Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, image display device, and radical polymerization initiator

Abstract

The present invention provides a curable composition containing a radical polymerization initiator represented by formula (1) and a radical polymerizable compound, a method for producing a cured product of the curable composition, a method for producing a cured product using the curable composition, a film, an optical element, and an image sensor. A solid-state imaging element, an image display device, or a novel radical polymerization initiator. In formula (1), Ar1 represents an aromatic group having an alkoxy group, an aromatic group having an alkylthio group, an aromatic group having a mono-or dialkylamino group, an aromatic group having an aryloxy group, an aromatic group having an arylthio group, an aromatic group having a mono-or diarylamino group, or an aromatic group having a monoalkylmonoarylamino group. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a curable composition, a method for producing a cured product, a film, an optical element, an image sensor, 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 curable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound.

[0003] As a conventional curable composition, a composition described in International Publication No. 2015 / 152153 is known.

[0004] International Publication No. 2015 / 152153 describes an oxime ester compound having an indole core. Summary of the invention

[0005] Technical issues to be solved by the invention

[0006] An object of the embodiments of the present invention is to provide a highly sensitive curable composition.

[0007] Furthermore, another embodiment of the present invention is to provide a method for producing a cured product using the curable composition, a film, an optical element, an image sensor, a solid-state imaging element, or an image display device.

[0008] Another problem to be solved by another embodiment of the present invention is to provide a novel radical polymerization initiator.

[0009] Means for solving technical problems

[0010] Means for solving the above-mentioned problems include the following.

[0011] <1> A curable composition comprising:

[0012] A radical polymerization initiator represented by formula (1); and

[0013] Free radical polymerizable compounds.

[0014] [Chemical formula 1]

[0015]

[0016] In formula (1), Ar1 represents an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, an aromatic group having an arylthio group having 6 to 18 carbon atoms, an aromatic group having a mono- or di-arylamino group having 6 to 18 carbon atoms, or an aromatic group having a monoalkyl or monoarylamino group having 7 to 18 carbon atoms, Ar2 represents a divalent aromatic group, a divalent heteroaromatic group, or a divalent group formed by bonding two or more of these groups, L1 represents a carbonyl group, a sulfonyloxy group, or a sulfonyl group, R1 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryl group, or a heteroaryloxy group, and R 15 ~R 19 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group or an aryloxy group, and two or more R 15 ~R 19 They may be linked to each other to form a ring structure, and the formed ring structure may be an aromatic ring. Y1 represents a hydrogen atom, an alkyl group or an aryl group, and n represents 0 or 1.

[0017] <2> according to <1> The curable composition, wherein

[0018] The above Y1 is a group represented by the following formula (2).

[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] <3> according to <1> or <2> The curable composition, 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] <4> according to <1> to <3> The curable composition according to any one of the preceding claims, wherein

[0028] The above-mentioned Ar1 is an aromatic group having an alkoxy group having 1 to 12 carbon atoms or an aromatic group having an alkylthio group having 1 to 12 carbon atoms.

[0029] <5> according to <1> to <4> The curable composition according to any one of the preceding claims, wherein

[0030] The above n is 0.

[0031] <6> according to <1> to <5> The curable composition described above further comprises a colorant.

[0032] <7> according to <6> The curable composition, wherein

[0033] The content of the colorant is 60% by mass or more based on the total solid content of the composition.

[0034] <8> according to <1> to <7> The curable composition described above further comprises a resin.

[0035] <9> according to <8> The curable composition, wherein

[0036] The resin includes a resin that is a graft polymer having a graft chain, wherein the graft chain includes at least one selected from 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.

[0037] <10> according to <8> or <9> The curable composition, wherein

[0038] The above-mentioned resin includes a resin having a (meth)acryloyl group, an epoxy group or an oxetane group.

[0039] <11> according to <1> to <10> The curable composition described above further comprises a pigment derivative.

[0040] <12> according to <1> to <11> The curable composition described in any one of the preceding claims further comprises a chain transfer agent.

[0041] <13> according to <1> to <12> The curable composition described above is used for excimer laser exposure with a wavelength of 150 nm to 300 nm.

[0042] <14> A method for manufacturing a solidified product, comprising: <1> to <13> A step of irradiating the curable composition according to any one of the preceding claims with an excimer laser having a wavelength of 150 nm to 300 nm.

[0043] <15> A film which is cured by <1> to <13> The curable composition described in any one of the above.

[0044] <16> An optical element comprising <15> The membrane.

[0045] <17> An image sensor comprising <15> The membrane.

[0046] <18> A solid-state imaging element comprising <15> The membrane.

[0047] <19> An image display device comprising <15> The membrane.

[0048] <20> A radical polymerization initiator represented by formula (1).

[0049] [Chemical formula 4]

[0050]

[0051] In formula (1), Ar1 represents an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, an aromatic group having an arylthio group having 6 to 18 carbon atoms, an aromatic group having a mono- or di-arylamino group having 6 to 18 carbon atoms, or an aromatic group having a monoalkyl or monoarylamino group having 7 to 18 carbon atoms, Ar2 represents a divalent aromatic group, a divalent heteroaromatic group, or a divalent group formed by bonding two or more of these groups, L1 represents a carbonyl group, a sulfonyloxy group, or a sulfonyl group, R1 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryl group, or a heteroaryloxy group, and R 15 ~R 19 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group or an aryloxy group, and two or more R 15 ~R 19 They may be linked to each other to form a ring structure, and the formed ring structure may be an aromatic ring. Y1 represents a hydrogen atom, an alkyl group or an aryl group, and n represents 0 or 1.

[0052] Effects of the Invention

[0053] According to an embodiment of the present invention, a highly sensitive curable composition is provided.

[0054] Furthermore, according to another embodiment of the present invention, a method for producing a cured product using the curable composition, a film, an optical element, an image sensor, a solid-state imaging element, or an image display device is provided.

[0055] Furthermore, according to another embodiment of the present invention, a novel free radical polymerization initiator is provided. DETAILED DESCRIPTION

[0056] 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 such embodiments.

[0057] 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.

[0058] 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).

[0059] 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 for exposure include active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] In this specification, a pigment refers to a colorant that is not easily dissolved in a solvent.

[0065] 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.

[0066] In the present specification, an oxime compound having E-isomer and Z-isomer stereoisomers may be either the E-isomer or the Z-isomer unless otherwise specified.

[0067] Hereinafter, the present invention will be described in detail.

[0068] (Curable composition)

[0069] The curable composition according to the present invention contains a radical polymerization initiator represented by formula (1) and a radical polymerizable compound.

[0070] Furthermore, the curable composition of the present invention can be preferably used as a photocurable composition, more preferably used as a curable composition for exposure based on light with a wavelength of 150nm to 300nm, and particularly preferably used as a curable composition for excimer laser exposure with a wavelength of 150nm to 300nm.

[0071] [Chemical formula 5]

[0072]

[0073] In formula (1), Ar1 represents an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, an aromatic group having an arylthio group having 6 to 18 carbon atoms, an aromatic group having a mono- or di-arylamino group having 6 to 18 carbon atoms, or an aromatic group having a monoalkyl or monoarylamino group having 7 to 18 carbon atoms, Ar2 represents a divalent aromatic group, a divalent heteroaromatic group, or a divalent group formed by bonding two or more of these groups, L1 represents a carbonyl group, a sulfonyloxy group, or a sulfonyl group, R1 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryl group, or a heteroaryloxy group, and R 15 ~R 19 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group or an aryloxy group, and two or more R 15 ~R 19 They may be linked to each other to form a ring structure, and the formed ring structure may be an aromatic ring. Y1 represents a hydrogen atom, an alkyl group or an aryl group, and n represents 0 or 1.

[0074] As a result of intensive studies, the present inventors have found that a highly sensitive curable composition can be obtained by adopting the above-mentioned configuration.

[0075] It is speculated that the free radical polymerization initiator represented by the above formula (1) contains an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, an aromatic group having an arylthio group having 6 to 18 carbon atoms, an aromatic group having a mono- or di-arylamino group having 6 to 18 carbon atoms, or an aromatic group having a monoalkyl-monoarylamino group having 7 to 18 carbon atoms as the above-mentioned Ar1 and further has an indole ring structure and an oxime ester structure, thereby improving the light absorption efficiency of the aromatic ring group having a heteroatom, namely the above-mentioned Ar1 and the indole structure, while promoting the generation of free radicals from the oxime ester structure, thereby obtaining a highly sensitive curable composition.

[0076] The curable composition involved in the present invention can be preferably used as a curable composition for optical filter. As an optical filter, a color filter and an infrared transmission filter, etc. can be mentioned, preferably a color filter. That is, the curable composition involved in the present invention can be preferably used as a curable composition for color filter. In more detail, it can be preferably used as a curable composition for pixel formation of a color filter. As the type of pixel, red pixel, green pixel, blue pixel, magenta pixel, cyan pixel, yellow pixel, etc. can be mentioned.

[0077] Preferred examples of infrared transmission filters include filters that satisfy spectral characteristics such that the maximum transmittance in the wavelength range of 400 nm to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1,100 nm to 1,300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). The infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).

[0078] (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.

[0079] (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.

[0080] (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.

[0081] (4): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400nm to 950nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1,100nm to 1,500nm.

[0082] (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.

[0083] Furthermore, the curable composition of the present invention can be preferably used for solid-state imaging devices. More specifically, it can be preferably used as a curable composition for an optical filter for a solid-state imaging device, and more preferably as a curable composition for a color filter for a solid-state imaging device.

[0084] The solid content concentration of the curable 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.

[0085] <Radical polymerization initiator represented by formula (1)>

[0086] The curable composition according to the present invention contains a radical polymerization initiator represented by the above formula (1).

[0087] 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.

[0088] 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.

[0089] In Ar1 in formula (1), for example, with respect to an aromatic group having an alkoxy group having 1 to 12 carbon atoms, the aromatic group may have only one alkoxy group having 1 to 12 carbon atoms, or may have two or more alkoxy groups having 1 to 12 carbon atoms, and the aromatic group may also have other groups such as an alkylthio group having 1 to 12 carbon atoms in addition to the alkoxy group having 1 to 12 carbon atoms.

[0090] Furthermore, two or more groups of the aromatic group may be bonded to form a ring structure. For example, two alkoxy groups having 1 to 12 carbon atoms may be bonded to form a heterocyclic structure.

