Compositions, films, optical filters, solid-state image sensors, and compounds

Abstract

The present invention provides compositions, films, optical filters, solid-state image sensors, and compounds that can form films with excellent heat resistance and suppressed color transfer. [Solution] A composition comprising a compound represented by formula (1) or formula (2), a curable compound, and a solvent. JPEG2026054591000046.jpg46170

Description

[Technical Field]

[0001] The present invention relates to bisthiazole fused ring s-indacene compounds and compositions containing the same. The present invention also relates to films, optical filters, and solid-state image sensors using compositions containing bisthiazole fused ring s-indacene compounds. [Background technology]

[0002] Solid-state image sensors such as CCDs (charge-coupled devices) and CMOSs ​​(complementary metal-oxide-semiconductors) are used in video cameras, digital still cameras, and mobile phones with camera functions. These solid-state image sensors are also equipped with optical filters, such as color filters. Color filters are manufactured, for example, using compositions containing colorants.

[0003] Patent Document 1 describes the manufacture of a color filter and the like using a composition containing a coloring agent that includes a specific xanthene dye. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2014 / 192973 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, there has been a demand for further improvements in heat resistance of films obtained using compositions containing colorants.

[0006] Furthermore, the inventors' investigations revealed that the films obtained from the composition disclosed in Patent Document 1 are prone to changes in spectral characteristics before and after heating, indicating room for improvement in heat resistance. They also found that the films are prone to color transfer to adjacent films.

[0007] Therefore, an object of the present invention is to provide a composition that can form a film with excellent heat resistance and suppression of color transfer. Furthermore, the present invention is to provide a film, an optical filter, a solid-state image sensor, and a compound. [Means for solving the problem]

[0008] The present invention provides the following:

[0009] <1> A composition comprising a compound represented by formula (1) or formula (2), a curable compound, and a solvent; [ka] In formula (1), R 1 ~R 6 Each of these independently represents a hydrogen atom or a substituent; In formula (2), R 11 ~R 16 Each of these independently represents a hydrogen atom or a substituent. <2> The above curable compound includes a polymerizable compound. <1> The composition described above. <3> Furthermore, it contains a photopolymerization initiator, <1> or <2> The composition described above. <4> <1> ~ <3> A film obtained using any one of the compositions described in the following. <5> <4> An optical filter containing the film described above. <6> <4> A solid-state image sensor containing the film described above. <7> Compounds represented by formula (1); [ka] In formula (1), R 1 ~R 6 Each of these independently represents a hydrogen atom or a substituent. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a composition that can form a film with excellent heat resistance and suppression of color transfer. Furthermore, the present invention can provide a film, an optical filter, a solid-state image sensor, and a compound. [Modes for carrying out the invention]

[0011] The details of the present invention will be described in detail below. In this specification, "~" is used to mean that the numbers before and after it include the lower and upper limits, respectively. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, weight-average molecular weight and number-average molecular weight are defined as polystyrene equivalent values ​​measured by gel permeation chromatography (GPC). In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, infrared radiation refers to light (electromagnetic waves) with a wavelength of 700 to 2500 nm. In this specification, total solids refers to the total mass of the components of the composition excluding the solvent. In this specification, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended function is achieved.

[0012] <Composition> The composition of the present invention is characterized by comprising a compound represented by formula (1) or formula (2), a curable compound, and a solvent.

[0013] The present invention provides a composition that can form a film with excellent heat resistance and suppressed color transfer. The reasons for these effects are presumed to be as follows.

[0014] The compounds represented by formula (1) or formula (2) have a highly planar structure, and are therefore presumed to readily form associations in the film and have high thermal stability. For this reason, a film with excellent heat resistance can be formed by using the composition of the present invention. Furthermore, it is presumed that the ease with which the compounds form associations in the film suppresses their movement and prevents them from leaching out of the film. For this reason, it is presumed that a film in which color transfer to adjacent films is suppressed can be formed by using the composition of the present invention.

[0015] The composition of the present invention can be used as a composition for forming optical filters. Examples of optical filters include color filters and infrared transmission filters. More specifically, the composition of the present invention can be preferably used as a composition for forming pixels in a color filter or as a composition for forming an infrared transmission filter. Examples of pixel types include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0016] The following describes each component used in the composition of the present invention.

[0017] <<Specific compounds (compounds represented by formula (1) or formula (2))>> The composition of the present invention contains a compound represented by formula (1) or formula (2). For the reason that the effects of the present invention are more significantly exerted, the composition of the present invention preferably contains a compound represented by formula (1). Hereinafter, the compound represented by formula (1) or formula (2) is also referred to as a specific compound.

[0018]

Chemical formula

[0019] In formula (1), R 1 ~R 6 each independently represents a hydrogen atom or a substituent; In formula (2), R 11 ~R 16 each independently represents a hydrogen atom or a substituent.

[0020] Examples of the substituents represented by R 1 ~R 6 in formula (1) and R 11 ~R 16 in formula (2) include the groups exemplified by the substituent T described below, the group represented by the formula (R-100) described below, and the group represented by the formula (R-200) described below, and an alkyl group, an aryl group, a heteroaryl group or a silyl group.

[0021] R 1 and R 6 in formula (1), and R 11 and R 16 in formula (2) are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or a silyl group. R 2 and R 5 in formula (1), and R 12 and R 15 in formula (2) are each independently preferably an alkyl group, an aryl group, a heteroaryl group, an alkenyl group or an alkynyl group. R 3 and R 4 in formula (1), and R13 and R 14 Each of these is preferably independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom.

[0022] Examples of the halogen atoms mentioned above include chlorine atoms, fluorine atoms, bromine atoms, and iodine atoms.

[0023] The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 10. The alkyl group can be linear, branched, or cyclic, with linear or branched being preferred. The alkyl group may have substituents or may be unsubstituted. Examples of substituents include those listed in substituent T below, the group represented by formula (R-100), and the group represented by formula (R-200), with hydroxyl groups, alkoxy groups, aryl groups, aryloxy groups, heteroaryl groups, heteroaryloxy groups, halogen atoms, the group represented by formula (R-100), or the group represented by formula (R-200) being preferred.

[0024] The number of carbon atoms in the above alkenyl and alkynyl groups is preferably 1 to 20, and more preferably 1 to 10. The lukenyl and alkynyl groups are preferably linear or branched. The lukenyl and alkynyl groups may have substituents or may be unsubstituted. Examples of substituents include the groups listed as substituent T later described, the group represented by formula (R-100), and the group represented by formula (R-200), and are preferably hydroxyl groups, alkoxy groups, aryl groups, aryloxy groups, heteroaryl groups, heteroaryloxy groups, halogen atoms, the group represented by formula (R-100), or the group represented by formula (R-200).

[0025] The number of carbon atoms in the above aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents or may be unsubstituted. Examples of substituents include the group listed as substituent T later described, the group represented by formula (R-100), and the group represented by formula (R-200), and is preferably a hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heteroaryl group, heteroaryloxy group, halogen atom, the group represented by formula (R-100), or the group represented by formula (R-200).

