Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/20—Oxygen atoms
  • C07D215/22—Oxygen atoms attached in position 2 or 4
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
  • C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
  • C07D295/116—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings with the doubly bound oxygen or sulfur atoms directly attached to a carbocyclic ring
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
  • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
  • C07D307/80—Radicals substituted by oxygen atoms
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/92—Naphthofurans; Hydrogenated naphthofurans
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
  • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
  • C07D313/02—Seven-membered rings
  • C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
  • C07D313/08—Seven-membered rings condensed with carbocyclic rings or ring systems condensed with one six-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
  • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D335/08—Naphthothiopyrans; Hydrogenated naphthothiopyrans
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/04—Ortho-condensed systems
  • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/04—Ortho-condensed systems
  • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
  • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
  • C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters

Definitions

• the present disclosure relates to a curable composition, a method for producing a cured product, a film, an optical element, an image sensor, a solid-state imaging device, an image display device, and a radical polymerization initiator.
• Optical filters such as color filters are manufactured using a curable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound.
• a curable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound.
• compositions described in Patent Documents 1 and 2 are known.
• Patent Document 1 describes a polymerizable composition containing a specific ⁇ -aminoketone compound having a carbazole structure.
• Patent Document 2 describes an active energy ray-curable ink containing a specific ⁇ -aminoketone compound having a specific fluorene structure.
• the problem to be solved by the embodiments of the present disclosure is to provide a curable composition that generates less outgassing from the obtained cured product. Further, the problem to be solved by another embodiment of the present disclosure is a method for producing a cured product of the curable composition, or a film, optical element, image sensor, solid-state imaging using the curable composition. It is to provide a device or an image display device. Furthermore, another problem to be solved by another embodiment of the present disclosure is to provide a novel radical polymerization initiator.
• Means for solving the above problems include the following aspects. ⁇ 1> A curable composition containing a radical polymerization initiator represented by the following formula 1 and a radically polymerizable compound.
• Ar 1 represents an aromatic ring or heteroaromatic ring
• X 1 represents -OR 11 or -NR 12 R 13
• Y 1 represents a divalent linking group
• R a is a hydrogen atom or a substituent.
• R 11 to R 13 each independently represent a hydrogen atom or a substituent.
• Ar 2 represents an aromatic ring or heteroaromatic ring
• X 2 represents -OR 24 or -NR 25 R 26
• Y 2 represents a single bond or a divalent linking group
• R 21 to R 26 each independently represents a hydrogen atom or a substituent
• R 25 and R 26 may combine to form a ring
• n represents an integer of 1-3.
• X 3 represents -OR 34 or -NR 35 R 36
• Y 3 represents a single bond, -O- or -S-
• R 31 represents an alkyl group or an aryl group
• R 32 to R 36 each independently represent a hydrogen atom, an alkyl group or an aryl group
• R 35 and R 36 may be linked to form a ring
• n represents an integer of 1 to 3
• R 39 each independently represents a substituent
• m represents an integer of 0-2.
• X 4 represents —OR 44 or —NR 45 R 46
• Y 4 represents a single bond, —O— or —S—
• R 41 represents an alkyl group or an aryl group
• R 42 to R 46 each independently represents a hydrogen atom, an alkyl group or an aryl group
• R 45 and R 46 may be linked to form a ring
• n represents an integer of 1 to 3
• L 1 and L 2 each independently represents a single bond, —CR 47 R 48 —, —O—, —S— or —NR 49 —
• each of R 47 to R 49 independently represents a hydrogen atom, an alkyl group or an aryl group
• p represents 0 or 1
• q represents an integer of 0 to 2
• ⁇ 5> The curable composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a colorant.
• ⁇ 6> The curable composition according to any one of ⁇ 1> to ⁇ 5>, further comprising an oxime compound.
• ⁇ 7> The molar absorption coefficient of the radical polymerization initiator represented by the above formula 1 for light with a wavelength of 248 nm at 25 ° C. in an acetonitrile solution is 1,000 L mol -1 cm -1 or more, ⁇ 1 > The curable composition according to any one of ⁇ 6>.
• ⁇ 8> A method for producing a cured product, comprising the step of irradiating the curable composition according to any one of ⁇ 1> to ⁇ 7> with light having a wavelength of 150 nm to 300 nm.
• ⁇ 9> A film obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 7>.
• An optical element comprising the film according to ⁇ 9>.
• An image sensor comprising the film according to ⁇ 9>.
• ⁇ 12> A solid-state imaging device having the film according to ⁇ 9>.
• An image display device comprising the film according to ⁇ 9>.
• ⁇ 14> A radical polymerization initiator represented by the following formula 1.
• Ar 1 represents an aromatic ring or heteroaromatic ring
• X 1 represents -OR 11 or -NR 12 R 13
• Y 1 represents a divalent linking group
• R a is a hydrogen atom or a substituent.
• R 11 to R 13 each independently represent a hydrogen atom or a substituent.
• Ar 2 represents an aromatic ring or heteroaromatic ring
• X 2 represents -OR 24 or -NR 25 R 26
• Y 2 represents a single bond or a divalent linking group
• R 21 to R 26 each independently represents a hydrogen atom or a substituent
• R 25 and R 26 may combine to form a ring
• n represents an integer of 1-3.
• X 3 represents -OR 34 or -NR 35 R 36
• Y 3 represents a single bond, -O- or -S-
• R 31 represents an alkyl group or an aryl group
• R 32 to R 36 each independently represent a hydrogen atom, an alkyl group or an aryl group
• R 35 and R 36 may be linked to form a ring
• n represents an integer of 1 to 3
• R 39 each independently represents a substituent
• m represents an integer of 0-2.
• X 4 represents —OR 44 or —NR 45 R 46
• Y 4 represents a single bond, —O— or —S—
• R 41 represents an alkyl group or an aryl group
• R 42 to R 46 each independently represents a hydrogen atom, an alkyl group or an aryl group
• R 45 and R 46 may be linked to form a ring
• n represents an integer of 1 to 3
• L 1 and L 2 each independently represents a single bond, —CR 47 R 48 —, —O—, —S— or —NR 49 —
• each of R 47 to R 49 independently represents a hydrogen atom, an alkyl group or an aryl group
• p represents 0 or 1
• q represents an integer of 0 to 2
• a curable composition that generates less outgassing from the obtained cured product.
• a method for producing a cured product of the curable composition, or a film, an optical element, an image sensor, a solid-state imaging device, or an image display using the curable composition An apparatus is provided.
• novel radical polymerization initiators are provided.
• ⁇ is used to include the numerical values before and after it as lower and upper limits.
• a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
• Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
• (meth)acrylate represents both or either acrylate and methacrylate
• (meth)acryl represents both or either acrylic and methacrylic
• (meth) ) acryloyl refers to either or both acryloyl and methacryloyl.
• Me in the structural formulas represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
• total solid content refers to the total mass of all components of the composition excluding the solvent.
• a pigment means a coloring agent that is difficult to dissolve in a solvent.
• the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. . The present disclosure will now be described in detail.
• the curable composition according to the present disclosure contains a radical polymerization initiator represented by Formula 1 below and a radically polymerizable compound.
• Ar 1 represents an aromatic ring or heteroaromatic ring
• X 1 represents -OR 11 or -NR 12 R 13
• Y 1 represents a divalent linking group
• R a is a hydrogen atom or a substituent.
• R 11 to R 13 each independently represent a hydrogen atom or a substituent.
• the radical polymerization initiator represented by the above formula 1 has a cyclic ketone structure and an oxygen atom or a nitrogen atom at the ⁇ -position of the cyclic ketone structure, the carbon atom of the carbonyl group in the cyclic ketone structure and The bond with the ⁇ -carbon atom to which the oxygen atom or nitrogen atom is bonded is cleaved to generate a radical.
• the radicals generated here are linked to the cyclic ketone structure and are less likely to generate volatile components, so the gas (outgas) discharged after curing from the cured product obtained by curing the curable composition is suppressed. I'm assuming it can.
• the curable composition according to the present disclosure is preferably used as a curable composition for optical filters.
• optical filters include color filters and infrared transmission filters, and color filters are preferred. That is, the curable composition according to the present disclosure is preferably used as a curable composition for color filters. More specifically, it can be preferably used as a curable composition for pixel formation of color filters. Pixel types include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
• 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 wavelength range is 1,100 nm to 1,300 nm.
• a filter that satisfies spectral characteristics such that the minimum transmittance is 70% or more (preferably 75% or more, more preferably 80% or more) is preferred.
• the infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5).
• 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 800 nm to 1,500 nm.
• a filter whose value is 70% or more preferably 75% or more, more preferably 80% or more.
• the maximum transmittance in the wavelength range of 400 nm to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 900 nm to 1,500 nm.
• the maximum transmittance in the wavelength range of 400 nm to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1,000 nm to 1,500 nm. is 70% or more (preferably 75% or more, more preferably 80% or more).
• the maximum transmittance in the wavelength range of 400 nm to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1,100 nm to 1,500 nm. is 70% or more (preferably 75% or more, more preferably 80% or more).
• the maximum value of transmittance in the wavelength range of 400 nm to 1,050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and in the wavelength range of 1,200 nm to 1,500 nm
• the curable composition according to the present disclosure is preferably used for solid-state imaging devices. More specifically, it is preferably used as a curable composition for optical filters used in solid-state imaging devices, and more preferably used as a curable composition for color filters used in solid-state imaging devices.
• the solid content concentration of the curable composition according to the present disclosure is preferably 5% by mass to 30% by mass.
• the lower limit is more preferably 7.5% by mass or more, and even more preferably 10% by mass or more.
• the upper limit is more preferably 25% by mass or less, and even more preferably 20% by mass or less.
• the curable composition according to the present disclosure contains a radical polymerization initiator represented by Formula 1 above.
• the radical polymerization initiator represented by Formula 1 above is preferably a radical photopolymerization initiator, and more preferably a radical photopolymerization initiator that generates radicals upon exposure to light with a wavelength of 150 nm to 300 nm.
• the exposure wavelength at which the radical initiator represented by formula 1 generates radicals is preferably 150 nm to 460 nm, more preferably 150 nm to 420 nm, still more preferably 150 nm to 380 nm, and particularly preferably 150 nm to 300 nm.
• Ar 1 in Formula 1 is preferably an aromatic ring from the viewpoint of suppressing outgassing generated from the obtained cured product (hereinafter also simply referred to as "outgassing suppressing property") and sensitivity, and has a carbazole ring structure.