[0091] In Ar1 in the formula (1), for example, the aromatic group having an alkoxy group having 1 to 12 carbon atoms is preferably a group in which the alkoxy group having 1 to 12 carbon atoms is directly bonded to the aromatic ring of the aromatic group.

[0092] In addition, Ar1 in formula (1) can also be rephrased as follows.

[0093] Ar1 represents an aromatic group having at least one group selected from an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an arylthio group having 6 to 18 carbon atoms, a mono- or di-arylamino group having 6 to 18 carbon atoms, and a monoalkyl-monoarylamino group having 7 to 18 carbon atoms.

[0094] From the viewpoint of sensitivity, Ar1 in formula (1) is preferably an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, or an aromatic group having an arylthio group having 6 to 18 carbon atoms, more preferably an aromatic group having an alkoxy group having 1 to 12 carbon atoms or an aromatic group having an alkylthio group having 1 to 12 carbon atoms, further preferably an aromatic group having an alkoxy group having 1 to 12 carbon atoms, particularly preferably an aromatic group having an alkoxy group having 1 to 3 carbon atoms, and most preferably an aromatic group having an isopropoxy group.

[0095] From the viewpoint of sensitivity, the number of carbon atoms in the alkyl group of the alkoxy group having 1 to 12 carbon atoms, the alkylthio group having 1 to 12 carbon atoms, the mono- or di-alkylamino group having 1 to 12 carbon atoms, or the monoalkylmonoarylamino group having 7 to 18 carbon atoms is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 3.

[0096] The aryl group in the aryloxy group having 6 to 18 carbon atoms, the arylthio group having 6 to 18 carbon atoms, the mono- or diarylamino group having 6 to 18 carbon atoms, or the monoalkylmonoarylamino group having 7 to 18 carbon atoms preferably has 6 to 10 carbon atoms from the viewpoint of sensitivity.

[0097] From the viewpoint of sensitivity, the aromatic group of Ar1 in formula (1) is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 12 carbon atoms, and particularly preferably a phenyl group having an alkoxy group having 1 to 12 carbon atoms.

[0098] When the aromatic group of Ar1 in formula (1) is a phenyl group, the bonding position of the group such as an alkoxy group having 1 to 12 carbon atoms and L1 is preferably the ortho position or the para position, more preferably the para position, from the viewpoint of sensitivity.

[0099] Furthermore, the aromatic group in Ar1 in formula (1) and the alkoxy group having 1 to 12 carbon atoms may further have a substituent. As the substituent, there is no particular limitation, and preferably a substituent having 0 to 100 carbon atoms may be mentioned, and more preferably a substituent having 0 to 50 carbon atoms may be mentioned. 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 alkylthio group, an arylthio group, a morpholino group, an alkoxyalkyl group, a carboxyl group, a carboxylalkyl group, etc. may be mentioned. Furthermore, these substituents may further have a substituent, and the substituents may be bonded to each other to form a ring structure.

[0100] Preferred specific examples of Ar1 in formula (1) are shown below. In addition, * represents a bonding position with L1.

[0101] [Chemical formula 6]

[0102]

[0103] Among them, from the viewpoint of sensitivity, Ar1 is preferably at least one group selected from the group consisting of Ar1-1, Ar1-2, Ar1-5, Ar1-14, Ar1-15, Ar1-18, Ar1-19, Ar1-23, Ar1-29, Ar1-32 and Ar1-34, more preferably at least one group selected from the group consisting of Ar1-1, Ar1-5, Ar1-19, Ar1-29 and Ar1-34, and particularly preferably Ar1-5.

[0104] From the viewpoint of sensitivity, Ar2 in formula (1) is preferably a divalent aromatic group, more preferably a divalent aromatic group having 6 to 10 carbon atoms, further preferably a phenylene group or a substituted phenylene group, and particularly preferably a phenylene group or a methylphenylene group.

[0105] Furthermore, the divalent aromatic group and divalent heteroaromatic group in Ar2 in formula (1) may further have a substituent. Examples of the substituent include the substituents described above.

[0106] Examples of the divalent aromatic group in Ar2 include a phenylene group, a naphthylene group, anthracenediyl group, and the like which may have a substituent.

[0107] Examples of the divalent heteroaromatic group in Ar2 include a furandiyl group and a thiophenediyl group which may have a substituent.

[0108] Examples of the divalent group formed by bonding two or more of the divalent aromatic groups and divalent heteroaromatic groups in Ar2 include a group formed by bonding a biphenyl group, a phenylene group, and a thiophenediyl group.

[0109] Furthermore, when Ar2 in formula (1) is a phenylene group or a substituted phenylene group, the bonding position of L1 to the nitrogen atom of the indole ring is preferably the meta position or the para position, and more preferably the para position, from the viewpoint of sensitivity.

[0110] Preferred specific examples of Ar2 in formula (1) are shown below: In addition, * represents the bonding position to L1 or the nitrogen atom of the indole ring.

[0111] [Chemical formula 7]

[0112]

[0113] Among them, from the viewpoint of sensitivity, Ar2-1 or Ar2-2 is particularly preferred as Ar2.

[0114] From the viewpoint of sensitivity, L1 in formula (1) is preferably a carbonyl group.

[0115] 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, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

[0116] From the perspective of sensitivity, R in formula (1) 15 ~R 18 Each independently preferably is a hydrogen atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, a nitro group or an alkoxy group having 1 to 8 carbon atoms, more preferably a hydrogen atom, a bromine atom, a methyl group, a nitro group or a methoxy group, and particularly preferably a hydrogen atom.

[0117] From the perspective of sensitivity, R in formula (1) 19 It is preferably a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom, a bromine atom, a methyl group or a phenyl group, and particularly preferably a hydrogen atom.

[0118] From the viewpoint of sensitivity, Y1 in formula (1) is preferably an alkyl group having a branched structure. The branched structure may be chain-shaped or cyclic, and is more preferably cyclic from the viewpoint of sensitivity. That is, Y1 is more preferably an alkyl group having a ring structure.

[0119] From the viewpoint of sensitivity, the position of the branched structure is preferably the γ-position of the oxime group, and it is more preferred that one hydrogen atom (γ hydrogen) exists at the γ-position.

[0120] Furthermore, from the viewpoint of sensitivity, Y1 in formula (1) is preferably an alkyl group having a heteroatom, and more preferably an alkyl group having an oxygen atom, a sulfur atom or a nitrogen atom.

[0121] In addition, from the viewpoint of sensitivity, Y1 in formula (1) is preferably an unsubstituted linear, branched or cyclic alkyl group, an aryl group or an alkyl group having at least one substituent selected from the following Group A, more preferably a methyl group or an alkyl group having at least one substituent selected from the above Group A, further preferably an alkyl group having at least one substituent selected from the above Group A, particularly preferably an alkyl group having at least one substituent selected from the following Group B, and most preferably an alkyl group having at least one substituent selected from the following Group C.

[0122] -Group A-

[0123] Cyano, alkenyl, alkynyl, -N(R a )2. -SR a 、-COOH、-OR a 、-O-COR c 、-O-CO-OR c 、-CONR a Rb 、-NR a -CO-R b 、-O-CO-NR a R b 、-NR a -CO-OR b 、-NR a -CO-NR a R b 、-SO-R c 、-SO2-R c 、-O-SO2-R c 、-SO2-NR a R b 、-NR a -SO2-R a 、-CO-NR a -COR b 、-CO-NR a -SO2-R b 、-SO2-NR a -CO-R b 、-SO2-NR a -SO2-R c 、-Si(R a ) L (OR b ) K , heterocyclic group, and -O(R d O) J -R a

[0124] Among them, R a and R b Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R c Each independently represents an alkyl group, an aryl group or a heteroaryl group, and R d Each independently represents an alkylene group, an arylene group or a group formed by combining two or more of them; L and K each independently represent an integer of 0 to 3, satisfying L+K=3; and J represents an integer of 1 to 100.

[0125] - Group B -

[0126] Alkenyl, -N(R a )2. -SR a 、-OR a

[0127] - Group C -

[0128] -N(R a )2. -SR a 、-OR a

[0129] Among them, R a Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.

[0130] The above R a Each independently is preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an alkyl group, and particularly preferably a cycloalkyl group.

[0131] The above R b Each independently is preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.

[0132] The above R c It is preferably an alkyl group or an aryl group, and is preferably an alkyl group.

[0133] The above R d Each independently is preferably an alkylene group, and more preferably an ethylene group or a propylene group.

[0134] Furthermore, the above R a ~R c Two or more of them may be bonded to form a ring structure.

[0135] Furthermore, from the viewpoint of sensitivity, Y1 in formula (1) is preferably a group represented by the following formula (2).

[0136] [Chemical formula 8]

[0137]

[0138] 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.

[0139] From the viewpoint of sensitivity, R2 in formula (2) is preferably an alkyl group.

[0140] From the viewpoint of sensitivity, R3 in formula (2) is preferably a hydrogen atom.

[0141] From the viewpoint of sensitivity, R4 in formula (2) is preferably an alkyl group.

[0142] Among them, from the viewpoint of 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.

[0143] From the viewpoint of sensitivity, L1 in formula (2) is preferably O, S or NR, and more preferably O or NR.

[0144] From the viewpoint of sensitivity, L2 in formula (2) is preferably CHR.

[0145] 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.

[0146] From the viewpoint of sensitivity, R in the above CHR is preferably a hydrogen atom.

[0147] 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.

[0148] Furthermore, from the viewpoint of sensitivity, Y1 in formula (1) is more preferably a group represented by the following formula (3).

[0149] [Chemical formula 9]

[0150]

[0151] 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.

[0152] From the viewpoint of sensitivity, L3 in formula (3) is preferably O, S or NR.

[0153] From the viewpoint of sensitivity, L4 in formula (3) is preferably CHR.

[0154] Preferred aspects of R in formula (3) are the same as preferred aspects of R in formula (2).

[0155] From the viewpoint of sensitivity, R5 in formula (3) is preferably a hydrogen atom.

[0156] 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.

[0157] Preferred specific examples of Y1 in formula (1) are shown below. In addition, * represents the bonding position to the oxime group.

[0158] [Chemical formula 10]

[0159]

[0160] Among them, from the viewpoint of sensitivity, Y1 is preferably at least one group selected from Y-1, Y-2, Y-3, Y-12, Y-13, Y-14, Y-15, Y-16, Y-17, Y-18, Y-22 and Y-26, more preferably at least one group selected from Y-1, Y-2, Y-3, Y-12, Y-13, Y-14, Y-15, Y-16, Y-17 and Y-18, and particularly preferably at least one group selected from Y-2, Y-13, Y-14, Y-15, Y-16, Y-17 and Y-18.

