N,N-dimethylaminobenzoate, N-(2-hydroxyethyl)-N-methyl-p-toluidine or Michler's ketone. The effect of the amine compound can be enhanced by the addition of a benzophenone-type aromatic ketone compound.

[0401] Examples of amine compounds that can be used as oxygen scavengers include substituted N,N-dialkylanilines described in European Patent Application Publication No. 339841.

[0402] Other accelerators, co-initiators and self-oxidizing agents include thiol compounds, sulfide compounds, disulfide compounds, phosphonium salt compounds, phosphine oxide compounds or phosphine compounds, which are described in, for example, European Patent Application Publication No. 438123, British Patent Application Publication No. 2180358 and Japanese Patent Application Publication No. 6-68309.

[0403] The content of the sensitizer in the total solid content of the photocurable composition is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 10% by mass, and further preferably 0.1% by mass to 5% by mass. The photocurable composition of the present invention may contain only one sensitizer or two or more sensitizers. When containing two or more sensitizers, it is preferred that the total amount of these sensitizers is within the above range.

[0404] <Polyalkyleneimine>

[0405] The photocurable composition of the present invention may also contain polyalkyleneimines. Polyalkyleneimines can be used, for example, as dispersing aids for pigments. A dispersing aid refers to a material used to improve the dispersibility of pigments in a photocurable composition. Polyalkyleneimines refer to polymers obtained by ring-opening polymerization of alkyleneimines and having at least a secondary amino group. In addition to secondary amino groups, polyalkyleneimines may also contain primary amino groups or tertiary amino groups. Polyalkyleneimines are preferably polymers having a branched structure containing primary amino groups, secondary amino groups, and tertiary amino groups, respectively. The number of carbon atoms in the alkyleneimines is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0406] The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, and particularly preferably 2,000 or less. In addition, when the molecular weight of the polyalkyleneimine can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of the polyalkyleneimine cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point rise method is used. In addition, when the boiling point rise method cannot be measured or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used. In addition, when the viscosity method cannot be measured or is difficult to measure by the viscosity method, the value of the number average molecular weight measured by the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.

[0407] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and further preferably 15 mmol / g or more.

[0408] As a specific example of alkylene imine, ethyleneimine, propyleneimine, 1,2-buteneimine, 2,3-buteneimine, etc. can be cited, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. Polyalkylene imine is particularly preferably polyethyleneimine. In addition, in polyethyleneimine, relative to the total of primary amino groups, secondary amino groups and tertiary amino groups, it is preferred to contain more than 10 mol% of primary amino groups, more preferably more than 20 mol%, and further preferably more than 30 mol%. As a commercial product of polyethyleneimine, EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (the above are made by NIPPON SHOKUBAICO., LTD.) and the like can be cited.

[0409] The content of the polyalkylene imine in the total solid content of the photocurable composition is preferably 0.1% by mass to 5% by mass. The lower limit is more preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is more preferably 4.5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less. In addition, the content of the polyalkylene imine is preferably 0.5% by mass to 20% by mass relative to 100 parts by mass of the pigment. The lower limit is more preferably 0.6% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit is more preferably 10% by mass or less, and further preferably 8% by mass or less. Only one polyalkylene imine may be used, or two or more may be used. When two or more are used, it is preferred that the total amount of these is within the above range.

[0410] <Curing accelerator>

[0411] The photocurable composition of the present invention can contain a curing accelerator. As a curing accelerator, thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, etc. can be cited. As a specific example of a curing accelerator, the compounds described in paragraph 0164 of International Publication No. 2022 / 085485 can also be used. The content of the curing accelerator in the total solid content of the photocurable composition is preferably 0.3% to 8.9% by mass, and more preferably 0.8% to 6.4% by mass.

[0412] <Infrared absorber>

[0413] The photocurable composition of the present invention may contain an infrared absorber. For example, when an infrared transmission filter is formed using the photocurable composition of the present invention, the wavelength of light transmitted through the film obtained by containing an infrared absorber in the photocurable composition can be shifted to a longer wavelength side. The infrared absorber is preferably a compound having a maximum absorption wavelength on a wavelength side longer than 700nm. The infrared absorber is preferably a compound having a maximum absorption wavelength in a range of more than 700nm and less than 1800nm. In addition, the absorbance A of the infrared absorber at a wavelength of 500nm is preferably 0.1%. 1 and the absorbance A at the maximum absorption wavelength 2 A 1 / A 2 It is preferably 0.08 or less, and more preferably 0.04 or less.

[0414] Examples of infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, crotonium compounds, oxocyanine compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiol metal complexes, metal oxides, and metal borides. Specifically, the compounds described in paragraphs 0114 to 0121 of International Publication No. 2022 / 065215, the compounds described in paragraphs 0144 to 0146 of International Publication No. 2021 / 049441, the croconic acid compounds described in Japanese Patent Application Publication No. 2021-195515, the near-infrared absorbing pigments described in Japanese Patent Application Publication No. 2022-022070, and the crotonium compounds described in International Publication No. 2019 / 021767 can also be used.

[0415] The content of the infrared absorber in the total solid content of the photocurable composition is preferably 1% to 40% by mass. The lower limit is more preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 25% by mass or less. The photocurable composition of the present invention may contain only one infrared absorber or two or more. When containing two or more infrared absorbers, it is preferred that the total amount of these is within the above range.

[0416] <Ultraviolet light absorber>

[0417] The photocurable composition of the present invention can contain an ultraviolet absorber. As an ultraviolet absorber, conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, triazine compounds, etc. can be cited. As a specific example of such compounds, the compounds described in paragraph 0179 of International Publication No. 2022 / 085485 can also be used. As an ultraviolet absorber, the reactive triazine ultraviolet absorber described in Japanese Patent Publication No. 2021-178918 and the ultraviolet absorber described in Japanese Patent Publication No. 2022-007884 can be used. The content of the ultraviolet absorber in the total solid content of the photocurable composition is preferably 0.01% to 10% by mass, and more preferably 0.01% to 5% by mass. The ultraviolet absorber can be used only one kind, or two or more kinds can be used. When using two or more kinds, it is preferred that the total amount of these is within the above range.

[0418] <Polymerization inhibitor>

[0419] The photocurable composition of the present invention can contain a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine salt (ammonium salt, cerium salt, etc.) can be mentioned. Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the photocurable composition is preferably 0.0001% by mass to 5% by mass. The polymerization inhibitor may be only one or more than two. In the case of more than two, it is preferred that the total amount of these is within the above range.

[0420] <Silane coupling agent>

[0421] The photocurable composition involved in the present invention can contain a silane coupling agent. In the present invention, a silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than this. In addition, a hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can produce a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, etc., preferably an alkoxy group. That is, a silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, as a functional group other than a hydrolyzable group, for example, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetane group, an amino group, a urea group, a thioether group, an isocyanate group, a phenyl group, etc., preferably an amino group, a (meth) acryloyl group and an epoxy group. As a specific example of a silane coupling agent, a compound described in paragraph 0177 of International Publication No. 2022 / 085485 can also be used. The content of the silane coupling agent in the total solid content of the photocurable composition is preferably 0.01% by mass to 15.0% by mass, and more preferably 0.05% by mass to 10.0% by mass.