[0026] The number of carbon atoms constituting the ring of the heteroaryl group described above is preferably 1 to 10, and more preferably 1 to 5. Examples of heteroatoms constituting the ring of the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. The heteroaryl group is preferably a monoring or a fused ring with 2 to 8 condensation units, and more preferably a monoring or a fused ring with 2 to 4 condensation units. The heteroaryl group may have substituents or may be unsubstituted. Examples of substituents include the group listed as substituent T described later, the group represented by formula (R-100), and the group represented by formula (R-200), and is preferably a hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heteroaryl group, heteroaryloxy group, halogen atom, the group represented by formula (R-100), or the group represented by formula (R-200).

[0027] The silyl group mentioned above is the group represented by formula (Si-1). [ka]

[0028] In formula (Si-1), R si1 ~R si3 Each of these independently represents an alkyl group or an aryl group, and * represents a bond. si1 ~R si3Preferably, each of these is an alkyl group independently.

[0029] R si1 ~R si3 The number of carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group can be linear, branched, or cyclic, with linear or branched being preferred and branched being more preferred. The alkyl group may have substituents or may be unsubstituted. Examples of substituents include the group listed in substituent T below, the group represented by formula (R-100), and the group represented by formula (R-200), and are preferably a hydroxyl group, alkoxy group, aryl group, aryloxy group, heteroaryl group, heteroaryloxy group, halogen atom, the group represented by formula (R-100), or the group represented by formula (R-200).

[0030] R si1 ~R si3 The number of carbon atoms in the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents or may be unsubstituted. Examples of substituents include the groups listed in substituent T below, the group represented by formula (R-100), and the group represented by formula (R-200), and are preferably hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heteroaryl groups, heteroaryloxy groups, halogen atoms, the group represented by formula (R-100), or the group represented by formula (R-200).

[0031] -Regarding substituent T- Examples of substituent T include the following groups. Halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), cycloalkyl groups (preferably cycloalkyl groups having 5 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl groups having 6 to 30 carbon atoms), heteroaryl groups (preferably heteroaryl groups having 1 to 30 carbon atoms), amino groups (preferably amino groups having 0 to 30 carbon atoms), alkoxy groups (preferably carbon atoms) 1-30 alkoxy groups), aryloxy groups (preferably aryloxy groups with 6-30 carbon atoms), heteroaryloxy groups (preferably heteroaryloxy groups with 1-30 carbon atoms), acyl groups (preferably acyl groups with 2-30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups with 2-30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl groups with 7-30 carbon atoms), heteroaryloxycarbonyl groups (preferably heteroaryloxycarbonyl groups with 2-30 carbon atoms), acyloxy groups (preferably (C2-C30 acyloxy group), acylamino group (preferably C2-C30 acylamino group), aminocarbonylamino group (preferably C2-C30 aminocarbonylamino group), alkoxycarbonylamino group (preferably C2-C30 alkoxycarbonylamino group), aryloxycarbonylamino group (preferably C7-C30 aryloxycarbonylamino group), sulfamoyl group (preferably C0-C30 sulfamoyl group), sulfamoylamino group (preferably C0-C30 sulfamoyl amino group), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably a heteroarylthio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms),Aryl sulfonylamino group (preferably aryl sulfonylamino group having 6 to 30 carbon atoms), heteroaryl sulfonyl group (preferably heteroaryl sulfonyl group having 1 to 30 carbon atoms), heteroaryl sulfonylamino group (preferably heteroaryl sulfonylamino group having 1 to 30 carbon atoms), alkyl sulfinyl group (preferably alkyl sulfinyl group having 1 to 30 carbon atoms), aryl sulfinyl group (preferably aryl sulfinyl group having 6 to 30 carbon atoms), heteroaryl sulf Nyl groups (preferably heteroarylsulfinyl groups having 1 to 30 carbon atoms), ureido groups (preferably ureido groups having 1 to 30 carbon atoms), hydroxyl groups, nitro groups, carboxyl groups, sulfo groups, phosphoric acid groups, carboxylic acid amide groups, sulfonic acid amide groups, imide groups, phosphino groups, mercapto groups, cyano groups, alkylsulfino groups, arylsulfino groups, arylazo groups, heteroarylazo groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, hydrazino groups, and imino groups. These groups may have further substituents if they are further substituted. Examples of substituents include the groups described above under substituent T, and the groups represented by formula (R-100) and formula (R-200) shown below.

[0032] -Regarding the base represented by formula (R-100)- -O-(R r1 -O) m -R r2 ...(R-100)

[0033] In formula (R-100), R r1 R represents an alkylene group with 1 to 10 carbon atoms. r2 represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms, and m represents an integer from 1 to 30.

[0034] -Regarding the base represented by formula (R-200)- -L R1 -(Y R1 ) n ...(R-200) In formula (R-200), L R1represents a single bond or an n+1 valent linking group, Y R1 represents an acidic or basic group. n represents an integer from 1 to 4, L R1 If it is a single bond, then n is 1.

[0035] L in formula (R-200) R1 represents a single bond or an n+1 valent linking group. R1 If it is a basic group, L R1 It is preferable that the linking group is an n+1 valent group.

[0036] L R1 The n+1 valent linking groups represented by include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, -O-, -S-, -CO-, -COO-, -OCO-, -SO2-, and -NR. L10 -, -N<, -NR L10 CO-, -CONR L10 -, -NR L10 SO2-, -SO2NR L10 - and groups consisting of combinations thereof are examples. L10 represents a hydrogen atom, an alkyl group, or an aryl group.

[0037] The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Furthermore, the aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 5. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The heterocyclic group is preferably a monocyclic ring or a fused ring with 2 to 4 condensation units. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatoms constituting the ring of the heterocyclic group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. Aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups may have substituents. Examples of substituents include alkyl groups and aryl groups.

[0038] Y in formula (R-200) R1 Y represents an acidic or basic group. R1 Examples of acid groups represented include carboxyl groups, sulfo groups, phosphate groups, boronic acid groups, imido acid groups, and salts thereof. Examples of atoms or groups of atoms constituting the salt include alkali metal ions (Li + kaNa + , K + (e.g.), alkaline earth metal ions (Ca 2+ Mg 2+ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. Examples of imido acid groups include -SO2NHSO2R X1 -CONHSO2R X2 -CONHCOR X3 or -SO2NHCOR X4 Preferably, -SO2NHSO2R X1 -CONHSO2R X2 , or -SO2NHCOR X4 More preferable is -SO2NHSO2R X1 or -CONHSO2R X2 This is even more preferable. X1 ~R X4 Each of these independently represents an alkyl group or an aryl group. X1 ~R X4 The alkyl and aryl groups represented by may have substituents. The substituents are preferably halogen atoms, and more preferably fluorine atoms. X1 ~R X4 Each of these is preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The alkyl group containing a fluorine atom has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group containing a fluorine atom has 6 to 20 carbon atoms, more preferably 6 to 12, and even more preferably 6.