[0161] The above Ar2, R1, R 15 ~R 19 The alkyl group, aryl group, divalent aromatic group, divalent heteroaromatic group, alkyl group in alkoxy group and the like in Y1 may further have a substituent. As the substituent, preferably, the substituents described above in Ar1 are mentioned.

[0162] From the viewpoint of sensitivity, n in formula (1) is preferably 0.

[0163] The free radical polymerization initiator represented by the above formula (1) preferably has absorption in any one of the ArF absorption region, i.e., wavelength 193nm, the KrF absorption region, i.e., wavelength 248nm, and the i-ray absorption region, i.e., wavelength 365nm, and more preferably has absorption in any one of the ArF absorption region, i.e., wavelength 193nm, and the KrF absorption region, i.e., wavelength 248nm.

[0164] 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 than, most preferably 20,000 L·g -1 cm -1 above.

[0165] The gram absorption coefficient of the radical polymerization initiator represented by the formula (1) is measured by the following method.

[0166] Weigh 12.5 mg of polymerization initiator accurately and put it into a 100 mL volumetric flask. Add acetonitrile to it and dissolve it completely. Take out 2 mL of the polymerization initiator solution with a volumetric pipette and add a certain amount of water to a 25 mL volumetric flask. Use it as the measurement sample.

[0167] The sample was added to a 1 cm square 5 mL quartz glass cuvette, and the absorbance was measured in air to calculate the gram absorption coefficient. The measuring instrument used was an ultraviolet-visible-near-infrared spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Corporation).

[0168] As specific examples of the free radical polymerization initiator represented by the above formula (1), preferably A-1 to A-193 can be cited, but it is not limited thereto. In addition, Ar1-1 to Ar1-34, Ar2-1 to Ar2-20 and Y-1 to Y-35 are the same groups as the above Ar1-1 to Ar1-34, Ar2-1 to Ar2-20 and Y-1 to Y-35, respectively. In addition, tBu represents a tert-butyl group, and Ph represents a phenyl group.

[0169] [Table 1]

[0170]

[0171] [Table 2]

[0172]

[0173] [Table 3]

[0174]

[0175] [Table 4]

[0176]

[0177] [Table 5]

[0178]

[0179] The curable composition according to the present invention may contain one radical polymerization initiator represented by the above formula (1) alone or two or more thereof. When two or more thereof are used, the total amount thereof is preferably within the following range.

[0180] 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 curable composition.

[0181] 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.

[0182] 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.

[0183] In addition, as a method for producing a free radical polymerization initiator represented by the above formula (1), for example, the following method can be cited: an aromatic compound having an electron donating group (EDG) such as an alkoxy group or an alkylthio group and an aromatic acid chloride having a halogen atom (especially preferably a fluorine atom) are synthesized into an aromatic ketone compound having a halogen atom and an electron donating group by a Friedel-Crafts reaction based on a Lewis acid (for example, aluminum chloride), and then an oxime precursor is synthesized by a nucleophilic substitution reaction with a substituted indole under alkaline conditions (for example, in the presence of potassium carbonate), and the hydroxyl group of the oxime group is acetylated by further performing oximation and oxime esterification. As an example, the following method can be cited.

[0184] Furthermore, the oximation can be carried out by a known method. That is, the ketone can be oximated with hydroxylamine and then esterified with an acid chloride oxime.

[0185] The oximation of a ketone can be carried out by a known method. Specifically, a ketone can be oximated at the α-position by treating it with isoamyl nitrite in a base, and then esterified with an acid chloride oxime.

[0186] [Chemical formula 11]

[0187]

[0188] <Other radical polymerization initiators>

[0189] The curable composition according to the present invention may contain a radical polymerization initiator other than the radical polymerization initiator represented by the above formula (1).

[0190] Examples of other radical polymerization initiators include oxime compounds, α-aminoacetophenone compounds, α-hydroxyketone compounds, and acylphosphine compounds.

[0191] Among them, oxime compounds are preferred.

[0192] 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.

[0193] 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 (manufactured by TRONLY) can be cited.

[0194] 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. Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0195] 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.

[0196] Furthermore, as the oxime compound, the compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 can be used.

[0197] Specific examples of the oxime compound include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

[0198] Furthermore, as the oxime compound, the following compounds can be particularly preferably exemplified.

[0199] [Chemical formula 12]

[0200]

[0201] [Chemical formula 13]

[0202]

[0203] [Chemical formula 14]

[0204]

[0205] The mass ratio when used simultaneously with other free radical polymerization initiators 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.

[0206] <Colorant>

[0207] The curable composition according to the present invention preferably contains a colorant.

[0208] 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.

[0209] The colorant can be a pigment or a dye.

[0210] Furthermore, as a colorant, from the viewpoint of colorability and dispersibility, at least one pigment selected from the group consisting of diketopyrrolopyrrole pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments, quinophthalone pigments, azo pigments, azomethine pigments and dioxazine pigments is preferred, and at least one pigment selected from the group consisting of diketopyrrolopyrrole pigments, phthalocyanine pigments and isoindoline pigments is more preferred.

[0211] 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.

[0212] The average primary particle size of the pigment is preferably 1nm to 200nm. The lower limit is more preferably 5nm or more, and further preferably 10nm or more. The upper limit is more preferably 180nm or less, further preferably 150nm or less, and particularly preferably 100nm 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 corresponding circle equivalent diameter 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.

[0213] 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.

[0214] As green colorants, phthalocyanine compounds and squaric acid 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.

[0215] 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.

[0216] 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, the red colorant is a diketopyrrolopyrrole compound, anthraquinone compound, or azo compound, and more preferably a diketopyrrolopyrrole compound. 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.

[0217] 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.

[0218] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a pigment, more preferably an azo pigment, azomethine pigment, isoindoline pigment, pteridine pigment, quinophthalone pigment, or perylene pigment, and more preferably an azo pigment or 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.

[0219] Furthermore, as a yellow colorant, an azobarbituric acid nickel complex having the following structure can also be used.

[0220] [Chemical formula 15]

[0221]

[0222] Furthermore, as the yellow colorant, the compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485 can also be used.

[0223] The yellow colorant is preferably CI Pigment Yellow 117, 129, 138, 139, 150, 185.

[0224] 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.

[0225] Examples of the violet colorant include violet pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0226] Examples of blue colorants include 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, and 88. In addition, aluminum phthalocyanine compounds having a phosphorus atom can also be used as blue colorants. Specific examples include 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.

[0227] 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 azos, anilino azos, triarylmethanes, anthraquinones, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethines, xanthenes, phthalocyanines, benzopyrans, indigos, and pyrromethenes can be cited.

[0228] 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.

[0229] 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 quinophthalone compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0030759, the The polymer dye described in Patent Gazette No. 10-2020-0061793, the colorant described in Japanese Patent Gazette 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 Gazette No. 2022-045895, the compound described in International Publication No. 2022 / 050051, etc. 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 a rod-shaped structure, or can be used for both structures.

[0230] 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.

[0231] 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, titanium oxynitride. For the purpose of improving dispersibility, suppressing cohesion, etc., the surface of titanium black can be modified as needed. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide. In addition, it is also possible to use a water-repellent substance as shown in Japanese Patent Publication No. 2007-302836. As a black colorant, color index (CI) pigment black 1, 7 can also be used. Regarding titanium black, it is preferred that the primary particle size and average primary particle size of each particle are small. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersed material. For example, a dispersion containing titanium black particles and silicon dioxide particles and having a content ratio of Si atoms to Ti atoms adjusted in the range of 0.20 to 0.50 can be cited. For the above dispersion, reference can also be made to paragraphs 0020 to 0105 of Japanese Patent Application Laid-Open No. 2012-169556, which is incorporated herein. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, and 13M-T (product names: manufactured by Mitsubishi Materials Corporation), and Tilack D (product name). As organic black colorants, bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds may be mentioned, and bisbenzofuranone compounds and perylene compounds are preferred. As bisbenzofuranone compounds, compounds described in JP-T 2010-534726, JP-T 2012-515233, JP-T 2012-515234, International Publication No. 2014 / 208348, and JP-T 2015-525260 may be mentioned, and for example, “Irgaphor” manufactured by BASF Corporation may be mentioned. As the perylene compound, CI Pigment Black 31, 32, etc. can be mentioned. As the azomethine compound, the compounds described in the Japanese Patent Publication No. 01-170601, the Japanese Patent Publication No. 02-034664, etc. can be mentioned, for example, it can be obtained as "CHROMO FINE BLACK A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. In addition, as an organic black colorant, perylene black (Lumogen Black FK4280, etc.) and Paliogen Black S0084 described in paragraphs 0016 to 0020 of Japanese Patent Publication No. 2017-226821 can also be used.

[0232] The curable 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.

[0233] From the viewpoint of further exerting the effect in the present invention, the content of the colorant is preferably 10% to 75% by mass relative to the total solid content of the curable 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.

[0234] <Radical polymerizable compound>

[0235] The curable composition according to the present invention contains a radical polymerizable compound.

[0236] Examples of the radical polymerizable compound include compounds having an ethylenically unsaturated group.

[0237] 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.

[0238] The molecular weight of the monomer type radical polymerizable compound (polymerizable monomer) is preferably less than 2,000, and more preferably 1,500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, and more preferably 200 or more.

[0239] 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.

[0240] 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.

[0241] 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 (these are manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co., LTD.), and the like are also preferably used.

[0242] The content of the radical polymerizable compound is preferably 0.1% to 50% by mass relative to the total solid content of the curable 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.

[0243] In the curable 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.

[0244] <Resin>

[0245] The curable composition according to the present invention preferably further contains a resin.

[0246] The curable composition of the present invention can use a resin as a radical polymerizable compound. The radical polymerizable compound preferably uses a radical polymerizable compound containing at least a resin. For example, the resin is formulated for purposes such as dispersing a pigment in a curable composition or for purposes such as an adhesive. In addition, the resin mainly used to disperse a pigment in a curable composition is also referred to as a dispersant. However, this use of the resin is an example, and the resin can also be used for purposes other than this use.

[0247] In addition, resins having radical polymerizable groups also belong to radical polymerizable compounds.

[0248] Furthermore, it is more preferable that the curable composition according to the present invention further contains a resin other than the radical polymerizable compound.