[0422] The silane coupling agent may be used alone or in combination of two or more. When used in combination of two or more types, the total amount of the silane coupling agent is preferably within the above range.

[0423] <Surfactant>

[0424] The photocurable composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant may be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. Regarding the surfactant, reference may be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated into this specification.

[0425] The fluorine content in the fluorine-based surfactant is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, and particularly preferably 7% to 25% by mass. Fluorine-based surfactants having a fluorine content within this range are effective in terms of thickness uniformity and liquid saving of the coating film, and also have good solubility in the photocurable composition.

[0426] As the fluorine-based surfactant, the compounds described in paragraphs 0167 to 0173 of International Publication No. 2022 / 085485, the fluorinated copolymers described in Japanese Patent Application Laid-Open No. 2022-000494, and the like can also be used.

[0427] As the nonionic surfactant, the compounds described in paragraph 0174 of International Publication No. 2022 / 085485 can also be used.

[0428] Examples of the silicone surfactant include DOWSIL (registered trademark: the same below) SH8400, SH8400FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie GmbH), etc.

[0429] Furthermore, as the silicone-based surfactant, compounds having the following structures can also be used.

[0430] [Chemical formula 34]

[0431]

[0432] The content of the surfactant in the total solid content of the photocurable composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005% to 3.0% by mass. The surfactant may be only one or two or more. In the case of two or more, the total amount of these is preferably within the above range.

[0433] <Antioxidants>

[0434] The photocurable composition involved in the present invention can contain an antioxidant. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be mentioned. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be mentioned. Preferably, it is a compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenolic group and a phosphite group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. As commercially available antioxidants, for example, ADEKA STAB (registered trademark: the same below) AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB A-80, ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION) etc. can be mentioned. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in International Publication No. 2017 / 006600, the compounds described in International Publication No. 2017 / 164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the photocurable composition is preferably 0.01% to 20% by mass, and more preferably 0.3% to 15% by mass. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

[0435] <Other ingredients>

[0436] The photocurable composition of the present invention may contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliary agents (e.g., conductive particles, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, etc.) as needed. By appropriately containing these ingredients, it is possible to adjust properties such as film physical properties. These ingredients can also use compounds described in paragraph 0182 of International Publication No. 2022 / 085485, xanthene-type epoxy resins described in Japanese Patent Publication No. 2021-195421, and xanthene-type epoxy resins described in Japanese Patent Publication No. 2021-195422.

[0437] The photocurable composition of the present invention may contain a metal oxide to adjust the refractive index of the obtained film. Examples of the metal oxide include TiO2, ZrO2, Al2O3, SiO2, etc. The primary particle size of the metal oxide is preferably 1 nm to 100 nm, more preferably 3 nm to 70 nm, and further preferably 5 nm to 50 nm. The metal oxide may have a core-shell structure. In addition, the core may be hollow.

[0438] The photocurable composition according to the present invention may contain a light resistance improver. As the light resistance improver, the compounds described in paragraph 0183 of International Publication No. 2022 / 085485 can also be used.

[0439] The photocurable composition of the present invention also preferably contains substantially no terephthalate. Here, “substantially contains” means that the content of terephthalate in the total amount of the photocurable composition is 1000 ppb or less, more preferably 100 ppb or less, and particularly preferably zero.

[0440] From the perspective of environmental regulation, the use of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts is sometimes regulated. In the photocurable composition involved in the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (especially perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts and perfluoroalkyl carboxylic acid (especially perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01ppb to 1,000ppb, more preferably in the range of 0.05ppb to 500ppb, and further preferably in the range of 0.1ppb to 300ppb. The photocurable composition involved in the present invention may also be substantially free of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts. For example, by using a compound that can replace perfluoroalkyl sulfonic acid and its salts and a compound that can replace perfluoroalkyl carboxylic acid and its salts, a photocurable composition that substantially does not contain perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts can also be selected. As compounds that can replace the regulated compounds, for example, compounds that are excluded from the regulated objects due to the difference in the number of carbon atoms of the perfluoroalkyl group can be cited. However, the above content does not prevent the use of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts. The photocurable composition involved in the present invention can also contain perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts within the maximum allowable range.

[0441] The water content of the photocurable composition of the present invention is preferably 3% by mass or less, more preferably 0.01% by mass to 1.5% by mass, and even more preferably 0.1% by mass to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0442] The photocurable composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface (flatness, etc.) and adjusting the film thickness. The value of the viscosity can be appropriately selected as needed, for example, at 25°C, preferably 0.3mPa·s to 50mPa·s, more preferably 0.5mPa·s to 20mPa·s. As a method for measuring the viscosity, for example, a cone plate type viscometer can be used to measure the viscosity at a temperature adjusted to 25°C.

[0443] Regarding the photocurable composition involved in the present invention, from the perspectives of environmental response, suppression of foreign matter generation, suppression of device pollution, etc., the amount of chloride ions in the photocurable composition is preferably 10,000 ppm or less, and more preferably 1000 ppm or less. In order to make the chloride ions in the photocurable composition within the above range, a method of using a raw material with a small chloride ion content, a method of removing chloride ions by water washing, ion exchange resin, filter filtration, etc., can be cited. As a method for measuring chloride ions, a known method can be used, for example, ion chromatography, combustion ion chromatography, etc. can be cited.

[0444] <Storage container>

[0445] The storage container of the photocurable composition is not particularly limited, and a known storage container can be used. In addition, as the storage container, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can also be used.

[0446] <Method for preparing photocurable composition>

[0447] The photocurable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photocurable composition, all the components can be dissolved and / or dispersed in a solvent at the same time to prepare the photocurable composition, or each component can be appropriately divided into two or more solutions or dispersions as needed, and these can be mixed when used (when applied) to prepare the photocurable composition.

[0448] And, when preparing the photocurable composition, it is preferred to include a pigment dispersion process. In the pigment dispersion process, as the mechanical force for dispersing the pigment, compression, extrusion, impact, shearing, cavitation, etc. can be cited. As the specific example of these processes, bead milling, sand milling, roller milling, ball milling, coating stirring, micro jet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, etc. can be cited. And, in the pulverization of the pigment in the sand mill (bead mill), it is preferably processed under the conditions of improving the pulverization efficiency by using micro beads with a small diameter, increasing the filling rate of micro beads, etc. mechanisms. And, after the pulverization process, it is preferably removed by filtering, centrifugation, etc. coarse particles. In addition, regarding the pigment dispersion process and the disperser, it is preferred to use the process and disperser described in paragraph 0022 of "Dispersion Technology Collection, JOHOKIKO CO., LTD., July 15, 2005", "Dispersion Technology and Practical Industrial Application Comprehensive Data Collection Centering on Suspension (Solid / Liquid Dispersion System), Business Development Center Publishing Department, October 10, 1978", and Japanese Patent Publication No. 2015-157893. In addition, in the pigment dispersion process, the particles can be refined by a salt milling process. For example, the materials, devices, processing conditions, etc. used in the salt milling process can refer to the records of Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. As microbeads for dispersion, zirconium dioxide, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, aluminum oxide, stainless steel, glass, or a combination of these can be used. Furthermore, it is possible to use an inorganic compound having a Mohs hardness of 2 or more. The above beads may be contained in the composition in an amount of 1 to 10,000 ppm.