• a fluorene ring structure a diaryl sulfide structure, a diaryl ether structure, a dibenzothiophene structure, a diarylmethane structure, a triarylmethane structure, a biphenyl structure, or a naphthalene ring structure.
• an aromatic ring having a diarylsulfide structure is more preferred, and an aromatic ring having a carbazole ring structure or a fluorene ring structure is particularly preferred.
• the aromatic ring or heteroaromatic ring in Ar 1 may have a substituent.
• the substituent is not particularly limited, preferably a substituent having 0 to 100 carbon atoms, more preferably a substituent having 0 to 50 carbon atoms.
• substituents examples include halogen atoms, hydroxy groups, amino groups, alkyl groups, cycloalkyl groups, heterocyclic groups, aryl groups, heteroaryl groups, acyl groups, nitro groups, cyano groups, sulfo groups, alkylaminocarbonyl group, alkoxycarbonyl group, alkylthio group, arylthio group, morpholino group, alkoxyalkyl group, carboxy group, carboxyalkyl group and the like.
• substituents may further have a substituent, or the substituents may combine to form a ring structure.
• the aromatic ring or heteroaromatic ring for Ar 1 may form a condensed ring by condensing a ring structure such as an aliphatic ring, a heterocyclic ring, an aromatic ring, or a heteroaromatic ring.
• X 1 in Formula 1 is preferably —NR 12 R 13 from the viewpoint of outgas suppression and sensitivity.
• R 11 in —OR 11 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and an alkyl group, from the viewpoints of outgas suppression and sensitivity. is particularly preferred, most preferably a methyl group.
• R 12 and R 13 in —NR 12 R 13 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group, or a methyl group, from the viewpoints of outgas suppression and sensitivity. It is particularly preferred to have The alkyl group and aryl group for R 11 to R 13 may have a substituent.
• Substituents include the substituents described above.
• R 12 and R 13 in —NR 12 R 13 may combine with each other to form a ring.
• the number of ring members of the above ring is not particularly limited, a 3- to 12-membered ring is preferable, a 3- to 7-membered ring is more preferable, and a 3- to 6-membered ring is particularly preferable.
• —NR 12 R 13 is aziridine, azetidine, thiomorpholine, dioxothiomorpholine, piperazine (whatever comes to mind as a secondary cyclic amine), pyrrolidyl group, piperidyl, from the viewpoint of outgassing suppression and sensitivity.
• —NR 12 R 13 is preferably a dialkylamino group, a pyrrolidyl group, a piperidyl group or a morpholino group, more preferably a dimethylamino group or a morpholino group, from the viewpoint of outgas suppression and sensitivity. preferable.
• the ring containing Y 1 in Formula 1 as a ring member is preferably a 5- to 8-membered ring, more preferably a 5- to 7-membered ring, from the viewpoints of outgas suppression, sensitivity, and solubility.
• a 5- or 6-membered ring is particularly preferable from the viewpoint of sensitivity
• a 7-membered ring is particularly preferable from the viewpoint of solubility.
• Y 1 in Formula 1 is an alkylene group, a group formed by bonding an alkylene group and an ether bond, or a group formed by bonding an alkylene group and a thioether bond, from the viewpoint of outgas suppression property and sensitivity.
• Y 1 has an ether bond or a thioether bond
• -O- or -S- in Y 1 is preferably directly bonded to Ar 1 from the viewpoint of outgas suppression and sensitivity.
• R a in Formula 1 is preferably an alkyl group or an aryl group, more preferably an alkyl group, from the viewpoint of outgassing suppression properties and sensitivity, a methyl group, an ethyl group, a benzyl group, or p - is particularly preferred to be a methylbenzyl group.
• the radical polymerization initiator represented by Formula 1 preferably has an arylcarbonyl group or a heteroarylcarbonyl group, and particularly preferably has a benzoyl group.
• the radical polymerization initiator represented by Formula 1 preferably has a nitro group, and more preferably has a nitro group on the aromatic ring.
• the radical polymerization initiator represented by Formula 1 preferably has a halogen atom, more preferably a chlorine atom or a bromine atom, from the viewpoint of adhesion, and on the aromatic ring It is particularly preferred to have a chlorine atom or a bromine atom.
• the radical polymerization initiator represented by Formula 1 suppresses the loss in the plane direction at the bottom and edge of the exposed portion (hereinafter also simply referred to as "undercut suppressing property".) From the viewpoint, sulfur atom and more preferably a sulfur atom directly attached to the aromatic ring. Preferred embodiments of the radical polymerization initiator represented by Formula 1 also apply to Formulas 2, 3A, 3B, and 4, which will be described later.
• the radical polymerization initiator represented by the above formula 1 is preferably a radical polymerization initiator represented by the following formula 2 from the viewpoint of outgas suppression and sensitivity.
• Ar 2 represents an aromatic ring or heteroaromatic ring
• X 2 represents —OR 24 or —NR 25 R 26
• Y 2 represents a single bond or a divalent linking group
• R 21 to R 26 each independently represents a hydrogen atom or a substituent
• R 25 and R 26 may combine to form a ring
• n represents an integer of 1-3.
• Ar 2 in formula 2 has the same definition as Ar 1 in formula 1, and preferred embodiments are also the same.
• X 2 , —OR 24 and —NR 25 R 26 in Formula 2 have the same meanings as X 1 , —OR 11 and —NR 12 R 13 in Formula 1, respectively, and preferred embodiments are also the same.
• R 21 in formula 2 has the same definition as R a in formula 1, and preferred embodiments are also the same.
• Y 2 in Formula 2 is preferably a single bond, —O— or —S—, more preferably —O— or —S—, from the viewpoint of outgas suppression and sensitivity.
• R 22 and R 23 in Formula 2 are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, from the viewpoint of outgassing suppression and sensitivity, A hydrogen atom is particularly preferred.
• n in Formula 2 is preferably 1 or 2 from the viewpoint of sensitivity.
• the radical polymerization initiator represented by the above formula 1 is more preferably a radical polymerization initiator represented by the following formula 3A or 3B from the viewpoint of outgas suppression and sensitivity, and is represented by the following formula 3A. It is more preferable that the radical polymerization initiator is used.
• X 3 represents -OR 34 or -NR 35 R 36
• Y 3 represents a single bond, -O- or -S-
• R 31 represents an alkyl group or an aryl group
• R 32 to R 36 each independently represent a hydrogen atom, an alkyl group or an aryl group
• R 35 and R 36 may be linked to form a ring
• n represents an integer of 1 to 3
• R 39 each independently represents a substituent
• m represents an integer of 0-2.
• X 3 , —OR 34 and —NR 35 R 36 in Formula 3 have the same meanings as X 1 , —OR 11 and —NR 12 R 13 in Formula 1, respectively, and preferred embodiments are also the same.
• R 31 in formula 3 has the same definition as R a in formula 1, and preferred embodiments are also the same.
• Y 3 , R 32 , R 33 and n in Formula 3 have the same meanings as Y 2 , R 22 , R 23 and n in Formula 2, respectively, and preferred embodiments are also the same.
• m in Formula 3A or Formula 3B is preferably 0 or 1, more preferably 1.
• Substituents for R 39 in Formula 3A or Formula 3B include the substituents described above. Among them, R 39 is preferably a halogen atom, an alkoxy group, an alkylthio group, or an aryl group from the viewpoint of outgas suppression and sensitivity.
• radical polymerization initiator represented by Formula 1 above is particularly preferably a radical polymerization initiator represented by Formula 4 below from the viewpoint of outgas suppression and sensitivity.
• X 4 represents —OR 44 or —NR 45 R 46
• Y 4 represents a single bond, —O— or —S—
• R 41 represents an alkyl group or an aryl group
• R 42 to R 46 each independently represents a hydrogen atom, an alkyl group or an aryl group
• R 45 and R 46 may be linked to form a ring
• n represents an integer of 1 to 3
• L 1 and L 2 each independently represents a single bond, —CR 47 R 48 —, —O—, —S— or —NR 49 —
• each of R 47 to R 49 independently represents a hydrogen atom, an alkyl group or an aryl group
• p represents 0 or 1
• q represents an integer of 0 to 2
• X 4 , —OR 44 and —NR 45 R 46 in Formula 4 have the same meanings as X 1 , —OR 11 and —NR 12 R 13 in Formula 1, respectively, and preferred embodiments are also the same.
• R 41 in formula 4 has the same definition as R a in formula 1, and preferred embodiments are also the same.
• Y 4 , R 42 , R 43 and n in Formula 4 have the same meanings as Y 2 , R 22 , R 23 and n in Formula 2, respectively, and preferred embodiments are also the same.
• L 1 in Formula 4 is preferably a single bond, -S- or -NR 49 -, more preferably -S- or -NR 49 -, from the viewpoint of outgas suppression and sensitivity, -NR 49 - is particularly preferred.
• R 47 to R 49 in Formula 4 are each independently preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and an ethyl group from the viewpoint of outgassing suppression and sensitivity. It is particularly preferred to have
• the alkyl group and aryl group in R 47 to R 49 may have a substituent. Substituents include the substituents described above.
• L 2 in Formula 4 is preferably a single bond or —CR 47 R 48 —, more preferably a single bond, from the viewpoint of outgas suppression and sensitivity.
• one binding position of L 2 in formula 4 is the ortho position of the binding position of Y 4 , that is, the position between Y 4 and L 1 from the viewpoint of outgas suppression and sensitivity. preferable.
• the two bonding positions of L 2 in formula 4 are preferably ortho-positions of the bonding position of L 1 from the viewpoint of outgas suppression and sensitivity.
• p in Formula 4 is preferably 1 from the viewpoint of outgas suppression and sensitivity.
• Z 1 in Formula 4 is preferably a halogen atom, a nitro group, a cyano group, or a benzoyl group from the viewpoint of outgas suppression, sensitivity, and adhesion, and is preferably a chlorine atom, a bromine atom, a nitro group, or a benzoyl A group is more preferable, a chlorine atom, a bromine atom or a nitro group is particularly preferable from the viewpoint of adhesion, and a benzoyl group is particularly preferable from the viewpoint of sensitivity.
• Z 2 in Formula 4 is preferably an aryl group, more preferably a phenyl group.
• the radical polymerization initiator represented by Formula 1 above preferably has absorption at a wavelength of 194 nm, which is the ArF absorption region, at a wavelength of 248 nm, which is the KrF absorption region, or at a wavelength of 365 nm, which is the i-line absorption region.