[0249] 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.

[0250] 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, polyamide-imide 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. One kind can be used alone from these resins, or two or more kinds can be mixed and used. As cyclic olefin 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) etc. made by JSR CORPORATION can be mentioned. Furthermore, as the resin, the resin described in the examples of International Publication No. 2016 / 088645, the resin described in Japanese Patent Application Laid-Open No. 2017-057265, the resin described in Japanese Patent Application Laid-Open No. 2017-032685, the resin described in Japanese Patent Application Laid-Open No. 2017-075248, the resin described in Japanese Patent Application Laid-Open No. 2017-066240, the resin described in Japanese Patent Application Laid-Open No. 2017-1 The resin described in Japanese Patent Application Publication No. 67513, the resin described in Japanese Patent Application Publication No. 2017-173787, the resin described in paragraphs 0041 to 0060 of Japanese Patent Application Publication No. 2017-206689, the resin described in paragraphs 0022 to 0071 of Japanese Patent Application Publication No. 2018-010856, the blocked polyisocyanate resin (cyanate resin) described in Japanese Patent Application Publication No. 2016-222891, the resin described in Japanese Patent Application Publication No. 2020-122052, the resin described in Japanese Patent Application Publication No. 2020-111656, the resin described in Japanese Patent Application Publication No. 2020-139021, and the resin described in Japanese Patent Application Publication No. 2017-138503, which contains a structural unit having a ring structure on the main chain and a structural unit having a biphenyl group on the side chain. Furthermore, as a resin, a resin having a fluorene skeleton can also be preferably used. Regarding the 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. Furthermore, as a resin, the resin described in paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325, the resin represented by Formula 1 described in Korean Patent Publication No. 10-2020-0078339, and the copolymer containing epoxy groups and acid groups described in International Publication No. 2022 / 030445 can also be used.

[0251] As the resin, it is preferred to use a resin having an acid group. As the acid group, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. can be cited. These acid groups can be only one kind, or can be two or more kinds. The resin having an acid group can be used as an alkali-soluble resin, for example. 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.

[0252] As the resin, the compounds described in paragraphs 0056 to 0059 of International Publication No. 2022 / 085485 can also be used.

[0253] 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.

[0254] Furthermore, as the 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 unit 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 the two repeating units are contained, 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.

[0255] [Chemical formula 16]

[0256]

[0257] In the 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. 1The divalent linking group represented by the present 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 composed of two or more of them. The alkylene may be any of linear, branched, and cyclic, preferably linear or branched. In addition, the alkylene may have a substituent or may be unsubstituted. As the substituent, a hydroxyl group, an alkoxy group, etc. may be mentioned.

[0258] 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.

[0259] The resin Ep may contain 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.

[0260] 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.

[0261] Examples of the ethylenically unsaturated group include a vinyl group, a styryl group, a (meth)allyl group, and a (meth)acryloyl group.

[0262] 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.

[0263] When the resin Ep contains repeating units having ethylenically unsaturated groups, the content of repeating units having ethylenically unsaturated groups in the resin Ep is preferably 1 mol% to 65 mol% in all 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.

[0264] Resin Ep preferably further comprises a repeating unit having an aromatic hydrocarbon ring. As an aromatic hydrocarbon ring, a benzene ring or a naphthalene ring is preferred, preferably a benzene ring. The aromatic hydrocarbon ring may have a substituent. As a substituent, an alkyl group or the like can be cited. When the resin having a cyclic ether group comprises a repeating unit having an aromatic hydrocarbon ring, the content of the repeating unit having an aromatic hydrocarbon ring 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 a repeating unit having an aromatic hydrocarbon ring, repeating units of monofunctional polymerizable compounds having an aromatic hydrocarbon ring such as vinyl toluene and benzyl (meth) acrylate can be cited.

[0265] As the resin, a resin containing a repeating unit derived from a compound represented by the formula (X) is also preferably used.

[0266] [Chemical formula 17]

[0267]

[0268] In the formula, R 1 represents a hydrogen atom or a methyl group, R 21 and R 22 Each independently represents an alkylene group, and n represents an integer of 0 to 15. 21 and R 22 The number of carbon atoms of the alkylene group represented is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

[0269] Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of para-cumylphenol, and examples of commercially available products include ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.).

[0270] 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 is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In the aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.

[0271] 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).

[0272] [Chemical formula 18]

[0273]

[0274] 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.

[0275] 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.

[0276] 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.

[0277] [Chemical formula 19]

[0278]

[0279] 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).

[0280] [Chemical formula 20]

[0281]

[0282] Ar 1 The 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.

[0283] 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.

[0284] [Chemical formula 21]

[0285]

[0286] In the formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

[0287] 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.

[0288] 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.

[0289] 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).

[0290] In the formulas (Ar-11) to (Ar-13), *1 represents 1 bonding position.

[0291] In formula (Ac-1), L 1 It represents -COO- or CONH-, and preferably represents -COO-.

[0292] As L in formula (Ac-1) 2 The divalent linking group represented by may include alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups formed by combinations of two or more thereof. 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. Examples of the substituent include hydroxyl groups and the like. L 2 The divalent linking group represented by is preferably -L 2a -O- represented group. 2aExamples 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.

[0293] 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.

[0294] In formula (Ac-2), L 11 It represents -COO- or CONH-, and preferably represents -COO-.

[0295] 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 composed of two or more thereof. 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 a straight chain, a branched chain, and a cyclic group. 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).

[0296] [Chemical formula 22]

[0297]

[0298] 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 12b 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-, etc., preferably a hydrocarbon group or a group consisting of a hydrocarbon group and -O-.

[0299] 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.

[0300] 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.

[0301] P 10 The polymer chain represented may contain a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated groups.

[0302] The curable composition involved in the present invention preferably contains a resin as a dispersant. As the dispersant, an acidic dispersant (acidic resin) and an alkaline dispersant (alkaline resin) can be mentioned. Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of alkaline groups. As the acidic dispersant (acidic resin), it is preferred that the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of alkaline groups is set to 100 mol%. The acid group possessed by 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. In addition, the alkaline dispersant (alkaline resin) refers to a resin in which the amount of base groups is greater than the amount of acid groups. As the alkaline dispersant (alkaline resin), it is preferred that the amount of alkaline groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of alkaline groups is set to 100 mol%.

[0303] The basic group contained in the basic dispersant is preferably an amino group.

[0304] 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.

[0305] 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 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.

[0306] The resin used as a dispersant is also preferably a polyimide dispersant containing a nitrogen atom in at least one of the main chain and the side chain. As a polyimide dispersant, a resin having a main chain and a side chain and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred, wherein the main chain contains a partial structure having a functional group with a pKa of less than 14, and the number of atoms in 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 polyimide 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.

[0307] 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. As such a resin, for example, a dendritic polymer (including a star polymer) can be cited. In addition, as a specific example of a dendritic polymer, polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962 can be cited.

[0308] 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%.

[0309] 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.

[0310] 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.

[0311] Furthermore, the resin containing an oxetane group in a side chain is preferably a graft polymer.

[0312] 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%.

[0313] In addition, as the dispersant, the resin described in Japanese Patent Publication No. 2018-087939, the block copolymers (FB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Publication No. 6432077, the polyethyleneimine having a polyester side chain described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having an acrylamide structural unit described in Japanese Patent Publication No. 2020-066687, the block polymer having an acrylamide structural unit described in Japanese Patent Publication No. 2020-066688, the dispersant described in International Publication No. 2016 / 104803, etc. can also be used.

[0314] As the dispersant, a polyamic acid type dispersion resin or a polyimide type dispersion resin can also be used. As such a resin, the dispersants described in International Publication No. 2022 / 019253, International Publication No. 2022 / 019254, and International Publication No. 2022 / 019255 can also be used.

[0315] The dispersant can be obtained as a commercial product, and specific examples thereof include the Disperbyk series manufactured by BYK-Chemie GmbH (e.g., Disperbyk-111, 161, 2001, etc.), the SOLSPERSE series manufactured by Japan Lubrizol Corporation (e.g., SOLSPERSE 20000, 76500, etc.), and the Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc., etc. In addition, the product described in paragraph 0129 of Japanese Patent Application Laid-Open No. 2012-137564 and the product described in paragraph 0235 of Japanese Patent Application Laid-Open No. 2017-194662 can also be used as the dispersant.

[0316] When the curable composition of the present invention contains a resin as a radical polymerizable compound, the content of the resin is preferably 1% to 70% by mass relative to the total solid content of the curable composition. The lower limit is more preferably 2% by mass or more, more 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 more preferably 60% by mass or less.

[0317] 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 curable 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.

[0318] Furthermore, the content of the alkali-soluble resin is preferably 1% to 70% by mass relative to the total solid content of the curable 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.

[0319] When the curable 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 curable 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.

[0320] The curable composition according to the present invention may contain only one resin or two or more resins. When containing two or more resins, the total amount thereof is preferably within the above range.

[0321] <Solvent>

[0322] The curable 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, reference can be made to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated into this specification. In addition, cyclic alkyl-substituted ester solvents and cyclic alkyl-substituted ketone solvents 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 mono Methyl 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, diacetate butane-1,3-diyl, 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, for environmental reasons, it is sometimes preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents (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).

[0323] 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. An organic solvent of mass ppt (parts pertrillion: parts per trillion) level can be used as needed, such as provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0324] 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.

[0325] 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 may contain a plurality of types.

[0326] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0327] The content of the solvent in the curable 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.

[0328] Moreover, from the viewpoint of environmental restrictions, the curable composition involved in the present invention preferably does not substantially contain environmentally restricted substances. In addition, in the present invention, substantially not containing environmentally restricted substances means that the content of environmentally restricted substances in the curable 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. For example, environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These are registered as environmentally restricted substances based on REACH (Registration Evaluation Authorization and Restriction of Chemicals: About Chemical Registration, Evaluation, Permit and Restriction) Act, PRTR (Pollutant Release and Transfer Register: Pollutant Emission and Transfer Registration System) Act, VOC (Volatile Organic Compounds: Volatile Organic Compounds) restrictions, etc., and the amount of use and operation methods are strictly restricted. When manufacturing the various components used in the curable composition, these compounds are sometimes used as solvents and sometimes mixed into the curable 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 restricted substances, the method of heating and reducing the boiling point of the system and setting it above the boiling point of the environmentally restricted substances can be cited, thereby removing and reducing environmentally restricted substances from the system by distillation. In addition, when a small amount of environmentally restricted substances are removed by distillation, in order to improve efficiency, it is also useful to azeotropize it with a solvent having the same boiling point as the solvent. In addition, when containing a compound with free radical polymerizability, an inhibitor can be added and removed by reduced pressure distillation to suppress free radical polymerization during the reduced pressure distillation removal and cause crosslinking between molecules. These distillation removal methods can be implemented at any stage such as the stage of raw materials, the stage of the reaction product of the raw materials (such as the resin solution after polymerization, the multifunctional monomer solution) or the stage of the curable composition made by mixing these compounds.