[0449] When preparing a photocurable composition, it is preferred to filter the photocurable composition with a filter in order to remove foreign matter and reduce defects, etc. The filter and filtering method described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485 can also be used.

[0450] (cured product and film)

[0451] The cured product according to the present invention is a cured product of the photocurable composition according to the present invention.

[0452] The film of the present invention is preferably a film obtained from the photocurable composition of the present invention and is a cured product (cured film) of the photocurable composition of the present invention. The film of the present invention can be used for optical filters such as color filters and infrared transmission filters.

[0453] Specifically, the film of the present invention can be preferably used as a color pixel of a color filter, and the color pixel includes red pixel, green pixel, blue pixel, magenta pixel, cyan pixel, yellow pixel, etc., preferably green pixel, blue pixel, and more preferably green pixel.

[0454] The film thickness of the film involved in the present invention can be appropriately adjusted according to the purpose. The film thickness of the film involved in the present invention is preferably 0.1μm to 20μm. The upper limit of the film thickness of the film involved in the present invention is more preferably 10μm or less, more preferably 5μm or less, particularly preferably 3μm or less, and most preferably 1.5μm or less. The lower limit of the film thickness is more preferably 0.2μm or more, and more preferably 0.3μm or more.

[0455] (Method for producing cured product and method for producing film)

[0456] The method for producing the cured product and the method for producing the film of the present invention are not particularly limited, but preferably include a step of irradiating the photocurable composition of the present invention with light having a wavelength of 150 nm to 300 nm.

[0457] Examples of the light having a wavelength of 150 nm to 300 nm include KrF rays (wavelength: 248 nm) and ArF rays (wavelength: 193 nm).

[0458] Furthermore, the light having a wavelength of 150 nm to 300 nm is preferably an excimer laser.

[0459] The shape of the obtained cured product is not particularly limited, but is preferably a film shape. That is, the method for producing a cured product is preferably a method for producing a cured film.

[0460] The film of the present invention can be manufactured by applying the photocurable composition of the present invention on a support. The method for manufacturing the film preferably further includes a step of forming a pattern (pixel). As a method for forming a pattern (pixel), photolithography and dry etching can be cited, preferably photolithography.

[0461] The pattern formation based on the photolithography method preferably includes a step of forming a photocurable composition layer on a support using the photocurable composition involved in the present invention, a step of exposing the photocurable composition layer in a pattern, and a step of developing and removing the unexposed portion of the photocurable composition layer to form a pattern (pixel). A step of baking the photocurable composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) may also be provided as needed.

[0462] In the process of forming a photocurable composition layer, a photocurable composition according to the present invention is used to form a photocurable composition layer on a support. As a support, there is no particular limitation and it can be appropriately selected according to the purpose. For example, a glass substrate, a silicon substrate, etc. can be cited, preferably a silicon substrate. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can be formed on the silicon substrate. In addition, a black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. In addition, in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, a base layer can be provided on the silicon substrate. The base layer can be formed using a composition obtained by removing a colorant from the photocurable composition described in this specification or a composition containing a resin, a polymerizable compound, a surfactant, etc. described in this specification. When measured with diiodomethane, the surface contact angle of the base layer is preferably 20° to 70°. And, when measured with water, it is preferably 30° to 80°.

[0463] As a coating method of the photocurable composition, a known method can be used. For example, the method described in paragraph 0207 of International Publication No. 2022 / 085485 can also be used.

[0464] The photocurable composition layer formed on the support can be dried (prebaked). When the film is manufactured by a low temperature process, prebaking is not required. When prebaking is performed, the prebaking temperature is preferably below 150°C, more preferably below 120°C, and further preferably below 110°C. The lower limit can be set to, for example, above 50°C, and can also be set to above 80°C. The prebaking time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and further preferably 80 seconds to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0465] Next, the photocurable composition layer is exposed in a pattern (exposure step). For example, a stepper, a scanner, or the like is used to expose the photocurable composition layer through a mask having a predetermined mask pattern, thereby exposing the layer in a pattern. Thus, the exposed portion can be cured.

[0466] As radiation (light) that can be used for exposure, g-rays, i-rays, etc. can be cited. In addition, light with a wavelength of 300nm or less (preferably light with a wavelength of 150nm to 300nm) can also be used. As light with a wavelength of 300nm or less, KrF rays (wavelength 248nm), ArF rays (wavelength 193nm), etc. can be cited, preferably KrF rays (wavelength 248nm). In addition, a long wavelength light source of 300nm or more can also be used.

[0467] Furthermore, during exposure, light can be continuously irradiated for exposure, or pulsed irradiation can be performed for exposure (pulse exposure). In addition, pulse exposure refers to an exposure method in which light irradiation and pause are repeated for a short period of time (e.g., less than milliseconds) to perform exposure.

[0468] The irradiation amount (exposure amount) is preferably 0.03 J / cm 2 ~2.5J / cm 2 , more preferably 0.05 J / cm 2 ~1.0J / cm 2 The oxygen concentration during exposure can be appropriately selected. In addition to exposure under the atmosphere, exposure can also be performed in a low oxygen environment with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen environment with an oxygen concentration exceeding 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). In addition, the exposure illuminance can be appropriately set, and can usually be selected from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 , 15000W / m 2 or 35000W / m 2 The oxygen concentration and exposure illuminance conditions can be appropriately combined, for example, the oxygen concentration can be set to 10% by volume and the illuminance can be set to 10000 W / m 2 , oxygen concentration is 35 volume % and illumination is 20000 W / m 2 wait.

[0469] Next, the unexposed portion of the photocurable composition layer is removed by development to form a pattern (pixel). The unexposed portion of the photocurable composition layer can be removed by development using a developer. As a result, the unexposed portion of the photocurable composition layer in the exposure process is dissolved into the developer, and only the photocured portion remains. For example, the temperature of the developer is preferably 20°C to 30°C. The development time is preferably 20 seconds to 180 seconds. In addition, in order to improve the removability of the residue, the following process can be repeated multiple times: the developer is shaken off every 60 seconds, and a new developer is supplied.

[0470] The developer may be an organic solvent, an alkali developer, or the like, and an alkali developer may be preferably used. The developer and the developing method described in paragraph 0214 of International Publication No. 2022 / 085485 may also be used.

[0471] After development, it is preferred to perform additional exposure treatment and heating treatment (post-baking) after drying. Additional exposure treatment and post-baking are curing treatments after development for making a completely cured material. The heating temperature in the post-baking is preferably 100°C to 240°C, for example, and more preferably 200°C to 240°C. The developed film can be post-baked in a continuous or intermittent manner using a heating mechanism such as a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. in a manner that achieves the above conditions. When performing additional exposure treatment, the light used for exposure is preferably light with a wavelength of less than 400nm. In addition, the additional exposure treatment can be performed by the method described in Korean Patent Gazette No. 10-2017-0122130.