• the molar extinction coefficient of the radical polymerization initiator represented by the above formula 1 at a wavelength of 194 nm, 248 nm or 365 nm is preferably 10 L mol -1 cm -1 or more, and 100 L mol -1 from the viewpoint of sensitivity. ⁇ cm ⁇ 1 or more is more preferable, and 1,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more is particularly preferable.
• the radical polymerization initiator represented by the above formula 1 has a molar absorption coefficient for light with a wavelength of 248 nm at 25 ° C. in an acetonitrile solution, from the viewpoint of sensitivity and adhesion, 1,000 L mol -1 . cm ⁇ 1 or more is preferable, 2,000 or more is more preferable, and 3,000 or more is particularly preferable.
• the upper limit is not limited, it is preferably 50,000 or less, more preferably 30,000 or less, and particularly preferably 10,000 or less. By setting the upper limit of the molar extinction coefficient to 10,000 or less, the transmittance of the exposure light source is improved, and the adhesion is improved.
• radical polymerization initiator represented by Formula 1 above preferably include A-1 to A-112, but needless to say, the initiator is not limited to these.
• Numerical values in parentheses below represent molar extinction coefficients (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ) for light with a wavelength of 248 nm at 25° C. in an acetonitrile solution.
• radical polymerization initiator represented by the above formula 1 A-6 (23,000), A-15 (21,200), A-22 (28,500), A-32 (32,000 ), A-46 (31,100), A-49 (35,500), A-64 (33,000), A-68 (19,800), A-92 (3,400), A-103 At least one radical polymerization initiator selected from the group consisting of (2,800) and A-109 (8,000) is preferred.
• the curable composition according to the present disclosure may contain one type of radical polymerization initiator represented by Formula 1 above, or may contain two or more types. When two or more types are used, the total amount thereof is preferably within the following range.
• the content of the radical polymerization initiator represented by the above formula 1 is preferably 0.01% by mass to 30% by mass based on the total solid content of the curable composition from the viewpoint of outgassing suppression and simplicity. More preferably 0.05% to 20% by mass, even more preferably 0.1% to 10% by mass, and particularly preferably 1% to 8% by mass.
• the radical polymerization initiator represented by Formula 1 above preferably has no absorption at a wavelength of 450 nm or more, and more preferably has no absorption at a wavelength of 420 nm or more. That is, the radical polymerization initiator represented by Formula 1 above is preferably white to pale yellow. The above colors are preferable because they have little effect on the spectrum of the color filter.
• the structure having absorption at the above wavelengths is preferably a carbazole structure, a diphenyl sulfide structure, a biphenyl structure, or a fluorene structure.
• the method for producing the radical polymerization initiator represented by Formula 1 is not particularly limited, and it may be produced by a known method, or may be produced by referring to a known method.
• the radical polymerization initiator represented by the above formula 1 is an ⁇ -aminoketone compound, it can be synthesized in the same manner as a known linear ⁇ -aminoketone compound. It can be synthesized by the described method.
• the ⁇ -position of the cyclic ketone compound linked to the aromatic group was anionized with sodium methoxide (base), reacted with an alkyl halide (R a -X), monoalkylated, and then halogenated (brominated) at the ⁇ -position.
• a method of reacting a compound with a secondary amine compound (HNR 12 R 13 ) in the presence of sodium methoxide (base) is also suitable. Furthermore, after monohalogenating (brominating) the ⁇ -position of the cyclic ketone compound, it is reacted with a secondary amine compound (HNR 12 R 13 ), and finally an alkyl halide (R a - A method of alkylating by reacting with X) is also suitable.
• radical polymerization initiator represented by formula 1 is an ⁇ -hydroxyketone compound
• a suitable method is to replace the reaction with the secondary amine compound with potassium hydroxide.
• a method for synthesizing a ketone compound serving as a precursor for example, a method for synthesizing a cyclic ketone linked to an aromatic group is disclosed in JP-A-2011-33793, JP-A-2011-209655, JP-A-2011-227295. No. 2012/169812, International Publication No. 2021/023144, and the like.
• Examples of the secondary amine compound to be subjected to the reaction include dimethylamine, diethylamine, dipropylamine, dibutylamine, dimethanolamine, diethanolamine, biperidine, morpholine, thiomorpholine, N-methylpiperazine, N-ethylpiperazine, and N-isopropyl.
• Aliphatic secondary amine compounds such as piperazine, pyrrolidine, dihexylamine, dioctylamine, didecylamine, ethylmethylamine, aziridine, azetidine, pyrrolidine, piperidine, norbornanedimethylamine, 1,3-bis(4-piperidyl)propane
• Alicyclic secondary amine compounds aromatic secondary amine compounds such as benzylmethylamine, diphenylamine and dibenzylamine can be used. Among them, dimethylamine or morpholine is particularly preferred.
• the curable composition according to the present disclosure may contain radical polymerization initiators other than the radical polymerization initiator represented by Formula 1 above.
• Other radical polymerization initiators include oxime compounds, ⁇ -aminoacetophenone compounds, ⁇ -hydroxyketone compounds, acylphosphine compounds and the like. Among them, oxime compounds are preferred.
• oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, J. Am. C. S. compounds described in Perkin II (1979, pp. 1653-1660); C. S. Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No.
• oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime) and the like.
• Photopolymerization initiator 2 described in JP-A-2012-014052 manufactured by ADEKA.
• the oxime compound it is also preferable to use a compound having no coloring property or a compound having high transparency and resistance to discoloration.
• An oxime compound having a fluorene ring can also be used as the oxime compound.
• Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. mentioned.
• an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
• Specific examples of such oxime compounds include compounds described in WO2013/083505.
• An oxime compound having a fluorine atom can also be used as the oxime compound.
• Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
• an oxime compound having a nitro group can be used as the oxime compound.
• the oxime compound having a nitro group is also preferably a dimer.
• Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
• An oxime compound having a benzofuran skeleton can also be used as the oxime compound.
• Specific examples include OE-01 to OE-75 described in WO 2015/036910.
• an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
• Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
• an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
• the electron-withdrawing group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
• a benzoyl group may have a substituent.
• substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
• a sulfanyl group or an amino group is more preferred.
• oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
• the compounds shown below can be particularly preferably exemplified.
• the mass ratio when used in combination with other radical polymerization initiators is not particularly limited. is preferably 10% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• a curable composition according to the present disclosure comprises a radically polymerizable compound.
• the radically polymerizable compound include compounds having an ethylenically unsaturated group.
• resin-type radically polymerizable compounds include resins containing repeating units having radically polymerizable groups.
• 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 even more preferably 500,000 or less.
• the lower limit of the weight average molecular weight is more preferably 3,000 or more, and even more preferably 5,000 or more.
• the molecular weight of the monomer-type radically polymerizable compound (polymerizable monomer) is preferably less than 2,000, more preferably 1,500 or less.
• the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.
• the compound having an ethylenically unsaturated group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
• Specific examples include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2013-253224.
• Examples of compounds having an ethylenically unsaturated group include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available).
• KAYARAD D-320 is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (As a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and the (meth)acryloyl group of these compounds is ethylene glycol and / or Examples thereof include compounds having a structure linked via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer).
• diglycerin EO ethylene oxide modified (meth) acrylate
• pentaerythritol tetraacrylate Shin-Nakamura Chemical Industry NK Ester A-TMMT, manufactured by Nippon Kayaku Co., Ltd.
• 1,6-hexanediol diacrylate KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.
• RP-1040 manufactured by Nippon Kayaku Co., Ltd.
• Aronix TO-2349 manufactured by Toagosei Co., Ltd.
• NK Oligo UA-7200 manufactured by Shin-Nakamura Chemical Co., Ltd.
• 8UH-1006, 8UH-1012 manufactured by Taisei Fine Chemical Co., Ltd.
• Examples of compounds having an ethylenically unsaturated group include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and isocyanuric acid ethylene oxide-modified tri(meth)acrylate. It is also preferable to use trifunctional (meth)acrylate compounds such as (meth)acrylate and pentaerythritol tri(meth)acrylate. Commercial products of trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305.
• M-303, M-452, M-450 manufactured by Toagosei Co., Ltd.
• a compound having an ethylenically unsaturated group may further have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
• an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
• Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
• a compound having a caprolactone structure can also be used as the compound having an ethylenically unsaturated group.
• the description of paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, and the contents thereof are incorporated herein.
• Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as a series from Nippon Kayaku Co., Ltd.
• a compound having an ethylenically unsaturated group and an alkyleneoxy group can also be used as the compound having an ethylenically unsaturated group.
• Such a compound is preferably a compound having an ethylenically unsaturated group and an ethyleneoxy group and/or a propyleneoxy group, more preferably a compound having an ethylenically unsaturated group and an ethyleneoxy group.
• Tri- to hexa-functional (meth)acrylate compounds having 4 to 20 ethyleneoxy groups are preferred, and more preferred.
• Examples of commercially available products include SR494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330 and the like.
• a polymerizable compound having a fluorene skeleton can also be used as the compound having an ethylenically unsaturated group.
• Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
• the compound having an ethylenically unsaturated group it is also preferable to use a compound that does not substantially contain environmental regulation substances such as toluene.
• environmental regulation substances such as toluene.
• Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of compounds having an ethylenically unsaturated group include 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 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.) Co., Ltd.) is also preferably used.
• the content of the radically polymerizable compound is preferably 0.1% by mass to 50% by mass with respect to the total solid content of the curable composition.
• the lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
• the upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less.
• only one type of radically polymerizable compound may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• the curable composition according to the present disclosure preferably contains a colorant.
• Colorants include chromatic colorants and black colorants.
• chromatic coloring agents include coloring agents having a maximum absorption wavelength in the wavelength range of 400 nm to 700 nm. Examples include green colorants, red colorants, yellow colorants, purple colorants, blue colorants, orange colorants, and the like.
• the other coloring agent is preferably a chromatic coloring agent, preferably at least one selected from a yellow coloring agent and a green coloring agent, and more preferably a yellow coloring agent.
• the coloring agent may be a pigment or a dye, but is preferably a pigment.
• the average primary particle size of the pigment is preferably 1 nm to 200 nm.
• the lower limit is more preferably 5 nm or more, and even more preferably 10 nm or more.
• the upper limit is more preferably 180 nm or less, still more preferably 150 nm or less, and particularly preferably 100 nm or less.
• the primary particle diameter of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. 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 diameter of the pigment.
• the average primary particle size in this specification is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment.
• the primary particles of the pigment refer to independent particles without agglomeration.
• green colorants examples include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
• the green colorant is preferably a pigment.