[0039] Y R1 Examples of basic groups represented by include amino groups, pyridinyl groups and their salts, ammonium groups, and phthalimidomethyl groups. Examples of atoms or groups of atoms constituting the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions. Examples of amino groups include -NR x11 R x12 Examples include the group represented by and the cyclic amino group.

[0040] -NR x11 R x12 In a base represented by R x11 and R x12 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred, and linear is more preferred. The alkyl group may have substituents. Examples of substituents include substituent T mentioned above. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents. Examples of substituents include substituent T mentioned above.

[0041] Examples of cyclic amino groups include pyrrolidine, piperidine, piperazine, and morpholine groups. These groups may further have substituents. Examples of substituents include the substituent T mentioned above.

[0042] In formula (R-200), n represents an integer between 1 and 4, preferably 1 or 2, and more preferably 1.

[0043] The specified compound may be a pigment or a dye. Furthermore, the specified compound may be a pigment derivative. When the specified compound is used as a pigment derivative, it is preferable that the specified compound has a group represented by formula (R-200) as a substituent.

[0044] Specific examples of the particular compounds include compounds 1-1 to 1-8 and 2-1 to 2-4 shown below. In the structural formulas shown below, Me represents a methyl group, and TIPS represents a triisopropylsilyl group. [ka] [ka]

[0045] The maximum absorption wavelength of a particular compound is preferably in the range of 400 to 700 nm, more preferably in the range of 450 to 650 nm, and even more preferably in the range of 500 to 600 nm.

[0046] The specific compound is preferably a coloring agent, and more preferably a chromatic coloring agent.

[0047] The content of the specific compound (a compound represented by formula (1) or formula (2)) in the total solid content of the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. Furthermore, the upper limit of the content of the specific compound is preferably 65% ​​by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less. The composition of the present invention may contain only one specific compound, or it may contain two or more specific compounds. If it contains two or more specific compounds, it is preferable that their total amount falls within the above range. When the composition of the present invention contains two or more specific compounds, the composition of the present invention is The compound may contain two or more compounds represented by formula (1), or two or more compounds represented by formula (2), or it may contain both the compound represented by formula (1) and the compound represented by formula (2).

[0048] <<Curable compound>> The composition of the present invention contains a curable compound. Examples of curable compounds include polymerizable compounds and resins. The resin may be a non-polymerizable resin (a resin without polymerizable groups) or a polymerizable resin (a resin having polymerizable groups). Examples of polymerizable groups include ethylenically unsaturated bond-containing groups, cyclic ether groups, methylol groups, and alkoxymethyl groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, vinylphenyl groups, allyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, and (meth)acryloylamide groups, with (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups being preferred, and (meth)acryloyloxy groups being more preferred. Examples of cyclic ether groups include epoxy groups and oxetanyl groups, with epoxy groups being preferred.

[0049] It is preferable to use a curable compound that contains at least a resin. Furthermore, when the composition of the present invention is used as a composition for photolithography, it is preferable to use a resin and a polymerizable compound (preferably a polymerizable monomer that is a monomer-type polymerizable compound) as the curable compound, and it is more preferable to use a resin and a polymerizable monomer (a monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group.

[0050] (polymerizable compound) Examples of polymerizable compounds include compounds having an ethylenically unsaturated bond-containing group, compounds having a cyclic ether group, compounds having a methylol group, and compounds having an alkoxymethyl group. Compounds having an ethylenically unsaturated bond-containing group can preferably be used as radical polymerizable compounds. Compounds having a cyclic ether group can preferably be used as cationic polymerizable compounds.

[0051] Examples of polymerizable compounds of the resin type include resins containing repeating units having polymerizable groups.

[0052] The molecular weight of monomer-type polymerizable compounds (polymerizable monomers) is preferably less than 2000, and more preferably 1500 or less. The lower limit of the molecular weight of polymerizable monomers is preferably 100 or more, and more preferably 200 or more. The weight-average molecular weight (Mw) of resin-type polymerizable compounds is preferably 2000 to 2000000. The upper limit of the weight-average molecular weight is preferably 1000000 or less, and more preferably 500000 or less. The lower limit of the weight-average molecular weight is preferably 3000 or more, and more preferably 5000 or more.

[0053] The polymerizable monomer having an ethylenically unsaturated bond-containing group is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include the compounds described in paragraphs 0075-0083 of International Publication No. 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

[0054] Compounds containing ethylenically unsaturated bond groups include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as 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 (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and compounds in which the (meth)acryloyl group of these compounds is linked via ethylene glycol and / or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer). Furthermore, compounds containing ethylenically unsaturated bond groups include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A-TMMT), and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD). Other options include HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronics TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin Nakamura Chemical Industry 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 (both manufactured by Taisei Fine Chemical Co., Ltd.), and Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0055] As compounds containing ethylenically unsaturated bond groups, it is also preferable to use trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0056] It is also preferable to use a compound having both an ethylenically unsaturated bond-containing group and a urethane bond (hereinafter also referred to as a polymerizable compound having a urethane bond) as the compound having an ethylenically unsaturated bond-containing group. By using such a compound, the heat resistance of the resulting film can be further improved. It is presumed that this effect is obtained because the urethane bond portion forms a physical cross-linking structure through intermolecular hydrogen bonding.

[0057] Polymerizable compounds having a urethane bond include, for example, urethane (meth)acrylates obtained by reacting a hydroxyl-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl-containing (meth)acrylate.

[0058] Examples of the above-mentioned (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0059] Examples of the polyfunctional isocyanates mentioned above include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; and their bilets, isocyanate nulates, trimethylolpropane adducts, etc.

[0060] Polymerizable compounds having urethane bonds can also be those described in paragraphs 0308 to 0315 of Japanese Patent Publication No. 2022-173080.

[0061] Compounds containing ethylenically unsaturated bond-containing groups can also be compounds having acidic groups such as carboxyl groups, sulfo groups, and phosphate groups. Examples of commercially available such compounds include Arronix M-305, M-510, M-520, and Arronix TO-2349 (manufactured by Toagosei Co., Ltd.).

[0062] Compounds having an ethylenically unsaturated bond-containing group can also be compounds having a caprolactone structure. For compounds having a caprolactone structure, refer to paragraphs 0042 to 0045 of Japanese Patent Publication No. 2013-253224, which are incorporated herein by reference. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.

[0063] As compounds having an ethylenically unsaturated bond-containing group, compounds having an ethylenically unsaturated bond-containing group and an alkylene oxy group can also be used. Such compounds are preferably compounds having an ethylenically unsaturated bond-containing group and an ethylene oxy group and / or a propylene oxy group, more preferably compounds having an ethylenically unsaturated bond-containing group and an ethylene oxy group, and even more preferably 3-6 functional (meth)acrylate compounds having 4-20 ethylene oxy groups. Examples of commercially available products include SR-494, a tetrafunctional (meth)acrylate having 4 ethylene oxy groups manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutylene oxy groups manufactured by Nippon Kayaku Co., Ltd.