[0472] When patterning is performed by dry etching, the method described in paragraph 0216 of International Publication No. 2022 / 085485 can also be used.

[0473] (Optical Components)

[0474] The optical element according to the present invention includes the film according to the present invention.

[0475] Examples of the optical element include optical filters, lenses, prisms, reflecting mirrors, and diffraction gratings. Among these, optical filters are preferred.

[0476] Examples of the type of optical filter include color filters and infrared transmission filters, and color filters are preferred. The color filter preferably has the film according to the present invention as its colored pixel.

[0477] In the optical filter, the film thickness of the film involved in the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

[0478] The width of the pixel included in the filter is preferably 0.4 μm to 10.0 μm. The lower limit is more preferably 0.4 μm or more, further preferably 0.5 μm or more, and particularly preferably 0.6 μm or more. The upper limit is more preferably 5.0 μm or less, further preferably 2.0 μm or less, particularly preferably 1.0 μm or less, and most preferably 0.8 μm or less. In addition, the Young's modulus of the pixel is preferably 0.5 GPa to 20 GPa, and more preferably 2.5 GPa to 15 GPa.

[0479] Each pixel included in the filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably less than 100nm, more preferably less than 40nm, and further preferably less than 15nm. There is no specified lower limit, for example, it is preferably more than 0.1nm. Regarding the surface roughness of the pixel, for example, it can be measured using AFM (atomic force microscope) Dimension3100 manufactured by Veeco. In addition, the water contact angle on the pixel can be set to an appropriately preferred value, usually in the range of 50° to 110°. For example, the contact angle can be measured using a contact angle meter CV-DT·A type (manufactured by Kyowa Interface Science Co., LTD.). In addition, it is preferred that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, more preferably 10 11 Ω·cm or more. The upper limit of the volume resistance value of the pixel is not specified, but is preferably 10 14 Ω·cm or less.

[0480] The volume resistance value of a pixel can be measured using an ultra-high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

[0481] In the optical filter, a protective layer may also be provided on the surface of the film involved in the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilicity and hydrophobicity, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 μm to 10 μm, and more preferably 0.1 μm to 5 μm. As a method for forming the protective layer, a method of forming by coating a protective layer forming composition, a chemical vapor deposition method, a method of attaching a formed resin with an adhesive material, etc. can be cited. As the components constituting the protective layer, (meth) acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, polyurethane resin, aromatic polyamide resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc., can contain more than two of these components. For example, in the case of a protective layer for the purpose of blocking oxygen, the protective layer preferably comprises polyol resin, SiO2 and Si2N4. And, in the case of a protective layer for the purpose of low reflection, the protective layer preferably comprises (meth) acrylic resin and fluororesin.

[0482] The protective layer may contain organic particles, inorganic particles, absorbents of light of a specific wavelength (e.g., ultraviolet rays, near infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants and other additives as needed. As examples of organic particles and inorganic particles, for example, polymer particles (e.g., silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silicon dioxide, calcium carbonate, barium sulfate and other particles can be cited. The absorbent of light of a specific wavelength can use a known absorbent. The content of these additives can be appropriately adjusted, preferably 0.1% to 70% by mass, and more preferably 1% to 60% by mass, relative to the total mass of the protective layer.

[0483] Furthermore, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Laid-Open No. 2017-151176 can also be used.

[0484] The optical filter may have a structure in which pixels are embedded in spaces partitioned into a grid shape by partition walls, for example.

[0485] (Image Sensor)

[0486] The image sensor according to the present invention includes the film according to the present invention.

[0487] Examples of the image sensor include solid-state image sensors, X-ray image sensors, and organic thin-film image sensors. Among them, the image sensor according to the present invention can be preferably used for solid-state image sensors.

[0488] The solid-state imaging device according to the present invention includes the film according to the present invention. The structure of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device, and examples thereof include the following structures.

[0489] That is, a substrate has a transmission electrode composed of a plurality of photodiodes and polysilicon etc. constituting a light receiving area of ​​a solid-state imaging element (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.), a light shielding film having only an opening for the light receiving portion of the photodiode is provided on the photodiode and the transmission electrode, a device protection film composed of silicon nitride etc. formed in a manner covering the entire surface of the light shielding film and the light receiving portion of the photodiode is provided on the light shielding film, and a color filter is provided on the device protection film. Furthermore, it may be a structure having a focusing mechanism (e.g., a microlens, etc., the same below) on the device protection film and below the color filter (on the side close to the substrate) or a structure having a focusing mechanism on the color filter, etc.

[0490] Furthermore, the color filter may also have the following structure: for example, each colored pixel is embedded in a space divided into a grid shape by a partition wall. Preferably, the refractive index of the partition wall at this time is lower than that of each colored pixel. As examples of imaging devices with such structures, devices described in Japanese Patent Publication No. 2012-227478, Japanese Patent Publication No. 2014-179577, and International Publication No. 2018 / 043654 can be cited. Furthermore, as shown in Japanese Patent Publication No. 2019-211559, an ultraviolet absorption layer can be provided in the structure of the solid-state imaging element to improve light resistance. In addition to being able to be used as a digital camera, an electronic device with a camera function (such as a mobile phone), etc., the imaging device having the solid-state imaging element involved in the present invention can also be used as a vehicle-mounted camera, a surveillance camera, etc.

[0491] (Image display device)

[0492] The image display device involved in the present invention includes the film involved in the present invention. As the image display device, a liquid crystal display device, an organic electroluminescent display device, etc. can be cited. The definition of the image display device and the details of each image display device are recorded in, for example, "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", "Display Device (written by Junsho Ibuki, Sangyo Tosho Publishing Co., Ltd., published in 1989)", etc. In addition, regarding the liquid crystal display device, it is recorded in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

[0493] (Radical polymerization initiator represented by formula (1))

[0494] The radical polymerization initiator according to the present invention is a radical polymerization initiator represented by the following formula (1).

[0495] The radical polymerization initiator according to the present invention is preferably a photoradical polymerization initiator, and more preferably a photoradical polymerization initiator that generates radicals by light having a wavelength of 150 nm to 300 nm.

[0496] [Chemical formula 35]

[0497]

[0498] In formula (1), Ar1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group, Ar2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group, R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, k represents 0 or 1, R6 each independently represents a halogen atom or a monovalent organic group, and one or more R 6 Can be used with Ar 1 Together they form a ring structure; Y1 represents a group represented by the following formula (2); m represents an integer of 0 to 4; and n represents 0 or 1.

[0499] [Chemical formula 36]

[0500]

[0501] In formula (2), R2 represents an alkyl group, wherein when L2 is CHR, R2 may be a hydrogen atom, R3 represents a hydrogen atom or an alkyl group, R4 represents an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, R each independently represents a hydrogen atom or an alkyl group, two or more of R2, R3, R4 and R may be linked to each other to form a ring structure, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to the oxime group.