• Specific examples of green colorants include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65 and 66 are included.
• a green colorant a halogenated zinc phthalocyanine having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule. Pigments can also be used. Specific examples include compounds described in International Publication No. 2015/118720.
• the compound described in Chinese Patent Application No. 106909027 the phthalocyanine compound having a phosphoric acid ester as a ligand described in WO 2012/102395, described in JP 2019-008014.
• the phthalocyanine compound, the phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, the aluminum phthalocyanine compound described in JP-A-2020-070426, JP-A-2020-076995 Core-shell type dyes described in, diarylmethane compounds described in JP-A-2020-504758, and the like can also be used.
• the green coloring agent is C.I. I. Pigment Green 7, 36, 58, 59, 62 and 63 are preferred, C.I. I. Pigment Green 7, 36, 58 and 59 are more preferred.
• red colorants examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, and diketopyrrolopyrrole compounds, anthraquinone compounds, azo It is preferably a compound, more preferably a diketopyrrolopyrrole compound. Also, the red colorant is preferably a pigment. Specific examples of red colorants include C.I. I.
• a red colorant a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole described in paragraphs 0016 to 0022 of Japanese Patent No.
• 10-2019-0140741 anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, JP 2020 -Perylene compounds described in JP-A-079396, perylene compounds described in JP-A-2020-083982, xanthene compounds described in JP-A-2018-035345, paragraph numbers 0025 to 0041 of JP-A-2020-066702
• the described diketopyrrolopyrrole compounds and the like can also be used.
• red colorant a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used.
• Lumogen F Orange 240 manufactured by BASF, red pigment, perylene pigment
• red colorant can also be used as a red colorant.
• the red coloring agent is C.I. I. Pigment Red 122, 177, 179, 254, 255, 264, 269, 272 and 291 are preferred, and C.I. I. Pigment Red 254, 264, 272 are more preferred.
• yellow colorants examples 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, an azomethine pigment, an isoindoline pigment, a pteridine pigment, a quinophthalone pigment or a perylene pigment, more preferably an azo pigment or an azomethine pigment.
• Specific examples of yellow colorants include C.I. I.
• a nickel azobarbiturate complex having the following structure can also be used as a yellow colorant.
• X 1 to X 16 each independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms.
• Specific examples of the compound represented by formula (QP1) include compounds described in paragraph number 0016 of Japanese Patent No. 6443711 .
• Y 1 to Y 3 each independently represent a halogen atom.
• n and m are integers from 0 to 6; p is an integer from 0 to 5; (n+m) is 1 or more.
• Specific examples of the compound represented by formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
• the yellow coloring agent is C.I. I. Pigment Yellow 117, 129, 138, 139, 150 and 185 are preferred.
• C.I. I. 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, 73, etc. of orange pigments.
• C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 are included.
• C.I. I. pigment blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. be done.
• An aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
• Dyes can also be used as chromatic colorants.
• the dye is not particularly limited, and known dyes can be used.
• a pigment multimer can also be used as a chromatic colorant.
• the dye multimer is preferably a dye dissolved in an organic solvent. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent.
• the particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682.
• a dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
• a plurality of dye structures in one molecule may be the same dye structure or different dye structures.
• the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
• the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
• the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
• Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
• the chromatic colorants include diarylmethane compounds described in JP-A-2020-504758, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, and JP-A-2020-117638.
• Xanthene compounds described phthalocyanine compounds described in International Publication No. 2020/174991, isoindoline compounds described in JP-A-2020-160279 or salts thereof,
• Korean Patent Publication No. 10-2020-0069442 described Compound represented by Formula 1, compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070 Compounds, compounds represented by Formula 1 described in Korean Patent Publication No.
• the chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-like structure, or may be used in both structures.
• Two or more chromatic colorants may be used in combination.
• black may be formed by a combination of two or more chromatic colorants.
• the black colorant is not particularly limited, and known ones can be used.
• inorganic black colorants include carbon black, titanium black, graphite, etc.
• Carbon black or titanium black is preferred, and titanium black is more preferred.
• Titanium black is black particles containing titanium atoms, preferably low order titanium oxide or titanium oxynitride. Titanium black can be surface-modified as necessary for the purpose of improving dispersibility, suppressing cohesion, and the like.
• Titanium black preferably has a small primary particle size and an average primary particle size of individual particles. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50, may be mentioned. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP-A-2012-169556 can be referred to, and the contents thereof are incorporated herein.
• titanium black examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
• organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferred.
• the bisbenzofuranone compound JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication No. 2014/208348, JP-A-2015-525260, etc.
• perylene compounds for example, available as "Irgaphor Black” manufactured by BASF.
• a perylene compound C.I. I. Pigment Black 31, 32 and the like.
• the azomethine compound include compounds described in JP-A-01-170601, JP-A-02-034664, and the like.
• perylene black Liogen Black FK4280, etc.
• paragraphs 0016 to 0020 of JP-A-2017-226821 may be used as the organic black colorant.
• the curable composition according to the present disclosure may contain one type of colorant alone or may contain two or more types. When two or more types are used, the total amount thereof is preferably within the following range.
• the content of the colorant is preferably 10% by mass to 75% by mass with respect to the total solid content of the curable composition.
• the upper limit is more preferably 70% by mass or less, and even more preferably 65% by mass or less.
• the lower limit is more preferably 20% by mass or more, and even more preferably 30% by mass or more.
• the curable composition according to the present disclosure preferably contains a resin.
• the curable composition according to the present disclosure can use a resin as the radically polymerizable compound. It is preferable to use a radically polymerizable compound containing at least a resin.
• the resin is blended, for example, for dispersing a pigment or the like in the curable composition or for a binder.
• a resin mainly used for dispersing a pigment or the like in a curable composition is also called a dispersant.
• such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
• a resin having a radically polymerizable group also corresponds to a radically polymerizable compound.
• the weight average molecular weight of the resin is preferably 3,000 to 2,000,000.
• the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
• the lower limit is preferably 4000 or more, more preferably 5000 or more.
• resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, Polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, and the like.
• norbornene resin is preferable from the viewpoint of improving heat resistance.
• Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No.
• a resin having a fluorene skeleton can also be preferably used.
• the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein.
• the resin the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339.
• a resin represented by the formula 1 can also be used.
• a resin having an acid group As the resin.
• acid groups include carboxy groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used.
• a resin having an acid group can be used, for example, as an alkali-soluble resin.
• the acid value of the resin having acid groups is preferably 30-500 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, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
• a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer"). It is also preferred to include
• R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
• R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
• the description in JP-A-2010-168539 can be referred to.
• paragraph number 0317 of JP-A-2013-029760 can be referred to, the content of which is incorporated herein.
• polymerizable groups include ethylenically unsaturated groups and cyclic ether groups.
• repeating unit Ep at least one type of repeating unit selected from repeating units represented by formula (Ep-1) and repeating units represented by formula (Ep-2).
• a resin hereinafter also referred to as resin Ep
• the resin Ep may contain only one of the repeating units represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2). -1) and the repeating unit represented by formula (Ep-2) may be included.
• the ratio of the repeating unit represented by the formula (Ep-1) to the repeating unit represented by the formula (Ep-2) is the molar ratio represented by the formula (Ep-1).
• Repeating unit: repeating unit represented by formula (Ep-2) preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20:80 to 80 :20 is more preferred.
• L 1 represents a single bond or a divalent linking group
• R 1 represents a hydrogen atom or a substituent.
• the substituent represented by R 1 includes an alkyl group and an aryl group, preferably an alkyl group.
• the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, more preferably 1-3.
• R 1 is preferably a hydrogen atom or a methyl group.
• the divalent linking group represented by L 1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S- and a group formed by combining two or more of these.
• the alkylene group may be linear, branched or cyclic, preferably linear or branched.
• the alkylene group may have a substituent or may be unsubstituted. A hydroxy group, an alkoxy group, etc. are mentioned as a substituent.
• the content of the repeating unit Ep in the resin Ep is preferably 1 mol % to 100 mol % of all repeating units in the resin Ep.
• the upper limit is preferably 90 mol % or less, more preferably 80 mol % or less.
• the lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
• the resin Ep may have other repeating units in addition to the repeating unit Ep.
• Other repeating units include a repeating unit having an acid group, a repeating unit having an ethylenically unsaturated group, and the like.
• the acid group includes a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, preferably a phenolic hydroxy group or a carboxy group, more preferably a carboxy group.
• ethylenically unsaturated groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups.
• the content of the repeating unit having an acid group in the resin Ep is preferably 5 mol% to 85 mol% of all repeating units in the resin Ep.
• the upper limit is preferably 60 mol % or less, more preferably 40 mol % or less.
• the lower limit is preferably 8 mol% or more, more preferably 10 mol% or more.
• the content of the repeating unit having an ethylenically unsaturated group in the resin Ep is 1 mol% to 65 mol% of the total repeating units of the resin Ep. is preferred.
• the upper limit is preferably 45 mol % or less, more preferably 30 mol % or less.
• the lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.
• the resin Ep preferably further contains a repeating unit having an aromatic hydrocarbon ring.
• the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
• the aromatic hydrocarbon ring may have a substituent. An alkyl group etc. are mentioned as a substituent.
• the content of the repeating unit having an aromatic hydrocarbon ring is 1 mol% of the total repeating units of the resin having a cyclic ether group. ⁇ 65 mol% is preferred.
• the upper limit is more preferably 45 mol % or less, even more preferably 30 mol % or less.
• the lower limit is more preferably 2 mol % or more, still more preferably 3 mol % or more.
• Repeating units having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring, such as vinyl toluene and benzyl (meth)acrylate.
• the resin it is also preferable to use a resin containing a repeating unit derived from the compound represented by formula (X).
• R 1 represents a hydrogen atom or a methyl group
• R 21 and R 22 each independently represent an alkylene group
• n represents an integer of 0-15.
• the number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3. preferable.
• n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
• Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol.
• Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
• resin Ac a resin having an aromatic carboxy group
• the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit.
• the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
• an aromatic carboxy group is a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
• the number of carboxy groups bonded to the aromatic ring is preferably 1-4, more preferably 1-2.
• the resin Ac is preferably a resin containing at least one repeating unit selected from repeating units represented by formula (Ac-1) and repeating units represented by formula (Ac-2).
• Ar 1 represents a group containing an aromatic carboxyl group
• L 1 represents -COO- or CONH-
• L 2 represents a divalent linking group
• Ar 10 represents a group containing an aromatic carboxyl group
• L 11 represents -COO- or CONH-
• L 12 represents a trivalent linking group
• P 10 represents a polymer chain.