[0329] <Pigment derivatives>

[0330] The curable composition of the present invention may contain 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.

[0331] Examples of the pigment skeleton constituting the pigment derivative include a quinoline pigment skeleton, a benzimidazolone pigment skeleton, a benzoindole pigment skeleton, a benzothiazole pigment skeleton, an iminium pigment skeleton, a squaric acid 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 quinophthalone pigment skeleton, an iminium pigment skeleton, a dithiol pigment skeleton, a triarylmethane pigment skeleton, and a pyrromethene pigment skeleton.

[0332] 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 -SO2NHSO2R is more preferably 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.

[0333] Examples of the base include amino, pyridyl and salts thereof, ammonium salts and phthalimidomethyl groups. Examples of the atom or atom group constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, and phenolate ions.

[0334] 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 -1cm -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.

[0335] 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.

[0336] 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 curable 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.

[0337] <Chain transfer agent>

[0338] From the viewpoint of adhesion, the curable composition according to the present invention preferably further contains a chain transfer agent.

[0339] As the chain transfer agent, thiol compounds, thiocarbonylthio compounds, dimers of aromatic α-methylalkenyl compounds, etc. can be mentioned. Since even a small amount of the compounding amount can easily adjust the line width of the pattern, thiol compounds are preferred. In addition, the chain transfer agent is preferably a compound with little coloration.

[0340] -Mercaptan compounds-

[0341] 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, it is particularly preferred that the thiol compound is a compound having 4 thiol groups.

[0342] Furthermore, the thiol compound is also preferably a compound derived from a polyfunctional alcohol.

[0343] The thiol compound is preferably a compound represented by the following formula (SH-1).

[0344] L 1 -(SH) n Formula (SH-1)

[0345] In the formula, SH represents a thiol group, L 1 represents an n-valent group, where n represents an integer of 1 or greater.

[0346] 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.

[0347] In formula (SH-1), n ​​represents an integer greater than or equal to 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. It is particularly preferred that n is 4.

[0348] Specific examples of thiol compounds include compounds of the following structures. Commercially available thiol compounds include PEMP (thiol compound manufactured by SC Organic Chemical Co., Ltd.), Sanceler M (thiol compound manufactured by Sanshin Chemical Industry Co., Ltd.), and Karenz MT BD1 (thiol compound manufactured by Showadenko KK).

[0349] [Chemical formula 23]

[0350]

[0351] [Chemical formula 24]

[0352]

[0353] [Chemical formula 25]

[0354]

[0355] [Chemical formula 26]

[0356]

[0357] -Thiocarbonylthio compounds-

[0358] 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)).

[0359] [Chemical formula 27]

[0360]

[0361] In formula (SC-1) to formula (SC-5), Z 1 ~Z 11 Each independently represents a substituent.

[0362] 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(=0)(0R 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.

[0363] 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.

[0364] 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.

[0365] The heteroaryl group is preferably a monocyclic heteroaryl group or a condensed heteroaryl group having 2 to 8 condensed rings, and more preferably a monocyclic heteroaryl group or a condensed heteroaryl group having 2 to 4 condensed 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.

[0366] Specific examples of the bis(thiocarbonyl) disulfide compounds include tetraethylaminothiocarbonyl disulfide, tetramethylaminothiocarbonyl 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), bis(n-pentylmercapto-thiocarbonyl), bis(n-nonylmercapto-thiocarbonyl), bis(n-decylmercapto-thiocarbonyl), bis(tert-dodecylmercapto-thiocarbonyl), bis(n-tetradecylmercapto-thiocarbonyl), bis(n-hexadecylmercapto-thiocarbonyl), bis(n-octadecylmercapto-thiocarbonyl), and the like.

[0367] Specific examples of the dithioester compound include 2-phenyl-2-propylbenzodisulfate, 4-cyano-4-(phenylthiocarbonylthio)pentanoic acid, and 2-cyano-2-propylbenzodisulfate.

[0368] 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.

[0369] Specific examples of the dithiocarbamate compound include cyanomethylmethyl(phenyl)carbamate disulfate and cyanomethyldiphenylcarbamate-disulfate.

[0370] Specific examples of the xanthate compound include xanthate esters and the like.

[0371] -Dimer of aromatic α-methylalkenyl group-

[0372] Examples of the dimer of aromatic α-methylalkenyl include 2,4-diphenyl-4-methyl-1-pentene and the like.

[0373] 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.

[0374] 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.

[0375] 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 curable composition. The chain transfer agent may be used alone or in combination of two or more.

[0376] <Polyalkyleneimine>

[0377] The curable composition involved in the present invention can contain polyalkylene imine. Polyalkylene imine can be used as a dispersing aid for pigments, for example. A dispersing aid refers to a material used to improve the dispersibility of pigments in a curable composition. Polyalkylene imine refers to a polymer obtained by ring-opening polymerization of alkylene imine and having at least a secondary amino group. In addition to secondary amino groups, polyalkylene imine may also contain primary amino groups or tertiary amino groups. Polyalkylene imine is preferably a polymer having a branched structure containing primary amino groups, secondary amino groups and tertiary amino groups, respectively. The number of carbon atoms of alkylene imine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0378] 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.

[0379] 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.

[0380] As specific examples of alkylene imine, ethyleneimine, propyleneimine, 1,2-buteneimine, 2,3-buteneimine, etc. can be mentioned, preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. Polyalkylene imine is particularly preferably polyethyleneimine. And, relative to the total of primary amino group, secondary amino group and tertiary amino group, polyethyleneimine preferably contains more than 10 mol% of primary amino group, more preferably contains more than 20 mol%, and further preferably contains more than 30 mol%. As commercial products of polyethylene imine, EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (all manufactured by NIPPONSHOKUBAI CO., LTD.) and the like can be mentioned.

[0381] The content of the polyalkylene imine in the total solid content of the curable composition is preferably 0.1% 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% 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. Polyalkylene imine can be used only one or more. When using two or more, their total amount is preferably within the above range.

[0382] <Curing Accelerator>

[0383] The curable composition of the present invention can contain a curing accelerator. As a curing accelerator, a thiol compound, a methylol compound, an amine compound, a phosphonium salt compound, an amidine salt compound, an amide compound, a base generator, an isocyanate compound, an alkoxysilane compound, an onium salt compound, etc. can be cited. As a specific example of a curing accelerator, the compound 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 curable composition is preferably 0.3% to 8.9% by mass, and more preferably 0.8% to 6.4% by mass.

[0384] <Infrared absorber>

[0385] The curable composition of the present invention may contain an infrared absorber. For example, when an infrared transmission filter is formed using the curable composition of the present invention, the wavelength of the transmitted light can be shifted to a longer wavelength side with respect to the film obtained by containing an infrared absorber in the curable composition. 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 exceeding 700nm and below 1800nm. Furthermore, 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 Ratio A 1 / A 2 It is preferably 0.08 or less, and more preferably 0.04 or less.

[0386] Examples of infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squaryl compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, crotonium compounds, oxocyanine compounds, iminium 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 croconium compounds described in International Publication No. 2019 / 021767 can also be used.

[0387] The content of the infrared absorber in the total solid content of the curable 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 curable composition of the present invention may contain only one infrared absorber or two or more. When two or more infrared absorbers are included, their total amount is preferably within the above range.

[0388] <Ultraviolet light absorber>

[0389] The curable composition involved in 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 this compound, the compound 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 curable 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, their total amount is preferably within the above range.

[0390] <Polymerization Inhibitor>

[0391] The curable 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, first 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 curable composition is preferably 0.0001% by mass to 5% by mass. The polymerization inhibitor may be only one kind or more than two kinds. In the case of more than two kinds, their total amount is preferably within the above range.

[0392] <Silane coupling agent>

[0393] The curable 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, the silane coupling agent preferably has a compound of an alkoxysilyl group. In addition, as a functional group other than a hydrolyzable group, for example, a vinyl, (meth) allyl group, (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 curable composition is preferably 0.01% by mass to 15.0% by mass, and more preferably 0.05% by mass to 10.0% by mass.

[0394] 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 thereof is preferably within the above range.

[0395] <Surfactant>

[0396] The curable composition involved in the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants, etc. can be used. Preferably, the surfactant is a silicone surfactant or a fluorine-based surfactant. Regarding the surfactant, reference can be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which are incorporated into this specification.

[0397] 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 curable composition.

[0398] 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.

[0399] As the nonionic surfactant, the compounds described in paragraph 0174 of International Publication No. 2022 / 085485 can also be used.

[0400] Examples of the silicone surfactant include DOWSIL SH8400, SH8400 FLUID, 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.), Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie GmbH), etc.

[0401] Furthermore, as the silicone-based surfactant, compounds having the following structures can also be used.

[0402] [Chemical formula 28]

[0403]

[0404] The content of the surfactant in the total solid content of the curable composition is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% by mass to 3.0% by mass. The surfactant may be only one or two or more. In the case of two or more, their total amount is preferably within the above range.

[0405] <Antioxidants>

[0406] The curable 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 called a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be mentioned. Preferably, a compound has 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 phenol group and a phosphite group in the same molecule. In addition, the antioxidant can also preferably use a phosphorus antioxidant. Examples of the phosphorus 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. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB A0-60G, ADK STAB AO-80, ADK STAB A0-330 (all manufactured by ADEKA Corporation), etc. In addition, antioxidants may also include compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the curable composition is preferably 0.01% to 20% by mass, 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, their total amount is preferably within the above range.

[0407] <Other ingredients>

[0408] The curable composition involved in the present invention can contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliary agents (for example, 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 the compounds described in paragraph 0182 of International Publication No. 2022 / 085485, the xanthene-type epoxy resins described in Japanese Patent Publication No. 2021-195421, and the xanthene-type epoxy resins described in Japanese Patent Publication No. 2021-195422.

[0409] The curable 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.

[0410] The curable 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.