[0502] A preferred embodiment of the radical polymerization initiator represented by formula (1) in the radical polymerization initiator according to the present invention is the same as a preferred embodiment of the radical polymerization initiator represented by formula (1) in the photocurable composition.

[0503] Furthermore, the group represented by the above formula (2) is preferably a group represented by the following formula (2-1).

[0504] [Chemical formula 37]

[0505]

[0506] In formula (2-1), R3 represents a hydrogen atom or an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, L A represents an alkylene group having 1 to 6 carbon atoms, R each independently represents a hydrogen atom or an alkyl group, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to an oxime group.

[0507] Preferred embodiments of the group represented by the formula (2-1) in the radical polymerization initiator according to the present invention are the same as preferred embodiments of the group represented by the formula (2-1) in the photocurable composition.

[0508] Example

[0509] Below, give examples to further describe the present invention in detail. The materials, usage, ratio, processing content, processing sequence, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. And, in the present examples, "%", "parts" represent "mass %", "mass parts" respectively, unless otherwise specified.

[0510] The radical polymerization initiators A-1 to A-190 used in the examples are the same compounds as the radical polymerization initiators A-1 to A-190 described above as specific examples of the radical polymerization initiator represented by the formula (1).

[0511] <Synthesis Example 1: Synthesis of Radical Polymerization Initiator A-1>

[0512] <<Synthesis of Intermediate A-1a>>

[0513] Add 34.1 g of diphenyl ether and 300 mL of chlorobenzene to a three-necked flask and cool to 0°C. Add 26.1 g of aluminum chloride and drop 31.5 g of o-methylbenzoyl chloride. Stir at room temperature for 2 hours. Cool the reaction solution to 0°C again, add 27.2 g of aluminum chloride and drop 33.2 g of 2-cyclopentylethylformyl chloride. Stir at room temperature for 2 hours and add to ice water. Filter the precipitated solid and wash with methanol to obtain 56.8 g of intermediate A-1a.

[0514] [Chemical formula 38]

[0515]

[0516] 41.2 g of intermediate A-1a was added to a three-necked flask and dissolved in 300 mL of tetrahydrofuran. 20.8 g of hydroxylamine hydrochloride, 24.6 g of sodium acetate and 120 mL of pure water were added thereto, and heated and stirred at 60 ° C for 6 hours. The obtained reaction solution was separated with ethyl acetate and water, and the organic layer was dried over sodium sulfate and concentrated. Next, the concentrate was dissolved in tetrahydrofuran and cooled to 0 ° C in a three-necked flask in a nitrogen atmosphere. 24.4 g of pyridine was added, and 18.6 g of acetyl chloride was added dropwise. Stir at room temperature for 2 hours, extract the reaction solution with ethyl acetate and wash with water. The organic layer was dried over sodium sulfate and concentrated. The obtained solid was re-pulped and purified with methanol and filtered to obtain 15.4 g of free radical polymerization initiator A-1.

[0517] The free radical polymerization initiator A-1 was confirmed by NMR spectrum. 1 HNMR analysis. The results are shown below.

[0518] 1 HNMR (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ = 1.0-1.2 (m, 2H), 1.5-1.7 (m, 6H), 1.7-1.9 (m, 3H), 2.21 (s, 3H), 2.39 (s, 3H), 2.92 (dd, 2H), 7.0-7.2 (m, 5H), 7.28 (t, 1H), 7.46 (t, 1H), 7.71 (d, 2H), 7.87 (d, 2H), 8.32 (d, 2H)

[0519] [Chemical formula 39]

[0520]

[0521] <Synthesis Example 2: Synthesis of Radical Polymerization Initiator A-3>

[0522] A radical polymerization initiator A-3 was obtained in the same manner as in the synthesis of the radical polymerization initiator A-1, except that diphenyl ether was changed to dibenzofuran.

[0523] 1 HNMR (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ = 1.0-1.2 (m, 2H), 1.5-1.7 (m, 6H), 1.7-1.9 (m, 3H), 2.28 (s, 3H), 2.36 (s, 3H), 2.95 (dd, 2H), 7.2-7.4 (m, 3H), 7.44 (t, 1H), 7.63 (dd, 2H), 7.86 (dd, 1H), 8.06 (dd, 1H), 8.32 (d, 1H), 8.41 (d, 1H)

[0524] [Chemical formula 40]

[0525]

[0526] <Synthesis Example 3: Synthesis of Radical Polymerization Initiator A-10>

[0527] A radical polymerization initiator A-10 was obtained in the same manner as in the synthesis of the radical polymerization initiator A-1, except that diphenyl ether was changed to 9,9-dimethylxanthene.

[0528] 1HNMR (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ = 1.0-1.2 (m, 2H), 1.5-1.7 (m, 6H), 1.69 (s, 6H), 1.7-1.9 (m, 3H), 2.29 (s, 3H), 2.38 (s, 3H), 2.99 (dd, 2H), 7.2-7.4 (m, 3H), 7.44 (t, 1H), 7.63 (dd, 2H), 7.86 (dd, 1H), 8.06 (dd, 1H), 8.11 (d, 1H), 8.24 (d, 1H)

[0529] [Chemical formula 41]

[0530]

[0531] <Synthesis Example 4: Synthesis of Radical Polymerization Initiator A-25>

[0532] In the synthesis of the radical polymerization initiator A-1, a radical polymerization initiator A-25 was obtained in the same manner as above except that diphenyl ether was changed to dibenzofuran and o-toluoyl chloride was changed to o-bromobenzoyl chloride.

[0533] 1 HNMR (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ = 1.0-1.2 (m, 2H), 1.5-1.7 (m, 6H), 1.7-1.9 (m, 3H), 2.28 (s, 3H), 2.95 (dd, 2H), 7.2-7.4 (m, 3H), 7.49 (t, 1H), 7.78 (dd, 2H), 8.09 (dd, 1H), 8.21 (dd, 1H), 8.32 (d, 1H), 8.41 (d, 1H)

[0534] [Chemical formula 42]

[0535]

[0536] <Synthesis Example 5: Synthesis of Radical Polymerization Initiator A-88>

[0537] In the synthesis of the radical polymerization initiator A-1, a radical polymerization initiator A-88 was obtained in the same manner except that diphenyl ether was changed to 4,6-dibromodibenzofuran and o-toluoyl chloride was changed to 2,6-dibromobenzoyl chloride.

[0538] 1HNMR (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ = 1.0-1.2 (m, H), 1.5-1.7 (m, 6H), 1.7-1.9 (m, 3H), 2.28 (s, 3H), 7.14 (t, 1H), 7.58 (d, 2H), 7.80 (2, 1H), 7.87 (dd, 1H), 7.97 (dd, 1H)

[0539] [Chemical formula 43]

[0540]

[0541] <Synthesis Example 5: Synthesis of Radical Polymerization Initiator A-120>

[0542] <<Synthesis of Intermediate A-120a>>

[0543] In the synthesis of Intermediate A-1a, Intermediate A-120a was obtained in the same manner except that diphenyl ether was replaced by dibenzofuran, o-methylbenzoyl chloride was replaced by 2-bromobenzoyl chloride, and 2-cyclopentylethylcarbonyl chloride was replaced by 3-cyclopentylpropylcarbonyl chloride.