• Examples of the aromatic carboxy group-containing group represented by Ar 1 in formula (Ac-1) include structures derived from aromatic tricarboxylic acid anhydrides, structures derived from aromatic tetracarboxylic acid anhydrides, and the like.
• Examples of aromatic tricarboxylic anhydrides and aromatic tetracarboxylic anhydrides include compounds having the following structures.
• Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).
• the group containing an aromatic carboxyl group represented by Ar 1 may have a polymerizable group.
• the polymerizable group is preferably an ethylenically unsaturated group and a cyclic ether group, more preferably an ethylenically unsaturated group.
• Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). and the like.
• n1 represents an integer of 1 to 4, preferably 1 or 2, more preferably 2.
• n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and still more preferably 2.
• n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, preferably 1 More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
• Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- 1) or a group represented by the above formula (Q-2).
• *1 represents the bonding position with L1 .
• L 1 represents -COO- or CONH-, preferably -COO-.
• the divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these A group obtained by combining two or more of The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
• the alkylene group may be linear, branched or cyclic.
• the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• An alkylene group and an arylene group may have a substituent. A hydroxy group etc.
• the divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-.
• L 2a is an alkylene group; an arylene group; a group in which an alkylene group and an arylene group are combined; at least one selected from an alkylene group and an arylene group; Examples include a group obtained by combining at least one selected from -NH- and S-, and an alkylene group is preferred.
• the number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
• the alkylene group may be linear, branched or cyclic.
• An alkylene group and an arylene group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
• the group containing an aromatic carboxyl group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and preferred embodiments are also the same.
• L 11 represents -COO- or CONH-, preferably -COO-.
• the trivalent linking group represented by L 12 in formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and 2 of these Groups in which more than one species are combined are included.
• Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, even more preferably 1-15.
• the aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, even more preferably 6-10.
• the hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent.
• the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), more preferably a group represented by formula (L12-2).
• L 12b represents a trivalent linking group
• X 1 represents S
• *1 represents the bonding position with L 11 of formula (Ac-2)
• *2 represents formula ( The binding position of Ac-2) with P10 is shown.
• the trivalent linking group represented by L 12b includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, and a hydrocarbon group or a group of a combination of a hydrocarbon group and —O— is preferred.
• L 12c represents a trivalent linking group
• X 1 represents S
• *1 represents the bonding position with L 11 of formula (Ac-2)
• *2 represents formula ( The binding position of Ac-2) with P10 is shown.
• the trivalent linking group represented by L 12c includes a hydrocarbon group; and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S- and the like, preferably a hydrocarbon group.
• P 10 in formula (Ac-2) represents a polymer chain.
• the polymer chain represented by P10 preferably has at least one repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units.
• the weight average molecular weight of the polymer chain P10 is preferably 500-20,000. More preferably, the lower limit is 1,000 or more.
• the upper limit is more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. If the weight average molecular weight of P10 is within the above range, the dispersibility of the pigment in the composition is good.
• the resin having an aromatic carboxyl group is a resin having repeating units represented by formula (Ac-2), this resin is preferably used as a dispersant.
• the polymer chain represented by P10 may contain a polymerizable group.
• Polymerizable groups include ethylenically unsaturated groups.
• the curable composition according to the present disclosure preferably contains a resin as a dispersant.
• Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
• the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups.
• the acidic dispersant (acidic resin) a resin having an acid group content of 70 mol % or more is preferable when the total amount of the acid group and the basic group is 100 mol %.
• the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group.
• the acid value of the acidic dispersant (acidic resin) is preferably 10 mgKOH/g to 105 mgKOH/g.
• a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
• a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %.
• the basic group possessed by the basic dispersant is preferably an amino group.
• the resin used as the dispersant is also preferably a graft resin.
• graft resin for details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
• the resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains.
• the polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom.
• a resin having The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
• the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
• 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.
• resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
• the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated group in its side chain.
• the content of repeating units having an ethylenically unsaturated group in a side chain is preferably 10 mol% or more of the total repeating units of the resin, more preferably 10 mol% to 80 mol%, and 20 mol%. More preferably ⁇ 70 mol%.
• 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.
• the resin containing an oxetane group in its side chain is preferably a graft polymer.
• the resin containing an oxetane group in a side chain those described in Examples to be described later can be suitably used.
• the content of the repeating unit having an oxetane group in the side chain in the resin is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, in the total repeating units of the resin, and 20 mol. % to 70 mol % is more preferred.
• resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, and the like can also be used.
• Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
• Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
• the content of the resin is preferably 1% by mass to 70% by mass with respect to the total solid content of the curable composition.
• the lower limit is more preferably 2% by mass or more, still 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 even more preferably 60% by mass or less.
• the content of the resin having an acid group is preferably 1% by mass to 70% by mass with respect to the total solid content of the curable composition.
• the lower limit is more preferably 2% by mass or more, still 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 even more preferably 60% by mass or less.
• the content of the alkali-soluble resin is preferably 1% by mass to 70% by mass with respect to the total solid content of the curable composition.
• the lower limit is more preferably 2% by mass or more, still 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 even more preferably 60% by mass or less.
• the content of the resin as a dispersant is 0.1% by mass to 30% by mass with respect to the total solid content of the curable composition. preferable.
• the upper limit is more preferably 25% by mass or less, and even more preferably 20% by mass or less.
• the lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
• the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the colorant.
• the upper limit is more preferably 80 parts by mass or less, even 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, still more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more.
• the curable composition according to the present disclosure may contain only one resin, or may contain two or more resins. When two or more resins are included, the total amount thereof is preferably within the above range.
• the curable composition according to the present disclosure preferably contains a solvent.
• An organic solvent is mentioned as a solvent.
• the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
• Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference can be made to paragraph 0223 of WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used.
• organic solvents include polyethylene glycol monomethyl ether, dichloromethane, 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, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
• aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).
• an organic solvent with a low metal content it is preferable 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) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015). .
• Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
• the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
• the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers may be contained.
• the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
• 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 30% by mass to 90% by mass. More preferred.
• the curable composition according to the present disclosure preferably does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations.
• substantially free of environmentally regulated substances means that the content of environmentally regulated substances in the curable composition is 50 mass ppm or less, and that it is 30 mass ppm or less. It is preferably 10 mass ppm or less, more preferably 1 mass ppm or less, particularly preferably 1 mass ppm or less.
• Environmental control substances include, for example, benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
• distillation methods are the stage of raw materials, the stage of reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or the curable composition prepared by mixing these compounds. Any stage, such as stages, is possible.
• a curable composition according to the present disclosure may contain a pigment derivative.
• Pigment derivatives are used, for example, as dispersing aids.
• Pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
• Dye skeletons constituting pigment derivatives include quinoline dye skeletons, benzimidazolone dye skeletons, benzoisoindole dye skeletons, benzothiazole dye skeletons, iminium dye skeletons, squarylium dye skeletons, croconium dye skeletons, oxonol dye skeletons, and pyrrolopyrrole dye skeletons.
• diketopyrrolopyrrole dye skeleton azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton, Isoindoline dye skeletons, isoindolinone dye skeletons, quinophthalone dye skeletons, iminium dye skeletons, dithiol dye skeletons, triarylmethane dye skeletons, pyrromethene dye skeletons, and the like can be mentioned.
• the acid group includes a carboxy group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group and salts thereof.
• Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
• the carboxylic acid amide group a group represented by —NHCOR X1 is preferable.
• sulfonic acid amide group a group represented by —NHSO 2 R X2 is preferable.
• the imidic acid group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or SO 2 NHCOR X6 , more preferably —SO 2 NHSO 2 R X3 .
• R X1 to R X6 each independently represent an alkyl group or an aryl group.
• the alkyl groups and aryl groups represented by R X1 to R X6 may have substituents.
• the substituent is preferably a halogen atom, more preferably a fluorine atom.
• Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
• Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
• a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can also be used as the pigment derivative.
• the maximum molar extinction coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength region of 400 nm to 700 nm is preferably 3,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, more preferably 1,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ It is more preferably 1 or less, and even more preferably 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
• the lower limit of ⁇ max is, for example, 1 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and may be 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
• pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, JP-A-03- 009961, compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, JP-A-04-285669 Compounds described in publications, compounds described in JP-A-06-145546, compounds described in JP-A-06-212088, compounds described in JP-A-06-240158, JP-A-10-030063 Compounds described, compounds described in JP-A-10-195326, compounds described in paragraphs 0086 to 0098 of WO 2011/024896, WO 2012/102399 described in paragraphs 0063 to 0094 Compounds, compounds described in paragraph number 0082 of WO 2017/038252, compounds described in paragraph number 0171 of JP 2015-151530, JP 2011-25
• the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, with respect to 100 parts by mass of the colorant.
• the total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, and further preferably 45% by mass or more, based on the total solid content of the curable composition.
• Preferably, 50% by mass or more is particularly preferable.
• the upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
• Curable compositions according to the present disclosure may also contain polyalkyleneimines.
• Polyalkyleneimines are used, for example, as dispersing aids for pigments.
• a dispersing aid is a material for enhancing the dispersibility of the pigment in the curable composition.
• a polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has at least a secondary amino group.
• the polyalkyleneimine may contain primary amino groups or tertiary amino groups in addition to secondary amino groups.
• the polyalkyleneimine is preferably a polymer having a branched structure each containing a primary amino group, a secondary amino group and a tertiary amino group.
• the number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
• 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, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
• the molecular weight of the polyalkyleneimine when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula.
• the molecular weight of the specific amine compound 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 elevation method is used.
• the value of the number average molecular weight measured by the viscosity method is used.
• the value of the number average molecular weight in terms of polystyrene measured by the GPC (gel permeation chromatography) method is used.
• the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
• alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc., preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. In addition, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more, of the primary amino group with respect to the total of the primary amino group, the secondary amino group and the tertiary amino group. , more preferably 30 mol % or more.
• Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, P-1000 (manufactured by Nippon Shokubai Co., Ltd.).
• the content of the polyalkyleneimine in the total solid content of the curable composition is preferably 0.1% by mass to 5% by mass.
• the lower limit is more preferably 0.2% by mass or more, still 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, even more preferably 4% by mass or less, and particularly preferably 3% by mass or less.
• the content of the polyalkyleneimine is preferably 0.5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the pigment.
• the lower limit is more preferably 0.6 parts by mass or more, still more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more.