[0064] As compounds containing ethylenically unsaturated bond groups, polymerizable compounds having a fluorene skeleton can also be used. Commercially available examples include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0065] As for compounds containing ethylenically unsaturated bond groups, it is also preferable to use compounds that substantially do not contain environmentally regulated substances such as toluene. Examples of commercially available such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

[0066] Compounds having a cyclic ether group include compounds having an epoxy group and compounds having an oxetanyl group, with compounds having an epoxy group being preferred. Compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more.

[0067] The compound having a cyclic ether group may be a low molecular weight compound (e.g., molecular weight less than 1000) or a high molecular weight compound (macromolecule) (e.g., molecular weight 1000 or more; in the case of a polymer, weight-average molecular weight 1000 or more). The weight-average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight-average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0068] As compounds having a cyclic ether group, the compounds described in paragraphs 0034 to 0036 of Japanese Patent Publication No. 2013-011869, the compounds described in paragraphs 0147 to 0156 of Japanese Patent Publication No. 2014-043556, the compounds described in paragraphs 0085 to 0092 of Japanese Patent Publication No. 2014-089408, and the compounds described in Japanese Patent Publication No. 2017-179172 can also be used.

[0069] Commercially available compounds containing cyclic ether groups include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX-850 (all manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, and EPOLEAD PB. 3600, PB 4700 (all manufactured by Daicel Corporation), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (all manufactured by Daicel Corporation), jER1031S, jER157S65, jER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation), Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX (all manufactured by Toagosei Co., Ltd.), Adegaglycyrrhizol Examples include ED-505 (manufactured by ADEKA Corporation, epoxy group-containing monomer), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (all manufactured by Osaka Organic Chemical Industry Co., Ltd., oxetanyl group-containing monomer).

[0070] Compounds having a methylol group (hereinafter also referred to as methylol compounds) include compounds in which the methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Compounds having an alkoxymethyl group (hereinafter also referred to as alkoxymethyl compounds) include compounds in which the alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Preferred compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluryl, methylolated glycoluryl, alkoxymethylated urea, and methylolated urea. Compounds described in paragraphs 0134 to 0147 of Japanese Patent Publication No. 2004-295116 and paragraphs 0095 to 0126 of Japanese Patent Publication No. 2014-089408 can also be used.

[0071] (resin) The composition of the present invention may use a resin as the curable compound. It is preferable to use a curable compound that contains at least a resin. The resin is used, for example, to disperse pigments or other materials in the composition, or as a binder. A resin primarily used to disperse pigments or other materials in a composition is also called a dispersant. However, such uses of the resin are merely examples, and the resin may be used for purposes other than those mentioned above. A resin having polymerizable groups also falls under the category of a polymerizable compound.

[0072] The weight-average molecular weight of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0073] Examples of resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, and polyurea resins. One of these resins may be used alone, or two or more may be used in mixture form. Among cyclic olefin resins, norbornene resin is preferred from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Furthermore, the resins include the resins described in paragraphs 0091-0099 of International Publication No. 2022 / 065215, the blocked polyisocyanate resin described in Japanese Patent Publication No. 2016-222891, the resins described in Japanese Patent Publication No. 2020-122052, the resins described in Japanese Patent Publication No. 2020-111656, the resins described in Japanese Patent Publication No. 2020-139021, the resins described in Japanese Patent Publication No. 2017-138503 that include structural units having a ring structure in the main chain and structural units having biphenyl groups in the side chains, the resins described in paragraphs 0199-0233 of Japanese Patent Publication No. 2020- The alkali-soluble resin described in Japanese Patent Publication No. 186325, the resin represented by Formula 1 described in Korean Published Patent No. 10-2020-0078339, the copolymer containing epoxy and acid groups described in International Publication No. 2022 / 030445, the resin described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Application Publication No. 2020-186325, the resin represented by Formula 1 described in Korean Published Patent No. 10-2020-0078339, the resin described in Japanese Patent Application Publication No. 2021-134350, and the copolymer described in Japanese Patent Application Publication No. 2020-041046 can also be used. Furthermore, a resin having a fluorene skeleton can preferably be used as the resin. An example of a resin having a fluorene skeleton is the resin described in U.S. Patent Application Publication No. 2017 / 0102610.Furthermore, as the resin, the resin described in paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325, the resin represented by formula 1 described in Korean Published Patent No. 10-2020-0078339, the resin described in Japanese Patent Publication No. 2021-134350, and the resin described in Japanese Patent Publication No. 2022-174597 can also be used.

[0074] It is preferable to use a resin having acidic groups as the resin. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups. These acidic groups may be present individually or in combination of two or more types. The resin having acidic groups can also be used as a dispersant. The acid value of the resin having acidic groups is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, even more preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

[0075] It is also preferable to use a resin having polymerizable groups. The polymerizable groups are preferably ethylenically unsaturated bond-containing groups and cyclic ether groups, and more preferably ethylenically unsaturated bond-containing groups.

[0076] The resin may also preferably contain a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acidic groups is greater than the amount of basic groups. As an acidic dispersant (acidic resin), it is preferable that the amount of acidic groups is 70 mol% or more when the total amount of acidic groups and basic groups is set to 100 mol%. The acidic group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH / g. Furthermore, a basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acidic groups. As a basic dispersant (basic resin), it is preferable that the amount of basic groups exceeds 50 mol% when the total amount of acidic groups and basic groups is set to 100 mol%. The basic group of the basic dispersant is preferably an amino group.

[0077] The resin used as a dispersant is preferably a graft resin. Details of graft resins can be found in paragraphs 0025 to 0094 of Japanese Patent Application Publication No. 2012-255128, which are incorporated herein by reference.

[0078] The resin used as a dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of its main chain and side chains. Preferably, the polyimine-based dispersant has a main chain having a substructure with functional groups having a pKa of 14 or less, and side chains with 40 to 10,000 atoms, and contains a basic nitrogen atom in at least one of its main chain and side chains. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basic properties. For polyimine-based dispersants, refer to paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, the contents of which are incorporated herein by reference.

[0079] The resin used as a dispersant is preferably a resin with a structure in which multiple polymer chains are bonded to the core. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0080] The resin used as a dispersant is preferably a resin containing repeating units having ethylenically unsaturated bond-containing groups in their side chains. The content of repeating units having ethylenically unsaturated bond-containing groups in their side chains is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol% of the total repeating units of the resin.

[0081] As a dispersant, the resin described in Japanese Patent Publication No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, polyethyleneimine having polyester side chains described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066687, the block polymer having acrylamide structural units described in Japanese Patent Publication No. 2020-066688, and the dispersant described in International Publication No. 2016 / 104803 can also be used.

[0082] Dispersants are also available commercially, and specific examples include the DISPERBYK series from BIC Chemie, the SOLSPERSE series from Lubrizol Nippon, the Efka series from BASF, and the Azisper series from Ajinomoto Fine Techno Co., Ltd. In addition, the products described in paragraph 0129 of Japanese Patent Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Publication No. 2017-194662 can also be used as dispersants.