[0544] [Chemical formula 44]

[0545]

[0546] 9.9 g of intermediate A-120a was added to a three-necked flask and dissolved in 100 mL of tetrahydrofuran. 2.8 g of sodium methoxide was added and cooled at 0° C. 3.8 g of isoamyl nitrite was added dropwise and stirred at room temperature for 2 hours. The obtained reaction solution was separated with ethyl acetate and water, and the organic layer was dried with sodium sulfate and concentrated.

[0547] Next, the concentrate was dissolved in 150 mL of tetrahydrofuran and cooled to 0° C. in a three-necked flask in a nitrogen atmosphere. 2.5 g of pyridine was added, and 1.5 g of acetyl chloride was added dropwise. The mixture was stirred at room temperature for 2 hours, and the reaction solution was extracted with ethyl acetate and washed with water. The organic layer was dried over sodium sulfate and concentrated. The obtained solid was re-pulped and purified with methanol and filtered to obtain 5.6 g of free radical polymerization initiator A-120.

[0548] The free radical polymerization initiator A-120 was investigated based on 1 HNMR analysis. The results are shown below.

[0549] 1HNMR (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ = 1.0-1.2 (m, 2H), 1.5-1.7 (m, 6H), 1.7-1.9 (m, 3H), 2.11 (dd, 2H), 2.38 (s, 3H), 7.2-7.4 (m, 3H), 7.49 (t, 1H), 7.78 (dd, 2H), 8.09 (dd, 1H), 8.21 (dd, 1H), 8.32 (d, 1H), 8.41 (d, 1H)

[0550] [Chemical formula 45]

[0551]

[0552] <Synthesis Example 2: Synthesis method of radical polymerization initiator other than the above>

[0553] Free radical polymerization initiators A-2, A-4 to A-9, A-11 to A-24, A-26 to A-87, A-89 to A-119, and A-121 to A-190 were obtained in a similar manner to Synthesis Example 1 except that the raw materials were changed.

[0554] <Preparation of dispersion>

[0555] The mixed solution of the raw materials listed in Table 6 below was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm in diameter). Next, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism was used to disperse the mixture at a pressure of 2,000 kg / cm 2 The dispersion treatment was carried out under the conditions of 500 g / min and a flow rate of 500 g / min. The dispersion treatment was repeated a total of 10 times to obtain a dispersion liquid. The numerical values ​​representing the amount of preparation recorded in the following Table 6 are parts by mass. In addition, the numerical values ​​of the amount of dispersant prepared are numerical values ​​calculated based on solid content.

[0556] [Table 6]

[0557]

[0558] Details of the materials represented by the abbreviations in Table 6 showing the formulation of the above dispersion are as follows.

[0559] <Coloring agent>

[0560] PR264: CI Pigment Red 264 [diketopyrrolopyrrole compound, red pigment (R pigment)]

[0561] PR254: CI Pigment Red 254 [diketopyrrolopyrrole compound, red pigment (R pigment)]

[0562] PR291: CI Pigment Red 291 [brominated diketopyrrolopyrrole compound, red pigment (R pigment)]

[0563] PO71: CI Pigment Orange 71 [diketopyrrolopyrrole compound, orange pigment (O pigment)]

[0564] PG36: CI Pigment Green 36 [Copper Phthalocyanine Complex, Green Pigment (G Pigment)]

[0565] PG58: CI Pigment Green 58 [zinc phthalocyanine complex, green pigment (G pigment)]

[0566] PY129: CI Pigment Yellow 129 [azomethine copper complex, yellow pigment (Y pigment)]

[0567] PY139: CI Pigment Yellow 139 [isoindoline compound, yellow pigment (Y pigment)]

[0568] PY185: CI Pigment Yellow 185 [isoindoline compound, yellow pigment (Y pigment)]

[0569] PY215: CI Pigment Yellow 215 [pteridine compound, yellow pigment (Y pigment)]

[0570] PB16: CI Pigment Blue 16 [metal-free phthalocyanine compound, blue pigment (B pigment)]

[0571] PB15:6: CI Pigment Blue 15:6 [Copper phthalocyanine complex, blue pigment (B pigment)]

[0572] IR pigment: A compound having the following structure (a near-infrared absorbing pigment (a colorant that also absorbs in the visible light region). In the following structural formula, Me represents a methyl group and Ph represents a phenyl group.)

[0573] [Chemical formula 46]

[0574]

[0575] TiBk: Titanium Black [Black Pigment (Bk Pigment)]

[0576] Zr oxynitride: Zirconium oxynitride [black pigment (Bk pigment)]

[0577] <Pigment derivatives>

[0578] S-1~S-4: The following compounds

[0579] [Chemical formula 47]

[0580]

[0581] <Dispersant>

[0582] P-1: A 30% by mass propylene glycol monomethyl ether acrylate (PGMEA) solution of a resin having the following structure: The numerical values ​​indicated in the main chain are molar ratios, and the numerical values ​​indicated in the side chain are the number of repeating units. Mw: 20,000.

[0583] [Chemical formula 48]

[0584]

[0585] P-2: 30 mass % PGMEA solution of the resin of the following structure. The values ​​indicated in the main chain are molar ratios, and the values ​​indicated in the side chain are the number of repeating units. Mw: 28,000. In the formula, r=15, s=63, t=5, u=17, n=9.

[0586] [Chemical formula 49]

[0587]

[0588] P-3: 30 mass % PGMEA solution of a resin having the following structure. The numerical values ​​indicated in the main chain are molar ratios, and the numerical values ​​indicated in the side chain are the number of repeating units. Mw: 21,000.

[0589] [Chemical formula 50]

[0590]

[0591] P-4: 30 mass% PGMEA solution of a resin having the following structure: The numerical value indicated in the side chain is the number of repeating units. Mw: 9,000.

[0592] [Chemical formula 51]

[0593]

[0594] P-5: 30 mass% PGMEA solution of a resin having the following structure: The numerical value indicated in the side chain is the number of repeating units. Mw: 10,000.

[0595] [Chemical formula 52]

[0596]

[0597] <Solvent>

[0598] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0599] S-2: Propylene glycol monomethyl ether (PGME)

[0600] S-3: Cyclohexanone

[0601] <Production of Photocurable Composition>

[0602] The dispersions described in Tables 7 to 11 below, the resins described in Tables 7 to 11 below, the radical polymerizable compounds described in Tables 7 to 11 below, the radical polymerization initiators described in Tables 7 to 11 below, the chain transfer agents described in Tables 7 to 11 below, the sensitizers described in Tables 7 to 11 below, the solvents described in Tables 7 to 11 below, 1 part by mass of an epoxy compound (EHPE-3150, manufactured by Daicel Corporation), 1 part by mass of an ultraviolet absorber (TINUVIN326, manufactured by BASF), 1 part by mass of the surfactant 1 shown below, and 0.1 part by mass of a polymerization inhibitor (p-methoxyphenol) were mixed to prepare photocurable compositions of Examples and Comparative Examples.