• the upper limit is more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one kind of polyalkyleneimine may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
• a curable composition according to the present disclosure may contain a curing accelerator.
• Curing accelerators include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like.
• the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of WO 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, JP 2013-041165 Compounds described in paragraph numbers 0186 to 0251 of the publication, ionic compounds described in JP 2014-055114, compounds described in paragraph numbers 0071 to 0080 of JP 2012-150180, JP 2011-253054 Alkoxysilane compounds having an epoxy group described in JP-A-2005-200157, compounds described in paragraphs 0085 to 0092 of Japanese Patent No. 5765059, and carboxy group-containing epoxy curing agents described in JP-A-2017-036379.
• the content of the curing accelerator in the total solid content of the curable composition is preferably 0.3% by mass to 8.9% by mass, more preferably 0.8% by mass to 6.4% by mass. preferable.
• a curable composition according to the present disclosure may contain an infrared absorbing agent.
• the wavelength of light transmitted through the film obtained by including an infrared absorbing agent in the curable composition is set to a longer wavelength. can be shifted to the side.
• the infrared absorbing agent is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm.
• the infrared absorbing agent is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm or more and 1800 nm or less.
• the ratio A 1 /A 2 between the absorbance A 1 at a wavelength of 500 nm and the absorbance A 2 at the maximum absorption wavelength of the infrared absorbent is preferably 0.08 or less, more preferably 0.04 or less.
• infrared absorbers examples include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, and azomethine. compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like.
• pyrrolopyrrole compound compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, WO 2015/166873 Compounds described in Paragraph Nos. 0010 to 0033 and the like.
• examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987.
• Examples of croconium compounds include compounds described in JP-A-2017-082029.
• As the iminium compound for example, compounds described in JP-A-2008-528706, compounds described in JP-A-2012-012399, compounds described in JP-A-2007-092060, International Publication No. 2018/043564 and the compounds described in paragraphs 0048 to 0063 of.
• Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, vanadium phthalocyanine compounds described in International Publication No. 2020/071486, and phthalocyanine compounds described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-077153. Dithiolene metal complexes include compounds described in Japanese Patent No. 5733804.
• metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide.
• metal borides include lanthanum boride.
• Commercially available lanthanum boride products include LaB 6 -F (manufactured by Nippon New Metal Co., Ltd.).
• a metal boride the compound as described in international publication 2017/119394 can also be used.
• commercially available products of indium tin oxide include F-ITO (manufactured by DOWA Hitech Co., Ltd.).
• the infrared absorbing agent the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in WO 2016/154782, and the patent No. 5884953. No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraphs 0090 to 0107 of International Publication No.
• the content of the infrared absorbing agent in the total solid content of the curable composition is preferably 1% by mass to 40% by mass.
• the lower limit is more preferably 2% by mass or more, still 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 even more preferably 25% by mass or less.
• the curable composition according to the present disclosure may contain only one infrared absorber, or may contain two or more infrared absorbers. When two or more kinds of infrared absorbing agents are included, the total amount thereof is preferably within the above range.
• a curable composition according to the present disclosure may contain an ultraviolet absorber.
• ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, and paragraph numbers 0317-0317 of JP-A-2013-068814.
• UV absorbers examples include UV-503 (manufactured by Daito Chemical Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. .
• UV-503 manufactured by Daito Chemical Co., Ltd.
• Tinuvin series and Uvinul series manufactured by BASF Tinuvin series and Uvinul series manufactured by BASF
• benzotriazole compound the MYUA series made from Miyoshi oil and fats (Chemical Daily, February 1, 2016) is mentioned.
• the ultraviolet absorber is a compound described in paragraph numbers 0049 to 0059 of Japanese Patent No.
• a thioaryl group-substituted benzotriazole-type ultraviolet absorber described in can also be used.
• the content of the ultraviolet absorber in the total solid content of the curable composition is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• a curable composition according to the present disclosure may contain a polymerization inhibitor.
• Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.).
• 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. Only one kind of polymerization inhibitor may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
• a curable composition according to the present disclosure may contain a silane coupling agent.
• a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
• the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction.
• Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
• Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group and isocyanate group. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferred.
• silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM
• silane coupling agent examples include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. , the contents of which are incorporated herein.
• 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 0.05% by mass to 10.0% by mass. is more preferred. Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount thereof is preferably within the above range.
• a curable composition according to the present disclosure may contain a surfactant.
• a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
• the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
• surfactants reference can be made to surfactants described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
• the fluorine content in the fluorosurfactant is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, and particularly preferably 7% to 25% by mass.
• a fluorosurfactant having a fluorine content within this range is effective in uniformity of the thickness of the coating film and liquid saving, and has good solubility in the curable composition.
• JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
• Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144.
• the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and an acrylic compound in which the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable.
• fluorine-based surfactants include MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Mega Fac DS-21.
• fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant.
• fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
• a block polymer can also be used for the fluorine-based surfactant.
• the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
• a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
• fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present disclosure.
• the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
• % indicating the ratio of repeating units is mol%.
• a fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorosurfactant.
• Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K.
• compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
• m represents 1 or 2
• n represents an integer of 1 to 4
• a represents 1 or 2
• X a + is a valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH4 + .
• Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fuji
• Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.
• a compound with the following structure can also be used as a silicone-based surfactant.
• 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 is preferably 0.005% by mass to 3.0% by mass. more preferred. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.
• a curable composition according to the present disclosure may contain an antioxidant.
• Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred. A substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent.
• the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
• Phosphorus-based antioxidants can also be suitably used as antioxidants.
• a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
• antioxidants examples include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
• antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, compounds described in WO 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
• the content of the antioxidant in the total solid content of the curable composition is preferably 0.01% by mass to 20% by mass, more preferably 0.3% by mass to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• the curable composition according to the present disclosure optionally contains sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliary agents (e.g., conductive particles, antifoaming agents, A retardant, a leveling agent, a release accelerator, a fragrance, a surface tension modifier, a chain transfer agent, etc.) may be contained.
• sensitizers e.g., curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliary agents
• auxiliary agents e.g., conductive particles, antifoaming agents, A retardant, a leveling agent, a release accelerator, a fragrance, a surface tension modifier, a chain transfer agent, etc.
• the curable composition according to the present disclosure may also contain latent antioxidants, if desired.
• the latent antioxidant is a compound in which the site functioning as an antioxidant is protected with a protective group, and is heated at 100°C to 250°C, or at 80°C to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant by removing a protecting group by heating is included.
• Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
• Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
• the curable composition according to the present disclosure may contain metal oxides to adjust the refractive index of the resulting film.
• metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 and SiO 2 .
• the primary particle size of the metal oxide is preferably 1 nm to 100 nm, more preferably 3 nm to 70 nm, even more preferably 5 nm to 50 nm.
• Metal oxides may have a core-shell structure. Moreover, in this case, the core portion may be hollow.
• the curable composition according to the present disclosure may contain a light resistance improver.
• a light resistance improver compounds described in paragraph numbers 0036 to 0037 of JP-A-2017-198787, compounds described in paragraph numbers 0029-0034 of JP-A-2017-146350, JP-A-2017-129774 Compounds described in paragraph numbers 0036 to 0037, 0049 to 0052 of JP 2017-129674 JP 2017-129674 paragraph numbers 0031 to 0034, 0058 to 0059 compounds described in JP 2017-122803 paragraph numbers 0036 to 0037 , compounds described in 0051 to 0054, compounds described in paragraph numbers 0025 to 0039 of WO 2017/164127, compounds described in paragraph numbers 0034 to 0047 of JP 2017-186546, JP 2015-025116 Compounds described in paragraph numbers 0019 to 0041 of JP-A-2012-145604, compounds described in paragraph numbers 0101-0125 of JP-A-2012-103475
• the curable composition according to the present disclosure is substantially free of terephthalate.
• substantially free means that the content of terephthalic acid ester is 1000 mass ppb or less, more preferably 100 mass ppb or less, in the total amount of the curable composition. , is particularly preferably zero.
• perfluoroalkylsulfonic acid and its salts may be regulated.
• perfluoroalkylsulfonic acid especially perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
• the content of perfluoroalkylcarboxylic acid especially perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
• the content of perfluoroalkylcarboxylic acid is 0.01 ppb to the total solid content of the curable composition It is preferably in the range of 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, even more preferably in the range of 0.1 ppb to 300 ppb.
• the curable composition according to the present disclosure may be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts.
• a compound that can substitute for perfluoroalkylsulfonic acid and its salt and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and salts thereof may be selected.
• Examples of compounds that can substitute for regulated compounds include compounds that are excluded from the scope of regulation due to differences in the number of carbon atoms in perfluoroalkyl groups.
• Curable compositions according to the present disclosure may contain perfluoroalkylsulfonic acids and salts thereof and perfluoroalkylcarboxylic acids and salts thereof within the maximum permissible range.
• the water content of the curable composition according to the present disclosure is preferably 3% by mass or less, more preferably 0.01% to 1.5% by mass, and 0.1% to 1.0% by mass. A range is more preferred.
• the water content can be measured by the Karl Fischer method.
• the curable composition according to the present disclosure can be used by adjusting the viscosity for the purpose of adjusting the film surface state (such as flatness) and adjusting the film thickness.
• the viscosity value can be appropriately selected as necessary, and is preferably, for example, 0.3 mPa ⁇ s to 50 mPa ⁇ s, more preferably 0.5 mPa ⁇ s to 20 mPa ⁇ s at 25°C.
• a method for measuring the viscosity for example, a cone-plate type viscometer can be used, and the viscosity can be measured in a state where the temperature is adjusted to 25°C.
• the curable composition according to the present disclosure preferably has a chloride ion content of 10,000 ppm or less, preferably 1000 ppm or less, from the viewpoint of environmental friendliness, suppression of foreign matter generation, suppression of device contamination, and the like. is more preferable.
• a chloride ion content 10,000 ppm or less, preferably 1000 ppm or less, from the viewpoint of environmental friendliness, suppression of foreign matter generation, suppression of device contamination, and the like. is more preferable.
• a known method can be used as a method for measuring chloride ions, and examples thereof include ion chromatography and combustion ion chromatography.
• the storage container for the curable composition is not particularly limited, and known storage containers can be used.
• a storage container a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and curable compositions. It is also preferred to use bottles. Examples of such a container include the container described in JP-A-2015-123351.
• the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the curable composition, and suppressing deterioration of components.
• a curable composition according to the present disclosure can be prepared by mixing the aforementioned ingredients.
• all components may be simultaneously dissolved and/or dispersed in a solvent to prepare the curable composition, or if necessary, each component may be appropriately mixed into two or more solutions or dispersions.