[0411] The curable 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 curable composition is 1000 ppb or less, more preferably 100 ppb or less, and particularly preferably zero.

[0412] From the perspective of environmental restrictions, the use of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts is sometimes restricted. In the curable 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 curable 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 be a substitute for perfluoroalkyl sulfonic acid and its salts and a compound that can be a substitute for perfluoroalkyl carboxylic acid and its salts, a curable composition that substantially does not contain perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts can also be selected. As a compound that can be a substitute for the restricted compound, for example, a compound that is excluded from the restricted object according to the difference in the number of carbon atoms of the perfluoroalkyl group can be cited. However, the above content does not hinder the use of perfluoroalkyl sulfonic acid and its salt and perfluoroalkyl carboxylic acid and its salt. The curable composition involved in the present invention can also contain perfluoroalkyl sulfonic acid and its salt and perfluoroalkyl carboxylic acid and its salt within the maximum allowable range.

[0413] The water content of the curable 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.

[0414] The curable composition of the present invention can be used to adjust the viscosity for the purpose of adjusting the film surface (flatness, etc.) and adjusting the film thickness. The value of 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.

[0415] Regarding the curable composition involved in the present invention, from the viewpoints of environmental response, suppression of foreign matter, suppression of device pollution, etc., the amount of chloride ions in the curable composition is preferably 10,000 ppm or less, and more preferably 1000 ppm or less. In order to make the chloride ions in the curable composition within the above range, methods such as using raw materials with a small chloride ion content, and removing chloride ions by water washing, ion exchange resin, filter filtration, etc. can be cited. As a method for determining chloride ions, known methods can be used, for example, ion chromatography, combustion ion chromatography, etc. can be cited.

[0416] <Storage Container>

[0417] The storage container of the curable composition is not particularly limited, and a known storage container can be used. In addition, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can also be used as the storage container.

[0418] <Method for preparing curable composition>

[0419] The curable composition of the present invention can be prepared by mixing the above components. When preparing the curable composition, all the components can be dissolved and / or dispersed in a solvent at the same time to prepare the curable composition, or each component can be appropriately divided into two or more solutions or dispersions as needed, and they can be mixed when used (when applied) to prepare the curable composition.

[0420] And, preferably, when preparing curable composition, the process of dispersing pigment is included. In the pigment dispersion process, as the mechanical force for dispersing pigment, compression, extrusion, impact, shearing, pitting etc. can be cited. As the specific example of these processes, bead milling, sand milling (Sand Mill), roller milling, ball milling, coating stirring, micro jet, high-speed impeller, sand milling (SandGrinder), flow jet mixing (Flow Jet Mixer), high-pressure wet atomization, ultrasonic dispersion etc. can be cited. And, preferably, in the pulverization of pigment under sand milling (bead milling), it is processed under the following conditions, and the condition is to improve the pulverization efficiency by using microbeads with small diameter and improving the filling rate of microbeads etc. And, preferably, after pulverization treatment, coarse particles are removed by filtration, centrifugation etc. In addition, regarding the pigment dispersion process and the disperser, it is preferred to use the process and the disperser described in paragraph 0022 of "Dispersion Technology Collection, JOHOKIKOCO., 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, equipment, and processing conditions 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 thereof 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.

[0421] When preparing a curable composition, it is preferred to filter the curable 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.

[0422] (cured product and film)

[0423] The cured product according to the present invention is a cured product obtained by curing the curable composition according to the present invention.

[0424] The film involved in the present invention is a film obtained by the curable composition involved in the present invention, preferably a film formed by curing the curable composition involved in the present invention. The film involved in the present invention can be used for color filters, infrared transmission filters and other filters. Specifically, it can be preferably used as a colored pixel of a color filter. As a colored pixel, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be cited, preferably green pixels, blue pixels, and more preferably green pixels.

[0425] The film thickness of the film involved in the present invention can be appropriately adjusted according to the purpose, and is preferably 0.1 μm to 20 μm. The upper limit of the film thickness is more preferably 10 μm or less, more preferably 5 μm or less, particularly preferably 3 μm or less, and most preferably 1.5 μm or less. The lower limit of the film thickness is more preferably 0.2 μm or more, and more preferably 0.3 μm or more.

[0426] (Method for producing cured product and method for producing film)

[0427] The method for producing the cured product and the method for producing the film according to the present invention are not particularly limited, but preferably include a step of irradiating the curable composition according to the present invention with light having a wavelength of 150 nm to 300 nm.

[0428] 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).

[0429] Furthermore, the light having a wavelength of 150 nm to 300 nm is preferably an excimer laser.

[0430] The shape of the obtained cured product is not particularly limited, but is preferably a film shape.

[0431] The film of the present invention can be manufactured by applying the curable composition of the present invention on a support. Preferably, the method for manufacturing the film further includes a step of forming a pattern (pixel). As a method for forming the pattern (pixel), photolithography and dry etching can be cited, preferably photolithography.

[0432] The pattern formation based on the photolithography method preferably includes a step of forming a curable composition layer on a support using the curable composition involved in the present invention, a step of exposing the curable composition layer in a pattern, and a step of developing and removing the unexposed portion of the curable composition layer to form a pattern (pixel). A step of baking the curable composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) may also be provided as needed.

[0433] In the process of forming a curable composition layer, a curable composition layer is formed on a support using the curable composition of the present invention. 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 curable 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, the surface contact angle of the base layer is preferably 30° to 80°.

[0434] As a method for applying the curable 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.

[0435] The curable composition layer formed on the support can be dried (prebaked). When the film is manufactured by a low temperature process, prebaking may not be performed. In the case of prebaking, 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.

[0436] Next, the curable composition layer is exposed in a pattern (exposure step). For example, a stepper, a scanner, or the like is used to expose the curable composition layer through a mask having a predetermined mask pattern, thereby exposing the curable composition layer in a pattern. Thus, the exposed portion can be cured.

[0437] 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.

[0438] 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.

[0439] 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.

[0440] Next, the unexposed portion of the curable composition layer is removed by development to form a pattern (pixel). The unexposed portion of the curable composition layer can be removed by development using a developer. As a result, the unexposed portion of the curable 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.

[0441] 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.

[0442] 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 complete curing. 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 batch 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. In the case of 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.

[0443] When patterning is performed by dry etching, the method described in paragraph 0216 of International Publication No. 2022 / 085485 can also be used.

[0444] (Optical Components)

[0445] The optical element according to the present invention includes the film according to the present invention.

[0446] Examples of the optical element include optical filters, lenses, prisms, reflecting mirrors, and diffraction gratings. Among these, optical filters are preferred.

[0447] 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.

[0448] 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.

[0449] 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.

[0450] Each pixel included in the filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably less than 100 nm, more preferably less than 40 nm, and further preferably less than 15 nm. There is no regulation on the lower limit, but for example, it is preferably greater than 0.1 nm. 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 appropriate 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, the volume resistance value of the pixel is preferably 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 is not specified, but is preferably 10 14 For example, the volume resistance value of a pixel can be measured using an ultra high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

[0451] 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 oxidation resistance, 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 molded resin with an adhesive material, etc. can be cited. As the component constituting the protective layer, there can be mentioned (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, polyamideimide resin, polyolefin resin, cycloolefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aromatic polyamide resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, M o , SiO2, Si2N4, etc., and may contain two or more of these components. For example, in the case of a protective layer for the purpose of blocking oxygen, it is preferred that the protective layer contains a polyol resin, SiO2 and Si2N4. And, in the case of a protective layer for the purpose of low reflection, it is preferred that the protective layer contains a (meth) acrylic resin and a fluororesin.

[0452] The protective layer may contain organic / inorganic particles, absorbents of light of specific wavelengths (e.g., ultraviolet rays, near infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants and other additives as needed. As examples of organic / 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, etc. can be cited. The absorbent of light of specific wavelengths can use known absorbents. 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.

[0453] 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.

[0454] The optical filter may have a structure in which pixels are embedded in spaces partitioned into a grid shape by partition walls, for example.

[0455] (Image Sensor)

[0456] The image sensor according to the present invention includes the film according to the present invention.

[0457] Examples of the image sensor include solid-state imaging elements, X-ray imaging elements, and organic thin-film imaging elements. Among them, the image sensor can be preferably used in solid-state imaging elements.

[0458] 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.

[0459] 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 on the lower side of the color filter (the side close to the substrate) or a structure having a focusing mechanism on the color filter, etc.

[0460] Furthermore, the color filter may also have a structure in which each colored pixel is embedded in a space separated by a partition wall, for example, in a grid shape. Preferably, the refractive index of the partition wall in this case is lower than that of each colored pixel. As an example of an imaging device having such a structure, the 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 may 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 and an electronic device with a camera function (such as a mobile phone), the imaging device having the solid-state imaging element involved in the present invention can also be used as a vehicle camera or a surveillance camera.

[0461] (Image display device)

[0462] 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 or 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)" and the like. 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 recorded in the above-mentioned "Next Generation Liquid Crystal Display Technology".

[0463] (Radical polymerization initiator represented by formula (1))

[0464] The radical polymerization initiator according to the present invention is a radical polymerization initiator represented by the following formula (1).

[0465] 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.

[0466] [Chemical formula 29]

[0467]

[0468] In formula (1), Ar1 represents an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, an aromatic group having an arylthio group having 6 to 18 carbon atoms, an aromatic group having a mono- or di-arylamino group having 6 to 18 carbon atoms, or an aromatic group having a monoalkyl or monoarylamino group having 7 to 18 carbon atoms, Ar2 represents a divalent aromatic group, a divalent heteroaromatic group, or a divalent group formed by bonding two or more of these groups, L1 represents a carbonyl group, a sulfonyloxy group, or a sulfonyl group, R1 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryl group, or a heteroaryloxy group, and R 15 ~R 19 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group or an aryloxy group, and two or more R 15 ~R 19 They may be linked to each other to form a ring structure, and the formed ring structure may be an aromatic ring. Y1 represents a hydrogen atom, an alkyl group or an aryl group, and n represents 0 or 1.

[0469] 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 curable composition.

[0470] Example

[0471] Hereinafter, the present invention will be described in more detail by giving examples. The materials, usage amounts, ratios, processing contents, processing sequences, 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. In addition, in the present examples, "%", "parts" represent "mass %", "mass parts" respectively, unless otherwise specified.

[0472] The radical polymerization initiators A-1 to A-193 used in the examples are the same compounds as the radical polymerization initiators A-1 to A-193 described above as specific examples of the radical polymerization initiator represented by the formula (1).