[0083] The content of the curable compound in the total solid content of the composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 94% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less.

[0084] When the composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound in the total solid content of the composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0085] When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer in the total solid content of the composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0086] When the composition of the present invention contains a compound having an ethylenically unsaturated bond-containing group as a curable compound, the content of the compound having an ethylenically unsaturated bond-containing group in the total solid content of the composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0087] When the composition of the present invention contains a compound having a cyclic ether group as a curable compound, the content of the compound having a cyclic ether group in the total solid content of the composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0088] When the composition of the present invention contains a resin as a curable compound, the resin content in the total solids of the composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

[0089] When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant in the total solid content of the composition is preferably 0.1 to 40% by mass. The upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Furthermore, the content of the resin as a dispersant is preferably 1 to 100 parts by mass per 100 parts by mass of pigment. The upper limit is preferably 80 parts by mass or less, more preferably 75 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.

[0090] The composition of the present invention may contain only one curable compound or two or more curable compounds. When two or more curable compounds are included, it is preferable that their total amount be within the above range.

[0091] <<Solvent>> The compositions of the present invention contain a solvent. Examples of solvents include water and organic solvents, with organic solvents being preferred. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For further details, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. Ester solvents and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of 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, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene Examples include propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, the amount of aromatic hydrocarbons used as organic solvents (benzene, toluene, xylene, ethylbenzene, etc.) may be reduced for environmental reasons (for example, it may be possible to reduce the amount to 50 ppm (parts per million) or less, 10 ppm or less, or 1 ppm or less relative to the total amount of organic solvent).

[0092] It is preferable that the metal content of the organic solvent be low. For example, the metal content of the organic solvent is preferably 10 ppb (parts per billion) or less by mass. If necessary, an organic solvent with a metal content at the ppt (parts per trillion) level may be used; such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).

[0093] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using filters. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0094] Organic solvents may contain isomers (compounds with the same number of atoms but different structures). Furthermore, they may contain only one type of isomer or multiple types.

[0095] The peroxide content in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially peroxide-free.

[0096] The solvent content in the composition is preferably 10 to 97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less. The composition may contain only one type of solvent or two or more types. If two or more types are included, it is preferable that their total amount falls within the above range.

[0097] <<Other colorants>> The composition of the present invention may contain colorants other than the specific compounds described above (hereinafter also referred to as "other colorants"). Examples of other colorants include chromatic colorants and black colorants. Other colorants may be pigments or dyes. Pigments and dyes may be used in combination.

[0098] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment can be determined by observing the primary particles of the pigment with a transmission electron microscope and obtaining the resulting photograph. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding equivalent circle diameter is calculated as the primary particle diameter of the pigment. In this specification, the average primary particle diameter is the arithmetic mean of the primary particle diameters of 400 primary particles of pigment. Furthermore, primary particles of pigment refer to independent particles that are not aggregated.

[0099] The crystallite size of the pigment is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the full width at half maximum of the diffraction angle peak using an X-ray diffractometer, and is calculated using Scherrer's formula. The crystallite size of the pigment can be adjusted by known methods such as adjusting the manufacturing conditions or grinding after manufacturing.

[0100] The specific surface area of ​​the pigment is 1 to 300 m². 2 It is preferable that it be / g. The lower limit is 10m 2 It is preferable that the amount be 30m or more. 2 It is more preferable that the amount is 250mg or more. The upper limit is 250mg. 2 It is preferable that it be less than / g, and 200m 2 It is more preferable that the value be less than or equal to / g. The specific surface area can be measured according to DIN 66131: determination of the specific surface area of ​​solids by gas adsorption, in accordance with the BET (Brunauer, Emmett, and Teller) method.

[0101] (Coloring agent) Examples of chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants.

[0102] Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds. Diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds are preferred, and diketopyrrolopyrrole compounds are more preferred. Furthermore, the red colorant is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.

[0103] Specific examples of red colorants include CI (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, Examples of red pigments include 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, and 297. Furthermore, as a red coloring agent, the compound described in paragraph 0034 of International Publication No. 2022 / 085485 and the brominated diketopyrrolopyrrole compound described in Japanese Patent Publication No. 2020-085947 can also be used.

[0104] As the red coloring agent, CI Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, CI Pigment Red 254, 264, and 272 are more preferred, and CI Pigment Red 254 and 264 are even more preferred.

[0105] Examples of green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Furthermore, the green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

[0106] Specific examples of green colorants include green pigments such as CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Alternatively, zinc phthalocyanine halides, which have an average of 10-14 halogen atoms, 8-12 bromine atoms, and 2-5 chlorine atoms per molecule, can also be used as green colorants. A specific example is the compound described in International Publication No. 2015 / 118720. Furthermore, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as green colorants.

[0107] As the green coloring agent, CI Pigment Green 7, 36, 58, 62, and 63 are preferred.

[0108] Examples of orange colorants include diketopyrrolopyrrole compounds and azo compounds. Preferably, the orange colorant is a pigment (orange pigment). Specific examples of orange colorants include CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.

[0109] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a pigment (yellow pigment). Specific examples of yellow colorants include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120 Examples of yellow pigments include 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, and 236.

[0110] As a yellow coloring agent, a nickel azobarbiturate complex with the following structure can also be used. [ka]

[0111] As a yellow coloring agent, the compounds described in paragraphs 0031-0033 of International Publication No. 2022 / 085485, the methine dye described in Japanese Patent Publication No. 2019-073695, and the methine dye described in Japanese Patent Publication No. 2019-073696 can be used.

[0112] Examples of purple colorants include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred. The purple colorant is preferably a pigment (purple pigment). Specific examples of purple colorants include purple pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0113] Examples of blue colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The blue colorant is preferably a pigment (blue pigment). Specific examples of blue colorants include blue pigments such as CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, aluminum phthalocyanine compounds containing a phosphorus atom can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022-0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478.

[0114] Dyes can also be used as chromatic colorants. There are no particular restrictions on the dyes used, and known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes. Xanthene dyes are preferred.

[0115] A pigment polymer can also be used as a chromatic colorant. The pigment polymer is preferably a dye that is dissolved in a solvent before use. The pigment polymer may also form particles. When the pigment polymer is in particle form, it is usually used in a dispersed state in a solvent. Particle-form pigment polymers can be obtained, for example, by emulsion polymerization, and the compound and production method described in Japanese Patent Application Publication No. 2015-214682 are specific examples. The pigment polymer has two or more pigment structures in one molecule, and preferably three or more pigment structures. There is no particular upper limit, but it can be 100 or less. The multiple pigment structures in one molecule may be the same pigment structure or different pigment structures. The weight-average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30000 or less, and even more preferably 20000 or less. The pigment polymer can also be a compound described in Japanese Patent Publication No. 2011-213925, Japanese Patent Publication No. 2013-041097, Japanese Patent Publication No. 2015-028144, Japanese Patent Publication No. 2015-030742, International Publication No. 2016 / 031442, etc.