• a curable composition may be prepared by mixing these liquids at the time of use (at the time of coating).
• a process of dispersing the pigment when preparing the curable composition.
• mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
• Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
• 2015-157893 can be preferably used.
• the particles may be made finer in the salt milling process.
• Materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.
• Beads used for dispersion can be zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof.
• an inorganic compound having a Mohs hardness of 2 or more can be used.
• the composition may contain 1 to 10000 ppm of the beads.
• any filter that has been conventionally used for filtration or the like can be used without particular limitation.
• fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
• polyamide resins such as nylon (eg nylon-6, nylon-6,6)
• polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high-molecular-weight polyolefin resin) and other materials.
• PP polypropylene
• nylon including high density polypropylene
• nylon including high density polypropylene
• the pore size of the filter is preferably 0.01 ⁇ m to 7.0 ⁇ m, more preferably 0.01 ⁇ m to 3.0 ⁇ m, even more preferably 0.05 ⁇ m to 0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
• the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
• Various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as filters. .
• fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
• Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Roki Techno.
• filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed. In addition, the filter can be appropriately selected according to the hydrophilicity/hydrophobicity of the composition.
• the cured product according to the present disclosure is a cured product obtained by curing the curable composition according to the present disclosure.
• the film according to the present disclosure is a film obtained from the curable composition according to the present disclosure, and is preferably a film obtained by curing the curable composition according to the present disclosure.
• Films according to the present disclosure can be used in optical filters such as color filters and infrared transmission filters. Specifically, it can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Green pixels and blue pixels are preferred, and green pixels are more preferred.
• the film thickness of the film according to the present disclosure can be appropriately adjusted according to the purpose, but is preferably 0.1 ⁇ m to 20 ⁇ m.
• the upper limit of the film thickness is more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less, and most preferably 1.5 ⁇ m or less.
• the lower limit of the film thickness is more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
• the method for producing a cured product according to the present disclosure and the method for producing a film according to the present disclosure are not particularly limited, but include a step of irradiating the curable composition according to the present disclosure with light having a wavelength of 150 nm to 380 nm. is preferable, and it is more preferable to include a step of irradiating light with a wavelength of 150 nm to 300 nm.
• Light with a wavelength of 150 nm to 380 nm includes i-rays (wavelength: 365 nm), KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), and the like.
• the shape of the cured product to be obtained is not particularly limited, but it is preferably in the form of a film.
• the film according to the present disclosure can be produced through a step of applying the curable composition according to the present disclosure to a support.
• the film manufacturing method further includes a step of forming a pattern (pixels).
• a method for forming the pattern (pixels) includes a photolithography method and a dry etching method, and the photolithography method is preferable.
• Pattern formation by photolithography includes the steps of forming a curable composition layer on a support using the curable composition according to the present disclosure, patternwise exposing the curable composition layer, and curable and a step of developing and removing unexposed portions of the composition layer to form a pattern (pixels). If necessary, a step of baking the curable composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
• the curable composition according to the present disclosure is used to form a curable composition layer on the support.
• the support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include glass substrates and silicon substrates, and silicon substrates are preferred. Also, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate.
• CCD charge-coupled device
• CMOS complementary metal oxide semiconductor
• the silicon substrate is formed with a black matrix that isolates each pixel.
• the silicon substrate may be provided with an underlying layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
• the underlayer is formed using a composition obtained by removing the colorant from the curable composition described herein, or a composition containing the resin, polymerizable compound, surfactant, etc. described herein. good too.
• the surface contact angle of the underlayer is preferably 20° to 70° when measured with diiodomethane. Further, it is preferably 30° to 80° when measured with water.
• a known method can be used as a method for applying the curable composition.
• dropping method drop cast
• slit coating method spray method
• roll coating method spin coating
• methods described in publications inkjet
• ejection system printing ejection system printing
• nozzle jet flexographic printing
• screen printing gravure printing
• reverse offset printing metal mask printing
• nanoimprint method ejection system printing
• a transfer method using a mold or the like ejection system printing
• the application method for inkjet is not particularly limited.
• the curable composition layer formed on the support may be dried (pre-baked). Pre-baking may not be performed when the film is manufactured by a low-temperature process.
• the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower.
• the lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher.
• the prebaking time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and even more preferably 80 seconds to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.
• the curable composition layer is exposed in a pattern (exposure step).
• the curable composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
• Radiation (light) that can be used for exposure includes g-line, i-line, and the like.
• Light with a wavelength of 300 nm or less (preferably light with a wavelength of 150 nm to 300 nm) can also be used.
• Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferred.
• a long-wave light source of 300 nm or more can also be used.
• the light when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure).
• pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
• the dose is, for example, preferably 0.03 J/cm 2 to 2.5 J/cm 2 , more preferably 0.05 J/cm 2 to 1.0 J/cm 2 .
• the oxygen concentration at the time of exposure can be selected as appropriate.
• the exposure may be performed under an oxygen-free atmosphere, or under a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
• the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done.
• the oxygen concentration and exposure illuminance may be appropriately combined.
• the illuminance may be 10000 W/m 2 at an oxygen concentration of 10% by volume and 20000 W/m 2 at an oxygen concentration of 35% by volume.
• the unexposed portions of the curable composition layer are removed by development to form a pattern (pixels).
• the development and removal of the unexposed portion of the curable composition layer can be performed using a developer.
• the curable composition layer in the unexposed area in the exposure step is eluted into the developer, leaving only the photocured area.
• the temperature of the developer is preferably 20° C. to 30° C., for example.
• the development time is preferably 20 seconds to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
• the developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used.
• an alkaline developer an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable.
• alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
• ethyltrimethylammonium hydroxide ethyltrimethylammonium hydroxide
• benzyltrimethylammonium hydroxide dimethylbis(2-hydroxyethyl)ammonium hydroxide
• choline pyrrole
• piperidine 1,8-diazabicyclo-[5.4.0]-7-undecene
• examples include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate.
• a compound having a large molecular weight is preferable for the alkaline agent from the standpoint of environment and safety.
• the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass.
• the developer may further contain a surfactant. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 times to 100 times. It is also preferable to wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the curable composition layer after development while rotating the support on which the curable composition layer after development is formed.
• the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support.
• the moving speed of the nozzle may be gradually decreased.
• Additional exposure processing and post-baking are post-development curing treatments for complete curing.
• the heating temperature in post-baking is, for example, preferably 100°C to 240°C, more preferably 200°C to 240°C.
• Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions.
• the additional exposure process is performed, the light used for exposure preferably has a wavelength of 400 nm or less. Also, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
• Pattern formation by a dry etching method forms a curable composition layer on a support using the curable composition according to the present disclosure, and the entire curable composition layer is cured to form a cured product layer.
• a step of forming a photoresist layer on the cured product layer a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern; and a cured product layer using the resist pattern as a mask. and dry etching using an etching gas.
• a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable.
• pattern formation by a dry etching method descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated herein.
• optical element An optical element according to the present disclosure has a film according to the present disclosure.
• Optical elements include optical filters, lenses, prisms, reflectors, diffraction gratings, and the like. Among them, an optical filter is preferable. Types of optical filters include color filters and infrared transmission filters, and color filters are preferred.
• a color filter preferably has a film according to the present disclosure as its colored pixels.
• the film thickness of the film according to the present disclosure can be appropriately adjusted according to the purpose.
• the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and still more preferably 0.3 ⁇ m or more.
• the width of pixels included in the optical filter is preferably 0.4 ⁇ m to 10.0 ⁇ m.
• the lower limit is more preferably 0.4 ⁇ m or more, still more preferably 0.5 ⁇ m or more, and particularly preferably 0.6 ⁇ m or more.
• the upper limit is more preferably 5.0 ⁇ m or less, still more preferably 2.0 ⁇ m or less, particularly preferably 1.0 ⁇ m or less, and most preferably 0.8 ⁇ m or less.
• the Young's modulus of the pixel is preferably 0.5 GPa to 20 GPa, more preferably 2.5 GPa to 15 GPa.
• Each pixel included in the optical filter preferably has high flatness.
• the pixel surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example.
• the surface roughness of a pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco.
• the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50° to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.).
• the volume resistance value of the pixel is high.
• the volume resistance value of the pixel is preferably 10 9 ⁇ cm or more, more preferably 10 11 ⁇ cm or more.
• the upper limit is not specified, it is preferably 10 14 ⁇ cm or less, for example.
• the volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
• a protective layer may be provided on the surface of the film according to the present disclosure.
• the protective layer By providing the protective layer, it is possible to impart various functions such as blocking oxygen, reducing reflection, making the film hydrophilic and hydrophobic, and blocking light of a specific wavelength (ultraviolet rays, near-infrared rays, etc.).
• the thickness of the protective layer is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m.
• Examples of the method of forming the protective layer include a method of applying a protective layer-forming composition, a chemical vapor deposition method, and a method of adhering a molded resin with an adhesive.
• Components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, and polyimides.
• the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
• the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
• the protective layer may optionally contain organic/inorganic particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index modifiers, antioxidants, adhesion agents, additives such as surfactants. may contain.
• organic/inorganic particles include polymeric particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
• a known absorber can be used as the absorber for light of a specific wavelength.
• the content of these additives can be appropriately adjusted, but is preferably 0.1% by mass to 70% by mass, more preferably 1% by mass to 60% by mass, based on the total mass of the protective layer.
• the protective layer the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
• the optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
• An image sensor according to the present disclosure has a membrane according to the present disclosure.
• Image sensors include solid-state imaging devices, X-ray imaging devices, organic thin-film imaging devices, and the like. Among them, it can be suitably used for a solid-state imaging device.
• a solid-state imaging device according to the present disclosure includes a film according to the present disclosure. The configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device.
• Transfer electrodes made of polysilicon or the like, and a plurality of photodiodes forming a light receiving area of a solid-state imaging device (such as a CCD (charge-coupled device) image sensor, a CMOS (complementary metal-oxide semiconductor) image sensor, etc.) on a substrate.
• a light-shielding film is provided on the photodiode and the transfer electrode so that only the light-receiving portion of the photodiode is opened. It has a device protective film with a thickness of 1.5 mm, and has a color filter on the device protective film.
• the color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
• the partition wall preferably has a lower refractive index than each color pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478, JP-A-2014-179577, and International Publication No. 2018/043654.
• an ultraviolet absorption layer may be provided in the structure of the solid-state imaging device to improve light resistance.