[0473] <Synthesis Example 1: Synthesis of Radical Polymerization Initiator A-1>

[0474] <<Synthesis of Intermediate A-1a>>

[0475] [Chemical formula 30]

[0476]

[0477] Add 21.6 g of anisole and 100 mL of chlorobenzene to a three-necked flask and cool to 0°C. Add 28.9 g of aluminum chloride and dropwise add 31.6 g of p-fluorobenzoyl chloride. Stir at room temperature (25°C, the same below) for 2 hours and add to ice water. Filter the precipitated solid and wash with methanol to obtain 43.7 g of intermediate A-1a.

[0478] [Chemical formula 31]

[0479]

[0480] <<Synthesis of Intermediate A-1b>>

[0481] 23.0 g of intermediate A-1a and 15.9 g of 1H-3-acetylindole were added to a three-necked flask and dissolved in 200 mL of dimethylformamide. 16.6 g of potassium carbonate was added, and the mixture was heated and stirred at 150° C. for 6 hours. The obtained reaction solution was added to water, and the obtained solid was filtered out. It was recrystallized with isopropanol to obtain 29.5 g of intermediate A-1b.

[0482] <<Synthesis of Radical Polymerization Initiator A-1>>

[0483] 18.4 g of intermediate A-1b was added to a three-necked flask and dissolved in 150 mL of tetrahydrofuran. 6.9 g of hydroxylamine hydrochloride, 8.2 g of sodium acetate and 50 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. 5.5 g of pyridine was added, and 4.7 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 12.5 g of free radical polymerization initiator A-1.

[0484] 1 HNMR (400MHz) δ = 2.20 (s, 3H), 2.51 (s, 3H), 3.81 (s, 3H), 7.01 (d, 2H), 7.35 (t, 2H), 7.1-8.0 (m, 9H)

[0485] <Synthesis Example 2: Synthesis of Radical Polymerization Initiator A-94>

[0486] In the synthesis of the free radical polymerization initiator A-1, a free radical polymerization initiator A-94 was obtained by the same method as the synthesis of the free radical polymerization initiator A-1, except that anisole was changed to 1-isopropoxynaphthalene and 1H-3-acetylindole was changed to 1H-3-(3-cyclopentan-1-one)indole.

[0487] 1 HNMR (400MHz) δ = 1.1-1.2 (m, 2H), 1.5-1.8 (m, 6H), 1.8-2.0 (m, 3H), 1.98 (d, 6H) 2.43 (s, 3H), 2.86 (dd, 2H), 4.11 (m, 1H), 6.89 (d, 1H), 7.34 (m, 2H), 7.60 (m, 5H), 7.68 (d, 1H), 7.70 (s, 1H), 8.09 (d, 2H), 8.40 (t, 2H), 8.48 (m, 1H)

[0488] <Synthesis Example 3: Synthesis of Radical Polymerization Initiator A-139>

[0489] <<Synthesis of Intermediate A-139b>

[0490] [Chemical formula 32]

[0491]

[0492] Intermediate A-139b was obtained by the same method as that for the synthesis of Intermediate A-1a, except that anisole was replaced by isopropoxybenzene in Intermediate A-1a and 1H-3-acetylindole was replaced by 1H-3-octanoylindole in Intermediate A-1b.

[0493] <<Synthesis of Radical Polymerization Initiator A-139>>

[0494] 12.1 g of intermediate A-139b was added to a three-necked flask and dissolved in 100 mL of tetrahydrofuran. 1.6 g of sodium methoxide was added and cooled at 0°C. 3.5 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 over sodium sulfate and concentrated. Next, the concentrate was dissolved in 150 mL of tetrahydrofuran and cooled to 0°C in a three-necked flask under a nitrogen atmosphere. 2.4 g of pyridine was added and 2.9 g of acetyl chloride was added dropwise. Stirred at room temperature for 2 hours, 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 7.3 g of free radical polymerization initiator A-139.

[0495] 1HNMR (400MHz) δ = 0.89 (t, 3H), 1.2-1.5 (m, 6H), 1.62 (m, 2H), 2.28 (s, 3H), 2.84 (dd, 2H), 7.01 (d, 2H), 7.35 (t, 2H), 7.1-8.0 (m, 9H)

[0496] <Synthesis Example 4: Synthesis Method of Radical Polymerization Initiators Other Than Above>

[0497] Radical polymerization initiators A-2 to A-93, A-95 to A-138, and A-140 to A-193 were obtained by a method similar to any one of Synthesis Examples 1 to 3 except that the raw materials and the like were changed.

[0498] <Production of Dispersion Liquid>

[0499] 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 raw materials 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.

[0500] [Table 6]

[0501]

[0502] Details of the materials represented by the abbreviations in Table 6 showing the formulation of the above dispersion are as follows.

[0503] <Colorant>

[0504] PR264: CI Pigment Red 264 [diketopyrrolopyrrole compound, red pigment (R pigment)]

[0505] PR254: CI Pigment Red 254 [diketopyrrolopyrrole compound, red pigment (R pigment)]

[0506] PR291: CI Pigment Red 291 [brominated diketopyrrolopyrrole compound, red pigment (R pigment)]

[0507] P071: CI Pigment Orange 71 [diketopyrrolopyrrole compound, orange pigment (0 pigment)]

[0508] PG36: CI Pigment Green 36 [Copper Phthalocyanine Complex, Green Pigment (G Pigment)]

[0509] PG58: CI Pigment Green 58 [zinc phthalocyanine complex, green pigment (G pigment)]

[0510] PY129: CI Pigment Yellow 129 [azomethine copper complex, yellow pigment (Y pigment)]

[0511] PY139: CI Pigment Yellow 139 [isoindoline compound, yellow pigment (Y pigment)]

[0512] PY185: CI Pigment Yellow 185 [isoindoline compound, yellow pigment (Y pigment)]

[0513] PY215: CI Pigment Yellow 215 [pteridine compound, yellow pigment (Y pigment)]

[0514] PB16: CI Pigment Blue 16 [metal-free phthalocyanine compound, blue pigment (B pigment)]

[0515] PB15:6:CI Pigment Blue 15:6 [Copper phthalocyanine complex, blue pigment (B pigment)]

[0516] 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.)

[0517] [Chemical formula 33]

[0518]

[0519] TiBk: Titanium Black [Black Pigment (Bk Pigment)]

[0520] Zr oxynitride: Zirconium oxynitride [black pigment (Bk pigment)]

[0521] <Pigment derivatives>

[0522] S-1~S-4: The following compounds

[0523] [Chemical formula 34]

[0524]

[0525] <Dispersant>

[0526] P-1: A 30% by mass propylene glycol monomethyl ether acrylate (PGMEA) solution of a resin having the following structure: The numerical values ​​indicated on the main chain are molar ratios, and the numerical values ​​indicated on the side chains are the number of repeating units. Mw: 20,000.

[0527] [Chemical formula 35]

[0528]

[0529] P-2: 30 mass % PGMEA solution of the resin of the following structure. The values ​​attached to the main chain are molar ratios, and the values ​​attached to the side chains are the number of repeating units. Mw: 28,000. In the formula, r=15, s=63, t=5, u=17, n=9.

[0530] [Chemical formula 36]

[0531]

[0532] P-3: 30 mass % PGMEA solution of the resin with the following structure. The numerical values ​​indicated on the main chain are molar ratios, and the numerical values ​​indicated on the side chains are the number of repeating units. Mw: 21,000.

[0533] [Chemical formula 37]

[0534]

[0535] P-4: 30 mass% PGMEA solution of the resin of the following structure. The numerical value attached to the side chain is the number of repeating units. Mw: 9,000.

[0536] [Chemical formula 38]

[0537]

[0538] P-5: 30 mass% PGMEA solution of the resin of the following structure. The numerical value attached to the side chain is the number of repeating units. Mw: 10,000.

[0539] [Chemical formula 39]

[0540]

[0541] <Solvent>

[0542] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0543] S-2: Propylene glycol monomethyl ether (PGME)

[0544] S-3: Cyclohexanone

[0545] <Manufacturing of Curable Composition>

[0546] 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 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 (TINUVIN 326, manufactured by BASF), 1 part by mass of a surfactant 1 shown below, and 0.1 part by mass of a polymerization inhibitor (p-methoxyphenol) were mixed to prepare curable compositions of Examples and Comparative Examples.

[0547] Surfactant 1: 1 mass % PGMEA solution of KF-6001 (dual-end carbinol-modified polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0548] [Table 7]

[0549]

[0550] [Table 8]

[0551]

[0552] [Table 9]

[0553]

[0554] [Table 10]

[0555]

[0556] [Table 11]

[0557]

[0558] Details of materials represented by abbreviations in Tables 7 to 11 showing the formulations of the curable compositions other than those described above are as follows.

[0559] <Resin>

[0560] Ba-1: Resin having the following structure (the numerical values ​​attached to the main chain are molar ratios. The weight average molecular weight is 11,000)

[0561] [Chemical formula 40]

[0562]

[0563] Ba-2: Resin having the following structure (the values ​​attached to the main chain are molar ratios. The weight average molecular weight is 15,000)

[0564] [Chemical formula 41]

[0565]

[0566] Ba-3: Resin having the following structure (the numerical values ​​attached to the main chain are molar ratios. The total value of x, y and z is 50. Mw = 15,000)

[0567] [Chemical formula 42]

[0568]

[0569] <Radical polymerizable compound>

[0570] D-1: KAYARAD DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

[0571] D-2: NK ESTER A-DPH-12E (ethylene oxide (EO) modified hexafunctional acrylate compound, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)

[0572] D-3: NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)

[0573] D-4: ARONIX M-510 (3-4 functional acrylate compound, manufactured by TOAGOSEI CO., LTD.)

[0574] D-5: LIGHT ACRYLATE DCP-A (bifunctional alicyclic acrylate compound, manufactured by KYOEISHA CHEMICAL Co., LTD.)