[0603] Surfactant 1: 1 mass % PGMEA solution of KF-6001 (dual-end carbinol-modified polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0604] [Table 7]

[0605]

[0606] [Table 8]

[0607]

[0608] [Table 9]

[0609]

[0610] [Table 10]

[0611]

[0612] [Table 11]

[0613]

[0614] Details of materials represented by abbreviations in Tables 7 to 11 showing formulations of the photocurable compositions other than those described above are as follows.

[0615] <Resin>

[0616] Ba-1: Resin having the following structure (the numerical values ​​indicated in the main chain are molar ratios. The weight average molecular weight is 11,000)

[0617] [Chemical formula 53]

[0618]

[0619] Ba-2: Resin having the following structure (the numerical values ​​indicated in the main chain are molar ratios. The weight average molecular weight is 15,000)

[0620] [Chemical formula 54]

[0621]

[0622] Ba-3: Resin having the following structure (the values ​​indicated in the main chain are molar ratios. The total value of x, y and z is 50. Mw = 15,000)

[0623] [Chemical formula 55]

[0624]

[0625] <Radical polymerizable compounds>

[0626] D-1: KAYARAD DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

[0627] D-2: NK ESTER A-DPH-12E (ethylene oxide (EO) modified hexafunctional acrylate compound, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)

[0628] D-3: NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)

[0629] D-4: ARONIX M-510 (3-4 functional acrylate compound, manufactured by TOAGOSEI CO., LTD.)

[0630] D-5: LIGHT ACRYLATE DCP-A (bifunctional alicyclic acrylate compound, manufactured by KYOEISHA CHEMICAL Co., LTD.)

[0631] <Other radical polymerization initiators used simultaneously>

[0632] a-1: Compound with the following structure

[0633] [Chemical formula 56]

[0634]

[0635] a-2: Compound with the following structure

[0636] [Chemical formula 57]

[0637]

[0638] a-3: Compound with the following structure

[0639] [Chemical formula 58]

[0640]

[0641] a-4: Compound with the following structure

[0642] [Chemical formula 59]

[0643]

[0644] a-5: Api-307, aminoacetophenone-based polymerization initiator manufactured by YOUWEI

[0645] a-6: Compound with the following structure

[0646] [Chemical formula 60]

[0647]

[0648] a-7: Compound with the following structure

[0649] [Chemical formula 61]

[0650]

[0651] <Comparative Radical Polymerization Initiator>

[0652] CA-1: The following compound

[0653] CA-2: The following compound

[0654] [Chemical formula 62]

[0655]

[0656] <Chain transfer agent>

[0657] F-1: Karenz MT PE1, tetrafunctional thiol compound manufactured by SHOWA DENKO KK

[0658] F-2: Karenz MT BD1, bifunctional thiol compound manufactured by SHOWA DENKO KK

[0659] F-3: A compound of the following structure (4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoic acid), manufactured by FUJIFILM Wako Pure Chemical Corporation

[0660] [Chemical formula 63]

[0661]

[0662] <Sensitizer>

[0663] G-1: 2-isopropylthioxanthone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0664] G-2: 4,4'-bis(diethylamino)benzophenone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0665] G-3: 7-diethylamino-4-methylcoumarin (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0666] G-4: 6-Chloro-2-Methylthiochroman-4-one (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0667] <Performance Evaluation>

[0668] <<Evaluation of exposure sensitivity, adhesion and residue>>

[0669] On an 8-inch (203.2 mm) silicon wafer with a primer layer, each of the photocurable compositions obtained above was applied by spin coating to a film thickness of 0.4 μm, and then heated at 100° C. for 2 minutes using a hot plate to form a composition layer. Next, a KrF scanning exposure machine was used through a mask having a 0.5 μm square pattern at an illumination of 35,000 W / m 2 , exposure 20mJ / cm 2 ~200mJ / cm 2 The obtained composition layer was exposed by irradiating light (KrF ray) with a wavelength of 248 nm. Then, a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) was used as a developer, and the exposed composition layer was spray developed for 60 seconds at 23°C. After that, pure water was used to rinse by rotary spraying to form pixels.

[0670] The obtained pixels were observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation). Based on the observed images, adhesion and residue were evaluated according to the following criteria.

[0671] -Evaluation criteria for exposure sensitivity-

[0672] The exposure amount required to achieve a pattern line width of 0.7 μm was calculated, and the exposure sensitivity was evaluated according to the following criteria.

[0673] A: Exposure is 60mJ / cm 2 the following.

[0674] B: Exposure exceeds 60mJ / cm 2 And 100mJ / cm 2 the following.

[0675] C: Exposure exceeds 100mJ / cm 2 and 150mJ / cm 2 the following.

[0676] D: Exposure exceeds 150mJ / cm 2 And 200mJ / cm 2 the following.

[0677] E: Exposure exceeds 200mJ / cm 2 .

[0678] -Adhesion Evaluation-

[0679] For the obtained pixels, at 100 mJ / cm 2 Among the portions exposed with an exposure amount of 1,071×1,071, the number of peeled pixels was counted by observing the portions with an optical microscope. The adhesion was determined based on the number of peeled pixels according to the following criteria.

[0680] A: The number of peeled pixels is 10 or less.

[0681] B: The number of peeled pixels is more than 10 and 20 or less.

[0682] C: The number of peeled pixels is more than 20 and 50 or less.

[0683] D: The number of peeled pixels is more than 50 and 200 or less.

[0684] E: The number of peeled pixels exceeds 200.

[0685] <<Undercut (undercut suppression)>>

[0686] The pattern was formed in the same order as the evaluation of the above-mentioned adhesion. The cross-sectional shape of the obtained pattern was observed using SEM (Scanning Electron Microscope: scanning electron microscope, magnification: 20,000 times), 5 patterns were extracted from the SEM photograph, the average slope of the cross section of the 5 patterns was calculated, and the pattern cross-sectional shape 1 was evaluated according to the following benchmark. In addition, the slope of the cross section of the pattern refers to the slope in the thickness direction of the pattern on the silicon wafer in the portion where the pattern is formed. Specifically, the angle of the portion formed by the surface of the silicon wafer and the edge in the thickness direction of the pattern is measured. The slope of the pattern exceeding 90 degrees relative to the surface of the silicon wafer means that the area of ​​the pattern increases from the silicon wafer side toward the surface side of the pattern, that is, an edge is generated on the bottom surface of the pattern, which is not preferred.

[0687] -Evaluation Criteria-

[0688] A: The angle is more than 80 degrees and less than 90 degrees.

[0689] B: The angle is more than 90 degrees and less than 100 degrees.

[0690] C: The angle is more than 100 degrees and less than 110 degrees.

[0691] D: The angle is more than 110 degrees and less than 150 degrees.

[0692] E: The angle exceeds 150 degrees.