• An imaging device equipped with a solid-state imaging device according to the present disclosure can be used not only for digital cameras and electronic devices (mobile phones, etc.) having an imaging function, but also for vehicle-mounted cameras and surveillance cameras.
• An image display device includes a film according to the present disclosure.
• image display devices include liquid crystal display devices and organic electroluminescence display devices.
• electroluminescence display devices For a definition of an image display device and details of each image display device, see, for example, “Electronic Display Device (by Akio Sasaki, Industrial Research Institute, 1990)", “Display Device (by Junsho Ibuki, Sangyo Tosho ( Co., Ltd.) issued in 1989).
• Liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)".
• the present disclosure can be applied to various types of liquid crystal display devices described in the above “next generation liquid crystal display technology”.
• the radical polymerization initiator according to the present disclosure is a radical polymerization initiator represented by Formula 1 below.
• the radical polymerization initiator according to the present disclosure is preferably a radical photopolymerization initiator, and more preferably a radical photopolymerization initiator that generates radicals by light with a wavelength of 150 nm to 300 nm.
• Ar 1 represents an aromatic ring or heteroaromatic ring
• X 1 represents -OR 11 or -NR 12 R 13
• Y 1 represents a divalent linking group
• R a is a hydrogen atom or a substituent.
• R 11 to R 13 each independently represent a hydrogen atom or a substituent.
• a preferred embodiment of the radical polymerization initiator represented by Formula 1 in the radical polymerization initiator according to the present disclosure is the same as the preferred embodiment of the radical polymerization initiator represented by Formula 1 described above in the curable composition.
• Ar 2 represents an aromatic ring or heteroaromatic ring
• X 2 represents —OR 24 or —NR 25 R 26
• Y 2 represents a single bond or a divalent linking group
• R 21 to R 26 each independently represents a hydrogen atom or a substituent
• R 25 and R 26 may combine to form a ring
• n represents an integer of 1-3.
• Preferred aspects of the compound represented by Formula 2 in the compound according to the present disclosure are the same as preferred aspects of the radical polymerization initiator represented by Formula 2 described above in the curable composition.
• the compound represented by Formula 2 above is preferably a compound represented by Formula 3A or Formula 3B below.
• X 3 represents -OR 34 or -NR 35 R 36
• Y 3 represents a single bond, -O- or -S-
• R 31 represents an alkyl group or an aryl group
• R 32 to R 36 each independently represent a hydrogen atom, an alkyl group or an aryl group
• R 35 and R 36 may be linked to form a ring
• n represents an integer of 1 to 3
• R 39 each independently represents a substituent
• m represents an integer of 0-2.
• Preferred aspects of the compound represented by Formula 3A or Formula 3B in the compound according to the present disclosure are respectively the same as preferred aspects of the radical polymerization initiator represented by Formula 3A or Formula 3B described above in the curable composition.
• the compound represented by Formula 2 above is particularly preferably a compound represented by Formula 4 below.
• X 4 represents —OR 44 or —NR 45 R 46
• Y 4 represents a single bond, —O— or —S—
• R 41 represents an alkyl group or an aryl group
• R 42 to R 46 each independently represents a hydrogen atom, an alkyl group or an aryl group
• R 45 and R 46 may be linked to form a ring
• n represents an integer of 1 to 3
• L 1 and L 2 each independently represents a single bond, —CR 47 R 48 —, —O—, —S— or —NR 49 —
• each of R 47 to R 49 independently represents a hydrogen atom, an alkyl group or an aryl group
• p represents 0 or 1
• q represents an integer of 0 to 2
• Preferred aspects of the compound represented by formula 4 in the compound according to the present disclosure are the same as preferred aspects of the radical polymerization initiator represented by formula 4 described above in the curable composition.
• Synthesis method of radical photopolymerization initiator A-46> 2-methyl- ⁇ -tetralone was changed to N-ethyl-9-(2-methylbenzoyl)-1,6-dihydrocyclopenta[c]carbazol-3(2H)-one, and methyl iodide was Photoradical polymerization initiator A-46 was synthesized in the same manner except that ethyl iodide was used.
• ⁇ Synthesis Example 8 Synthesis method of radical photopolymerization initiator A-64>
• 2-methyl- ⁇ -tetralone was converted to N-ethyl-11-(2-methylbenzoyl)-3,4-dihydro-2H-oxepino[3,2-c]carbazol-5(8H)-one.
• a radical photopolymerization initiator A-64 was synthesized in the same manner, except that methyl iodide was changed to ethyl iodide.
• Synthesis method of radical photopolymerization initiator A-68> N-ethyl-11-(2-methylbenzoyl)-3,4-dihydro-2H-oxepino[3,2-c]carbazol-5(8H)-one was converted to N-ethyl-11-nitro- Photoradical polymerization initiator A-68 was synthesized in the same manner except that 3,4-dihydro-2H-oxepino[3,2-c]carbazol-5(8H)-one was used.
• Synthesis method of radical photopolymerization initiator A-92> N-ethyl-11-(2-methylbenzoyl)-3,4-dihydro-2H-oxepino[3,2-c]carbazol-5(8H)-one was converted to 7-(4-(2- A radical photopolymerization initiator A-92 was synthesized in the same manner except that methylbenzoyl)phenyl)-3,4-dihydrobenzo[b]oxepin-5(2H)-one was used.
• Pigment Green 58 [zinc phthalocyanine complex, green pigment (G pigment)]
• PY129 C.I. I. Pigment Yellow 129 [azomethine copper complex, yellow pigment (Y pigment)]
• PY185 C.I. I. Pigment Yellow 185 [isoindoline compound, yellow pigment (Y pigment)]
• PY215 C.I. I. Pigment Yellow 215 [pretedin compound, yellow pigment (Y pigment)]
• PB16 C.I. I. Pigment Blue 16 [metal-free phthalocyanine compound, blue pigment (B pigment)]
• Pigment Blue 15:6 [copper phthalocyanine complex, blue pigment (B pigment)]
• IR dye a compound having the following structure (near-infrared absorbing pigment, in the following structural formula, Me represents a methyl group and Ph represents a phenyl group.)
• TiBk Titanium black [black pigment (Bk pigment)]
• Zr oxynitride zirconium oxynitride [black pigment (Bk pigment)]
• P-1 30 mass % propylene glycol monomethyl ether acrylate (PGMEA) solution of resin having the following structure.
• the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
• Mw 20,000.
• P-2 30% by mass PGMEA solution of resin having the following structure.
• the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units.
• P-3 30% by mass PGMEA solution of resin having the following structure.
• the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw: 21,000.
• P-4 30% by mass PGMEA solution of resin having the following structure.
• the numerical value attached to the side chain is the number of repeating units. Mw: 9,000.
• P-5 30% by mass PGMEA solution of resin having the following structure.
• the numerical value attached to the side chain is the number of repeating units. Mw: 10,000.
• Surfactant 1 1% by mass PGMEA solution of KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• a-2 resin with the following structure (numerical values attached to the main chain are molar ratios; weight average molecular weight: 15,000)
• D-1 KAYARAD DPHA (hexafunctional acrylate compound, manufactured by Nippon Kayaku Co., Ltd.)
• D-2 NK ester A-DPH-12E (ethylene oxide (EO)-modified hexafunctional acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd.)
• D-3 NK ester A-TMMT (tetrafunctional acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd.)
• D-4 Aronix M-510 (3- to 4-functional acrylate compound, manufactured by Toagosei Co., Ltd.)
• D-5 Light acrylate DCP-A (bifunctional alicyclic acrylate compound, manufactured by Kyoeisha Chemical Co., Ltd.)
• outgassing was collected for 1 hour in a vacuum clean oven at 100° C., and the amount of outgassing was calculated from the peak obtained from a gas chromatography mass spectrometer (GC/MS).
• GC/MS gas chromatography mass spectrometer
• TMAH tetramethylammonium hydroxide
• ⁇ Adhesion>> Each photosensitive composition was applied onto a silicon wafer using a spin coater, and then heated (pre-baked) at 100° C. for 120 seconds using a hot plate to obtain a coating film having a thickness of 1.0 ⁇ m. rice field. Then, using an i-line stepper exposure apparatus FPA-3000iS+ (manufactured by Canon Inc.), exposure was performed at an exposure dose of 400 mJ/cm 2 through a mask engraved with a checkered pattern of 0.8 ⁇ m. . Next, using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development is performed at 23° C.
• TMAH tetramethylammonium hydroxide
• a pattern was formed in the same procedure as the evaluation of adhesion.
• the cross-sectional shape of the obtained pattern was observed by SEM (Scanning Electron Microscope, magnification: 20,000 times), 5 patterns were extracted from the SEM photograph, and the average inclination of the cross-section of the 5 patterns was obtained.
• the pattern cross-sectional shape 1 was evaluated on the basis of.
• the inclination of the cross section of the pattern is the inclination in the thickness direction of the pattern on the silicon wafer at the portion where the pattern is formed. Specifically, the angle of the portion formed by the surface of the silicon wafer and the side of the pattern in the thickness direction was measured.
• solubility As an index of storage stability of the radical polymerization initiator represented by Formula 1 under low temperature conditions, solubility was evaluated by the following method. 100 g of each curable composition obtained above was placed in a sealed plastic container, stored at 0° C. for 3 months, returned to room temperature (25° C.), and the weight of the precipitate was confirmed. The curable composition after storage was filtered using filter paper (ADVANTEC No. 4A, manufactured by Advantec Toyo Co., Ltd.), and the weight of precipitates remaining on the filtered filter paper was weighed. -Evaluation criteria- A: No precipitate was observed (the amount of precipitate was 0 g). B: Precipitates were more than 0 g and less than 0.1 g. C: Precipitates were 0.1 g or more and less than 0.5 g. D: Precipitates were 0.5 g or more and less than 1.0 g. E: Precipitate was 1.0 g or more.
• the curable compositions of Examples generated less outgassing from the cured products obtained than the curable compositions of Comparative Examples.
• the curable compositions of Examples are also excellent in sensitivity, adhesion, undercut suppression, and solubility.
• the curable composition of each example can obtain the same effect even if it is irradiated with KrF rays instead of i rays.
• Conditions for KrF ray irradiation include, for example, exposure light: KrF ray (wavelength: 248 nm), exposure amount: 10 mJ/cm 2 to 500 mJ/cm 2 , maximum instantaneous illuminance: 250,000,000 W/m 2 (average illuminance: 30 ,000 W/m 2 ), pulse width: 30 ns, frequency: 4 kHz.

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