[0116] As a chromatic coloring agent, the following are used: the triarylmethane dye polymer described in Korean Published Patent No. 10-2020-0028160, the xanthene compound described in Japanese Patent Publication No. 2020-117638, the phthalocyanine compound described in International Publication No. 2020 / 174991, the isoindoline compound described in Japanese Patent Publication No. 2020-160279 or salts thereof, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069442, the compound represented by Formula 1 described in Korean Published Patent No. 10-2020-0069730, and the compound described in Korean Published Patent No. 1 Compounds represented by formula 1 described in Japanese Patent Publication No. 0-2020-0069070, compounds represented by formula 1 described in Korean Published Patent No. 10-2020-0069067, compounds represented by formula 1 described in Korean Published Patent No. 10-2020-0069062, zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, isoindoline compounds described in Japanese Patent Publication No. 2020-180176, phenothiazine compounds described in Japanese Patent Publication No. 2021-187913, zinc halide phthalocyanine described in International Publication No. 2022 / 004261, International Zinc halide phthalocyanine described in Publication No. 2021 / 250883, quinophthalone compound represented by Formula 1 in Korean Published Patent No. 10-2020-0030759, polymer dye described in Korean Published Patent No. 10-2020-0061793, colorant described in Japanese Patent Publication No. 2022-029701, isoindoline compound described in International Publication No. 2022 / 014635, aluminum phthalocyanine compound described in International Publication No. 2022 / 024926, compound described in Japanese Patent Publication No. 2022-045895, International Publication No. 2022 / 05005 The compound described in No. 1, the compound described in JP 2020-090676, the compound described in JP 2020-055956, the compound described in JP 2021-031681, the compound described in JP 2022-056354, the compound described in US Patent Application Publication No. 2021 / 0355327, the compound described in International Publication No. 2022 / 065357, the compound described in JP 2020-045436, the compound described in Korean Published Patent No. 10-2021-0146726, the compound described in JP 2018-178039,Compounds described in Chinese Patent Application Publication No. 113881244, Compounds described in Chinese Patent Application Publication No. 113881245, Compounds described in Chinese Patent Application Publication No. 113881246, Compounds described in JP 2022-104822, Compounds described in JP 2022-096701, Compounds described in JP 2020-023652, Green pigment described on pages 80-84 of the Journal of the Color Materials Association (published in 2022), Compounds described in JP 2022-143135, Compounds described in JP 2022-140287, International Publication No. Compounds described in JP 2022 / 136308, perylene compounds described in Chinese Patent Application Publication No. 113061349, cyanide pigments described in Korean Published Patent No. 10-2017-0018993, isoindoline compounds described in JP 2020-180176, compounds described in JP 2023-013209, compounds described in JP 2023-013166, xanthene compounds described in International Publication No. 2023 / 286526, compounds described in JP 2021-155746, compounds described in JP 2021-155747, JP The compounds described in Japanese Patent Publication No. 2021-155748, the compounds described in Japanese Patent Application Publication No. 2021-155749, the compounds described in International Publication No. 2018 / 051876, the compounds described in Japanese Patent Application Publication No. 2020-083981, the compounds described in Japanese Patent Application Publication No. 2023-056463, the compounds described in Japanese Patent Publication No. 2023-515473, the dioxane compounds described in Japanese Patent Publication No. 2022-549530, the pigment preparations described in Japanese Patent Application Publication No. 2022-061494, the diketopyrrolopyrrole pigments described in Japanese Patent Application Publication No. 2023-057917, and the compounds described in Japanese Patent Application Publication No. 2023-061273 The diketopyrrolopyrrole compounds described, the phthalocyanine described in Japanese Patent Publication No. 2023-519314, the quinophthalone described in Japanese Patent Publication No. 2023-080419, the phthalocyanine compounds described in Japanese Patent Publication No. 2023-103177, the isoindoline compounds described in Japanese Patent Publication No. 2020-026521, the squarylium compounds described in Korean Published Patent No. 10-2023-0043000, the squarylium compounds described in Korean Published Patent No. 10-2023-0050069, the diketopyrrolopyrrole compounds described in Japanese Patent Publication No. 2023-127878,Triarylmethane compounds described in Japanese Patent Publication No. 2023-150459, Triarylmethane compounds described in Japanese Patent Publication No. 2023-149735, Core-shell dyes described in Japanese Patent Publication No. 2023-123349, Xanthene compounds described in Japanese Patent Publication No. 2023-543717, Compounds described in Chinese Patent Application Publication No. 116102441, Compounds described in Japanese Patent Publication No. 2023-150459, Compounds described in Japanese Patent Publication No. 2023-167345, Korean Publication Compounds described in Japanese Patent Publication No. 10-2023-0061078, compounds described in Japanese Unexamined Patent Publication No. 2020-183509, colorants described in Japanese Unexamined Patent Publication No. 2020-079395, compounds represented by formula (1) described in U.S. Patent Application Publication No. 2022 / 0119643, dyes described in Japanese Unexamined Patent Publication No. 2023-048989, compounds described in Japanese Unexamined Patent Publication No. 2024-014738, pigments described in Chinese Patent Application Publication No. 115873417, etc. may also be used. Furthermore, the colorant may be a rotaxane. The pigment skeleton may be used in the cyclic structure of the rotaxane, in the rod-like structure, or in both structures.

[0117] Two or more chromatic colorants may be used in combination. Furthermore, when two or more chromatic colorants are used in combination, the combination of two or more chromatic colorants may form a black color. Examples of such combinations include the following embodiments (1) to (7). When the composition of the present invention contains two or more chromatic colorants, and exhibits a black color through a combination of two or more chromatic colorants, the composition of the present invention can be preferably used as a composition for forming an infrared transmission filter. (1) An embodiment containing a red coloring agent and a blue coloring agent. (2) An embodiment containing a red coloring agent, a blue coloring agent, and a yellow coloring agent. (3) An embodiment containing a red coloring agent, a blue coloring agent, a yellow coloring agent, and a purple coloring agent. (4) An embodiment containing a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, and a green coloring agent. (5) An embodiment containing a red coloring agent, a blue coloring agent, a yellow coloring agent, and a green coloring agent. (6) An embodiment containing a red coloring agent, a blue coloring agent, and a green coloring agent. (7) An embodiment containing a yellow coloring agent and a purple coloring agent.

[0118] (Black coloring agent) The black coloring agent is not particularly limited, and known agents can be used. The black coloring agent may be an inorganic black coloring agent or an organic black coloring agent. The black coloring agent is preferably a pigment. In this specification, the term "black coloring agent" refers to a coloring agent that exhibits absorption over the entire wavelength range of 400 to 700 nm.