[0693] <<Coating film uniformity>>

[0694] On a silicon wafer, each photocurable composition was applied using a spin coater, and then heated (prebaked) at 100°C for 120 seconds using a hot plate to obtain a coating film with a thickness of 1.0 μm. The surface was observed by an optical microscope (BX53M, manufactured by Olympus Corporation) at a magnification of 1,000 times, and the area of ​​the striped portion of the coating film on one screen was observed and evaluated. The evaluation criteria are as follows. The fewer the stripes, the better the uniformity of the coating film.

[0695] -Evaluation Criteria-

[0696] A: No streaks were observed at all.

[0697] B: Streaks exceed 0% and are less than 1%.

[0698] C: Streaks are 1% or more and less than 2%.

[0699] D: Streaks are 2% or more and less than 5%.

[0700] E: Streaks are 5% or more.

[0701] The evaluation results are summarized in Tables 12 to 14.

[0702] [Table 12]

[0703]

[0704] [Table 13]

[0705]

[0706] [Table 14]

[0707]

[0708] As shown in Tables 12 to 14, the photocurable compositions of Examples were superior in sensitivity to the photocurable compositions of Comparative Examples.

[0709] Furthermore, as shown in Tables 12 to 14, the photocurable compositions of Examples were also excellent in adhesion, undercut suppression, and coating film uniformity.

[0710] The photocurable composition of each example was exposed to i-ray (365 nm) using an i-ray stepper exposure apparatus FPA-3000iS+ (manufactured by Canon Inc.), and the same effect was obtained.

[0711] Furthermore, when evaluation was performed in the same manner except that the film thickness of the coating film (cured film) in each of Examples 1 to 190 was changed to 0.2 μm or 2.0 μm, the same evaluation results as those described above were obtained.

[0712] (Example 301: Fabrication of Solid-State Imaging Element)

[0713] The photocurable composition of Example 1 was applied to a silicon wafer by spin coating so that the film thickness after film formation was 0.4 μm. Then, the film was heated at 100° C. for 2 minutes using a hot plate. Then, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1,000 mJ / cm 2 , exposed through a mask with a 1.0 μm square dot pattern. Next, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), spin immersion development was performed at 23°C for 60 seconds. Then, rinsed with a rotary shower and then washed with pure water. Next, using a hot plate, heated at 200°C for 5 minutes, a red pattern formed by curing the photocurable composition of Example 1 on the silicon wafer was formed. Similarly, the photocurable composition of Example 6 (green) and the photocurable composition of Example 11 (blue) were patterned in sequence to form red, green and blue colored patterns (Bayer patterns).

[0714] In addition, as disclosed in US Pat. No. 3,971,065, the Bayer pattern refers to a pattern in which a 2×2 array of color filter elements having one red element, two green elements, and one blue element is repeated.

[0715] The obtained color filter was assembled into a solid-state imaging element by a known method. It was confirmed that when any of the photocurable compositions prepared in the examples was used, the solid-state imaging element had excellent adhesion in the cured film and a solid-state imaging element with a preferred image recognition capability was obtained.

[0716] The invention of Japanese Patent Application No. 2022-133897 filed on August 25, 2022 is incorporated herein by reference.

[0717] All documents, patent applications, and technical specifications described in the present invention are incorporated herein by reference to the same extent as if each individual document, patent application, or technical specification was specifically and individually indicated to be incorporated by reference.

Claims

1. A photocurable composition comprising: Colorants; A radical polymerization initiator represented by formula (1); and Free radical polymerizable compounds, In formula (1), Ar1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group, Ar2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group, R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, k represents 0 or 1, R6 each independently represents a halogen atom or a monovalent organic group, and one or more R 6 Optional with Ar 1 Together they form a ring structure, Y1 represents a group represented by the following formula (2), m represents an integer of 0 to 4, and n represents 0 or 1, In formula (2), R2 represents an alkyl group, wherein when L2 is CHR, R2 is optionally a hydrogen atom, R3 represents a hydrogen atom or an alkyl group, R4 represents an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, R each independently represents a hydrogen atom or an alkyl group, two or more of R2, R3, R4 and R are optionally linked to each other to form a ring structure, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents the linking portion to the oxime group.

2. The photocurable composition according to claim 1, wherein The Y1 is a group represented by the following formula (3), In formula (3), L3 and L4 each independently represent CHR, O, S or NR, at least one of L3 and L4 is CHR, R represents a hydrogen atom or an alkyl group, R5 each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 6, and * represents a linking portion to the oxime group.

3. The photocurable composition according to claim 1 or 2, wherein The R6 is a halogen atom, a nitro group, a cyano group or a group represented by the following formula (4), In formula (4), Ar3 represents an aryl group or a heteroaryl group, and * represents a linking portion with Ar1.

4. The photocurable composition according to claim 1 or 2, wherein The radical polymerization initiator represented by the formula (1) is a compound represented by the following formula (5), In formula (5), Ar3 represents an aryl group or a heteroaryl group, R7 represents an alkyl group or an aryl group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, Z represents an alkylene group having 1 to 3 carbon atoms, k represents 0 or 1, n represents 0 or 1, and p represents an integer of 1 to 6.

5. The photocurable composition according to claim 1 or 2, wherein The content of the colorant is 60% by mass or more based on the total solid content of the composition. The photocurable composition according to claim 1 or 2, further comprising a resin.

7. The photocurable composition according to claim 6, wherein The resin includes a resin that is a graft polymer having a graft chain, wherein the graft chain includes at least one selected from the group consisting of a polyether chain, a polyester chain, and a polyacrylic acid chain, and the graft chain has a weight average molecular weight of 1,000 or more.

8. The photocurable composition according to claim 6, wherein The resin includes a resin having a (meth)acryloyl group, an epoxy group or an oxetane group. 9 . The photocurable composition according to claim 1 , further comprising a pigment derivative. 10 . The photocurable composition according to claim 1 , further comprising a chain transfer agent. 11 . The photocurable composition according to claim 1 or 2 , further comprising a sensitizer. 12 . The photocurable composition according to claim 1 , which is used for excimer laser exposure with a wavelength of 150 nm to 300 nm. 13 . A method for producing a cured film, comprising the step of irradiating the photocurable composition according to claim 1 or 2 with an excimer laser having a wavelength of 150 nm to 300 nm. 14 . A film which is a cured product of the photocurable composition according to claim 1 or 2. 15 . A solid-state imaging element comprising the film according to claim 14 . 16 . An image display device comprising the film according to claim 14 .

17. A free radical polymerization initiator represented by formula (1), In formula (1), Ar1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group, Ar2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group, R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, and L represents a single bond or CR 11 R 12 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group or an aryl group, k represents 0 or 1, R6 each independently represents a halogen atom or a monovalent organic group, and one or more R 6 Optional with Ar 1 Together they form a ring structure, Y1 represents a group represented by the following formula (2-1), m represents an integer of 0 to 4, and n represents 0 or 1, In formula (2-1), R3 represents a hydrogen atom or an alkyl group, L1 and L2 each independently represent CHR, O, S or NR, L A represents an alkylene group having 1 to 6 carbon atoms, R each independently represents a hydrogen atom or an alkyl group, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to an oxime group.

Images