[0575] <Other radical polymerization initiators used simultaneously>

[0576] a-1: Compound with the following structure

[0577] [Chemical formula 43]

[0578]

[0579] a-2: Compound with the following structure

[0580] [Chemical formula 44]

[0581]

[0582] a-3: Compound with the following structure

[0583] [Chemical formula 45]

[0584]

[0585] a-4: Compound with the following structure

[0586] [Chemical formula 46]

[0587]

[0588] a-5: Api-307, aminoacetophenone polymerization initiator manufactured by YOUWEI

[0589] a-6: Compound with the following structure

[0590] [Chemical formula 47]

[0591]

[0592] <Comparative Radical Polymerization Initiator>

[0593] CA-1: The following compound

[0594] CA-2: The following compound

[0595] [Chemical formula 48]

[0596]

[0597] <Chain transfer agent>

[0598] F-1: Karenz MT PE1, a tetrafunctional thiol compound manufactured by SHOWA DENKO KK

[0599] F-2: Karenz MT BD1, a bifunctional thiol compound manufactured by SHOWA DENKO KK

[0600] F-3: A compound of the following structure (4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoic acid), manufactured by FUJIFILM Wako Pure Chemical Corporation

[0601] [Chemical formula 49]

[0602]

[0603] <Evaluation>

[0604] <<Sensitivity>>

[0605] Each curable composition was applied onto a silicon wafer using a spin coater, and then heated (prebaked) at 100° C. for 120 seconds using a hot plate to obtain a coating film having a film thickness of 1.0 μm.

[0606] Next, an i-ray stepper exposure apparatus FPA-3000iS+ (manufactured by Canon Inc.) was used to expose the film at a rate of 10 mJ / cm 2 The variable was irradiated with 50~1000mJ / cm 2 The exposure amount in the range of (exposure process). Then, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for 60 seconds of spin immersion development at 23°C, and then it was rinsed with pure water by 20 seconds of spin spraying, and further washed with pure water. After that, water droplets attached to the pattern surface were removed by blowing air, and the pattern was naturally dried to obtain a pattern.

[0607] Regarding the evaluation of sensitivity, the minimum exposure amount (optimal exposure amount) when the film thickness of the area irradiated with light in the above-mentioned exposure process after development is 95% or more relative to the film thickness before exposure 100% is measured, and this is used as the sensitivity for evaluation. The smaller the value of the above-mentioned minimum exposure amount (optimal exposure amount), the higher the sensitivity.

[0608] -Evaluation Criteria-

[0609] A: less than 10mJ / cm 2

[0610] B: 10mJ / cm 2 Above and less than 20mJ / cm 2

[0611] C: 20mJ / cm 2 Above and less than 50mJ / cm 2

[0612] D: 50mJ / cm 2 Above and less than 100mJ / cm 2

[0613] E: 100mJ / cm 2 above

[0614] <<Adhesion>>

[0615] Each curable composition was applied onto a silicon wafer using a spin coater, and then heated (prebaked) at 100° C. for 120 seconds using a hot plate to obtain a coating film having a film thickness of 1.0 μm.

[0616] Next, an i-ray stepper exposure apparatus FPA-3000iS+ (manufactured by Canon Inc.) was used to expose the film at 400 mJ / cm through a mask having a 0.8 μm checkered pattern. 2 The pattern was then exposed to an exposure dose of . Next, a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used for 60 seconds of spin immersion development at 23°C, and then rinsed with pure water by a 20-second spin spray, and further washed with pure water. After that, water droplets attached to the pattern surface were removed by blowing air, and the pattern was naturally dried to obtain a pattern.

[0617] The silicon wafer on which the pattern was formed was observed using a SEM (Scanning Flectron Microscope, magnification: 20,000 times), and the adhesion was evaluated by observing the ratio of frames in which the pattern was defective among 100 frames of the SEM photograph. The evaluation criteria were as follows.

[0618] -Evaluation Criteria-

[0619] A: The rate of pattern defect is 0%

[0620] B: The ratio of pattern defects is more than 0% and less than 10%

[0621] C: The ratio of pattern defects is more than 10% and less than 20%

[0622] D: The ratio of pattern defects is more than 20% and less than 50%

[0623] E: The ratio of pattern defects exceeds 50%

[0624] <<Undercut>>

[0625] 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 Flectron 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.

[0626] -Evaluation Criteria-

[0627] A: The angle is more than 80 degrees and less than 90 degrees

[0628] B: Angle more than 90 degrees and less than 100 degrees

[0629] C: Angle more than 100 degrees and less than 110 degrees

[0630] D: Angle more than 110 degrees and less than 150 degrees

[0631] E: Angle exceeds 150 degrees

[0632] <<Coating film uniformity>>

[0633] On a silicon wafer, each curable composition was applied using a spin coater, and then, using a hot plate, it was heated at 100°C for 120 seconds (pre-baking) to obtain a coating film with a film 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 uneven stripes of the coating film on one screen was observed and evaluated. The evaluation criteria are as follows. The fewer the uneven stripes, the better the uniformity of the coating film.

[0634] -Evaluation Criteria-

[0635] A: No streaking was observed

[0636] B: Uneven streaking exceeds 0% and is less than 1%

[0637] C: Stripe unevenness is 1% or more and less than 2%

[0638] D: Stripe unevenness is 2% or more and less than 5%

[0639] E: Stripe unevenness is more than 5%

[0640] The evaluation results are summarized in Tables 12 to 14.

[0641] [Table 12]

[0642]

[0643] [Table 13]

[0644]

[0645] [Table 14]

[0646]

[0647] As shown in Tables 12 to 14, the curable compositions of Examples were superior in sensitivity to the curable compositions of Comparative Examples.

[0648] Furthermore, as shown in Tables 12 to 14, the curable compositions of Examples were also excellent in adhesion, undercut suppression, and coating film uniformity.

[0649] The curable compositions of each embodiment can obtain the same effect even if irradiated with KrF rays instead of i-rays. The conditions for KrF irradiation can be set, for example, as follows: exposure light: KrF rays (wavelength 248 nm), exposure amount: 10 mJ / cm 2 ~500mJ / cm 2 , Maximum instantaneous illumination: 250,000,000W / m 2 (Average illumination: 30,000W / m 2 ), pulse width: 30 nanoseconds, frequency: 4kHz.

[0650] 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 193 was changed to 0.2 μm or 2.0 μm, the same evaluation results as those described above were obtained.

[0651] (Example 301: Fabrication of Solid-State Imaging Element)

[0652] The curable 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 curable composition of Example 1 on the silicon wafer was formed. Similarly, the curable composition of Example 6 (green) and the curable composition of Example 11 (blue) were patterned in sequence to form red, green and blue coloring patterns (Bayer patterns).

[0653] 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.

[0654] The obtained color filter was assembled into a solid-state imaging element according to a known method. It was confirmed that when any curable composition 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.

[0655] In addition, regarding the invention of Japanese Patent Application No. 2022-102997 filed on June 27, 2022, the entirety of the invention is incorporated into this specification by reference. Furthermore, all documents, patent applications, and technical specifications described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical specification were specifically and individually cited.

Claims

1. A curable composition comprising: A radical polymerization initiator represented by formula (1); and Free radical polymerizable compounds, In formula (1), Ar1 represents an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, an aromatic group having an arylthio group having 6 to 18 carbon atoms, an aromatic group having a mono- or di-arylamino group having 6 to 18 carbon atoms, or an aromatic group having a monoalkyl or monoarylamino group having 7 to 18 carbon atoms, Ar2 represents a divalent aromatic group, a divalent heteroaromatic group, or a divalent group formed by bonding two or more of these groups, L1 represents a carbonyl group, a sulfonyloxy group, or a sulfonyl group, R1 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryl group, or a heteroaryloxy group, and R 15 ~R 19 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group or an aryloxy group, and two or more R 15 ~R 19 They are optionally linked to each other to form a ring structure, and the formed ring structure is optionally an aromatic ring. Y1 represents a hydrogen atom, an alkyl group or an aryl group, and n represents 0 or 1.

2. The curable composition according to claim 1, wherein The Y1 is a group represented by the following formula (2), 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 a link to the oxime group.

3. The curable composition according to claim 1 or 2, 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.

4. The curable composition according to claim 1 or 2, wherein The Ar1 is an aromatic group having an alkoxy group having 1 to 12 carbon atoms or an aromatic group having an alkylthio group having 1 to 12 carbon atoms.

5. The curable composition according to claim 1 or 2, wherein The n is 0. The curable composition according to claim 1 or 2, further comprising a colorant.

7. The curable composition according to claim 6, wherein The content of the colorant is 60% by mass or more based on the total solid content of the composition.

8. The curable composition according to claim 1 or 2, further comprising a resin.

9. The curable composition according to claim 8, 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 a polyether chain, a polyester chain, and a polyacrylic acid chain, and the weight average molecular weight of the graft chain is 1000 or more.

10. The curable composition according to claim 8, wherein The resin includes a resin having a (meth)acryloyl group, an epoxy group or an oxetane group. 11 . The curable composition according to claim 1 or 2 , further comprising a pigment derivative. 12 . The curable composition according to claim 1 , further comprising a chain transfer agent. 13 . The curable composition according to claim 1 , which is used for excimer laser exposure with a wavelength of 150 nm to 300 nm.

14. A method for producing a solidified product, comprising: A step of irradiating the curable composition according to claim 1 or 2 with an excimer laser having a wavelength of 150 nm to 300 nm.

15. A film formed by curing the curable composition according to claim 1 or 2.

16. An optical element comprising the film according to claim 15.

17. An image sensor comprising the film according to claim 15. 18 . A solid-state imaging element comprising the film according to claim 15 .

19. An image display device comprising the film according to claim 15.

20. A free radical polymerization initiator represented by formula (1), In formula (1), Ar1 represents an aromatic group having an alkoxy group having 1 to 12 carbon atoms, an aromatic group having an alkylthio group having 1 to 12 carbon atoms, an aromatic group having a mono- or di-alkylamino group having 1 to 12 carbon atoms, an aromatic group having an aryloxy group having 6 to 18 carbon atoms, an aromatic group having an arylthio group having 6 to 18 carbon atoms, an aromatic group having a mono- or di-arylamino group having 6 to 18 carbon atoms, or an aromatic group having a monoalkyl or monoarylamino group having 7 to 18 carbon atoms, Ar2 represents a divalent aromatic group, a divalent heteroaromatic group, or a divalent group formed by bonding two or more of these groups, L1 represents a carbonyl group, a sulfonyloxy group, or a sulfonyl group, R1 represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryl group, or a heteroaryloxy group, and R 15 ~R 19 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, an alkoxy group or an aryloxy group, and two or more R 15 ~R 19 They are optionally linked to each other to form a ring structure, and the formed ring structure may be an aromatic ring. Y1 represents a hydrogen atom, an alkyl group or an aryl group, and n represents 0 or 1.

Images