[0119] Examples of inorganic black colorants include carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black refers to black particles containing titanium atoms, with lower-order titanium oxide and titanium oxynitride being preferred. The titanium black described in paragraph 0044 of International Publication No. 2022 / 085485 can be used. Zirconium nitride powder described in Japanese Patent Application Publication No. 2023-048173 can also be used as an inorganic black colorant.

[0120] Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The organic black colorant can be a compound described in paragraph 0166 of International Publication No. 2022 / 065215. Alternatively, perylene black (such as Lumogen Black FK4280) described in paragraphs 0016-0020 of Japanese Patent Publication No. 2017-226821 or a black azo pigment described in Japanese Patent Publication No. 2022-121935 may be used as the organic black colorant.

[0121] For the black coloring agent, you can also use the black coloring agents listed in sections 294-307 of the Journal of the Color Materials Association, Vol. 96, No. 9, 2023.

[0122] The content of other colorants in the total solids of the composition is preferably 0.1 to 50% by mass. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. Furthermore, the total content of the above-mentioned specific compound and other colorants in the total solid content of the composition is preferably 0.2 to 65% by mass. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. If the composition of the present invention contains two or more other colorants, it is preferable that their total amount is within the above range.

[0123] <<Infrared absorber>> The compositions of the present invention may contain an infrared absorbent. The infrared absorbent may be a dye or a pigment (particle). Examples of infrared absorbents include pyrrolopyrrole compounds, squarylium compounds, crokonium compounds, polymethine compounds, indigo compounds, phthalocyanine compounds, naphthalocyanine compounds, iminium compounds, quaterylene compounds, aminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, oxonol compounds, and hexaphylline compounds, and it is preferable that the infrared absorbent is at least one selected from pyrrolopyrrole compounds, squarylium compounds, polymethine compounds, indigo compounds, phthalocyanine compounds, and naphthalocyanine compounds. Specific examples of these include the compounds described in paragraph 0114 of International Publication No. 2022 / 065215. Furthermore, as infrared absorbers, the compounds described in paragraph 0121 of International Publication No. 2022 / 065215, the compounds described in Table 1 of U.S. Patent No. 11261172, the compounds described in paragraphs 0188 to 0192 of International Publication No. 2022 / 181422, the squarylium compounds described in Japanese Patent Publication No. 2020-075959, the copper complex described in Korean Patent Publication No. 10-2019-0135217, the croconic acid compounds described in Japanese Patent Publication No. 2021-195515, the infrared absorbing dyes described in Japanese Patent Publication No. 2022-022070, the croconium compounds described in International Publication No. 2019 / 021767, the compounds described in Japanese Patent Publication No. 2019-127549, and International Publication No. 2022 / The compound described in Patent Publication No. 059619, the compound described in Japanese Patent Publication No. 2022-151682, the squarylium compound described in Japanese Patent Publication No. 2022-188858, the compound described in Japanese Patent Publication No. 2022-184710, the compound described in Japanese Patent Publication No. 2022-189736, the squarylium compound described in Japanese Patent Publication No. 2023-004570, the squarylium compound described in International Publication No. 2019 / 230660, the compound described in International Publication No. 2020 / 218615, the diiminium compound described in Japanese Patent Publication No. 2023-068643, the squarylium compound described in Japanese Patent Publication No. 2023-052770, the phthalocyanine compound described in Korean Published Patent No. 10-2022-0163680,The indigo monoboron complex described in JP-A No. 2023-073064, the phthalocyanine compound described in JP-A No. 2023-066025, the phthalocyanine compound described in JP-A No. 2020-041127, the indigo compound described in JP-A No. 2023-073064, the indigo compound described in Korean Patent Publication No. 10-2023-0016355, the squarylium compound described in International Publication No. 2019 / 230570, the diiminium compound described in JP-A No. 2023-095824, the compound described in JP-A No. 2023-159964, the compound described in JP-A No. 2023-176615, the compound described in Special Table 2024-500537, the phthalocyanine compound described in JP-A No. 2024-019936, the compound described in Korean Registered Patent No. 10-2575190, the polymethine compound described in JP-A No. 2024-017061, the boron derivative described in Chinese Patent Application Publication No. 116715690, the phthalocyanine compound described in JP-A No. 2024-020454, the compound described in Chinese Patent Application Publication No. 116891482, and the compound described in Special Table 2024-511242 can also be used.

[0124] As the infrared absorber, tungsten oxide represented by the following formula described in paragraph 0025 of European Patent No. 362864 also can be used. M 1 a M 2 b W c O d (P(O) n R m ) e M 1 、M 2 represents an ammonium cation or a metal cation, a is 0.01 to 0.5, b is 0 to 0.5, c is 1, d is 2.5 to 3, e is 0.01 to 0.75, n is 1, 2 or 3, m is 1, 2 or 3, and R represents a hydrocarbon group which may have a substituent.

[0125] The content of the infrared absorber in the total solid content of the composition is preferably 0.1 to 40% by mass. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Furthermore, the total content of the above-mentioned specific compound, other colorants, and infrared absorbers in the total solid content of the composition is preferably 0.5 to 65% by mass. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. When the composition of the present invention contains two or more infrared absorbers, it is preferable that their total amount is within the above range.

[0126] <<Pigment derivative>> The composition of the present invention may contain a pigment derivative. The pigment derivative is used as a dispersion aid. A dispersion aid is a material used to improve the dispersibility of pigments in a composition.

[0127] Examples of pigment derivatives include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acidic group or a basic group.

[0128] Examples of the above-mentioned pigment structures include squarylium pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure, anthraquinone pigment structure, diantraquinone pigment structure, benzoisoindole pigment structure, thiadin indigo pigment structure, azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, perinone pigment structure, benzimidazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure, and benzoxazole pigment structure. Squaryllium pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, phthalocyanine pigment structure, quinacridone pigment structure, and benzimidazolone pigment structure are preferred, and squarylium pigment structure and pyrrolopyrrole pigment structure are more preferred.

[0129] Examples of acidic groups found in pigment derivatives include carboxyl groups, sulfo groups, phosphate groups, boronic acid groups, carboxylic acid amide groups, sulfonic acid amide groups, imido acid groups, and salts thereof. Examples of atoms or groups of atoms constituting the salts include alkali metal ions (Li + kaNa + , K + (e.g.), alkaline earth metal ions (Ca 2+ Mg 2+ Examples include ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions. Examples of carboxylic acid amide groups include -NHCOR X1 A group represented by is preferred. As a sulfonic acid amide group, -NHSO2R X2 A group represented by is preferred. As an imido acid group, -SO2NHSO2R X3 -CONHSO2R X4 -CONHCOR X5 or -SO2NHCOR X6 A group represented by -SO2NHSO2R is preferred. X3 R is more preferable. X1 ~R X6 Each of these independently represents an alkyl group or an aryl group. X1 ~R X6 The alkyl and aryl groups represented by may have substituents. The substituents are preferably halogen atoms, and more preferably fluorine atoms.

[0130] Basic groups found in pigment derivatives include amino groups, pyridinyl groups and their salts, ammonium groups, and phthalimidomethyl groups. Atoms or groups of atoms that make up the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0131] Specific examples of pigment derivatives include compounds described in paragraphs 0037-0054 of International Publication No. 2016 / 035695, compounds described in paragraphs 0061-0086 of International Publication No. 2017 / 146092, compounds described in paragraphs 0017-0068 of International Publication No. 2018 / 230387, compounds described in paragraphs 0085-0099 of International Publication No. 2020 / 054718, compounds described in paragraph 0099 of International Publication No. 2020 / 054718, compounds described in paragraph 0124 of International Publication No. 2022 / 085485, benzimidazolone compounds or salts thereof described in Japanese Patent Publication No. 2018-168244, and compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282.

[0132] The pigment derivative content is preferably 1 to 50 parts by mass per 100 parts by mass of pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0133] <<Photopolymerization initiator>> If the composition of the present invention contains a polymerizable compound, it is preferable that the composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitive to light in the ultraviolet to visible regions are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0134] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and glyoxylate compounds. The photopolymerization initiator is preferably a trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, hexaarylbiimidazole compound, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, glyoxylate compound, or 3-arylsubstituted coumarin compound; more preferably an oxime compound, α-hydroxyketone compound, α-aminoketone compound, or acylphosphine compound; even more preferably an α-aminoketone compound or oxime compound; and particularly preferably an oxime compound.

[0135] Examples of photopolymerization initiators include the compounds described in paragraphs 0065-0111 of JP 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiator described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, the photopolymerization initiator described in International Publication No. 2018 / 221177, the photopolymerization initiator described in International Publication No. 2018 / 110179, the photopolymerization initiator described in JP 2019-043864, the photopolymerization initiator described in JP 2019-044030, the peroxide-based initiator described in JP 2019-167313, and the aminoacetopheno(oxazolidine group) described in JP 2020-055992. Fluorine-based initiators, oxime-based photopolymerization initiators described in JP 2013-190459, polymers described in JP 2020-172619, compounds represented by formula 1 described in International Publication No. 2020 / 152120, compounds described in JP 2021-181406, photopolymerization initiators described in JP 2022-013379, compounds represented by formula (1) described in JP 2022-015747, fluorine-containing fluorene oxime ester-based photoinitiators described in JP 2021-507058, Chinese Patent Publication No. Initiators described in Patent Application Publication No. 110764367, initiators described in Japanese Patent Publication No. 2022-518535, initiators described in International Publication No. 2021 / 175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in Japanese Patent Publication No. 2022-078550, compounds described in Korean Published Patent No. 10-2017-0087330, compounds described in International Publication No. 2022 / 075452, and oxime ester compounds described in Chinese Patent Application Publication No. 110066225. , compounds described in Korean Published Patent No. 10-2022-0076157, compounds described in paragraphs 0042-0062 of International Publication No. 2019 / 013112 having a triarylamine or N-arylcarbazole skeleton, oxime ester-based photopolymerization initiators described in Japanese Patent No. 7219378, photopolymerization initiators described in Korean Published Patent No. 10-2021-0146174, photopolymerization initiators described in International Publication No. 2019 / 013112, photopolymerization initiators described in Japanese Patent Application Publication No. 2023-033731,Examples include the initiator described in JP 2022-515524, the initiator described in JP 2023-517304, the initiator described in Chinese Patent Application Publication No. 114149517, the aminoketone compound described in Chinese Patent Application Publication No. 115925596, the compound described in JP 2023-159489, the compound described in JP 2023-159487, the compound described in Taiwan Patent Application Publication No. 202336003, the compound described in Chinese Patent Application Publication No. 113527138, and the organosilicon compound described in JP 2022-502526.

[0136] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0137] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV), and Irgacure 819 and Irgacure TPO (both manufactured by BASF). Commercially available glyoxylate compounds include Esacure 563 (manufactured by IGM Resins BV).

[0138] Examples of oxime compounds include the compounds described in paragraph 0142 of International Publication No. 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of Japanese Patent Publication No. 2021-173858, and the compounds represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of Japanese Patent Publication No. 2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, and Irgacure Examples include OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, TR-PBG-B (all manufactured by TRONLY), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). Furthermore, it is also preferable to use compounds that do not produce color or compounds that are highly transparent and resistant to discoloration as oxime compounds. Examples of commercially available products include the ADEKA Arclus NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation).

[0139] As photopolymerization initiators, oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 may also be used.

[0140] A compound represented by formula (OX-1) can also be used as a photopolymerization initiator.

[0141] [ka] In formula (OX-1), X 1a This represents a divalent linking group containing at least one selected from the group consisting of aromatic rings and heterocycles. R 1a represents a hydrogen atom or an acyl group, R 2a represents an alkyl group or aryl group, R 3a and R 4a Each of these independently represents a hydrogen atom or an alkyl group. Alk 1 and Alk 2 Each of these independently represents an alkyl group. R 3a and R 4a They may be bonded together to form a ring. Alk 1 and Alk 2 They may be bonded together to form a ring. n represents either 0 or 1.

[0142] X in equation (OX-1) 1aExamples of divalent linking groups represented by include divalent aromatic ring groups, divalent heterocyclic groups, divalent groups formed by linking two or more aromatic ring groups via single bonds or linking groups, divalent groups formed by linking two or more heterocyclic groups via single bonds or linking groups, and divalent groups formed by linking an aromatic ring group and a heterocyclic group via single bonds or linking groups. Examples of linking groups that link aromatic ring groups to each other, heterocyclic groups to each other, or an aromatic ring group and a heterocyclic group include -CH2-, -O-, -CO-, -S-, and -NR. x -And combinations thereof, etc., are examples. x This represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heterocyclic group.

[0143] X in equation (OX-1) 1a It is preferable that the group is represented by any of formulas (X-1) to (X-13), more preferably by formula (X-1), formula (X-2), formula (X-4), formula (X-6), or formula (X-8), and even more preferably by formula (X-2) or formula (X-6). [ka]

[0144] R in the formula X1 ~R X9 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and * represents a bond.

[0145] R X1 ~R X9 The alkyl group represented by is preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.

[0146] R X1 ~R X9The number of carbon atoms in the alkenyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.

[0147] R X1 ~R X9 The number of carbon atoms in the alkynyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heteroaryl groups.

[0148] R X1 ~R X9 The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.

[0149] R X1 ~R X9 The heteroaryl group represented by is preferably a 5-membered or 6-membered ring. The heteroatoms of the heteroaryl group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms of the heteroaryl group is preferably 1 to 3. The heteroaryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0150] R in equation (OX-1) 1a represents a hydrogen atom or an acyl group, and an acyl group is preferred.

[0151] R in equation (OX-1) 2a This represents an alkyl group or an aryl group, and is preferably an alkyl group because the generated radical is highly reactive. R 2aThe number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. 2a The alkyl group represented is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. R 2a The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, but it is preferably an unsubstituted aryl group.

[0152] R in equation (OX-1) 3a and R 4a Each of these independently represents either a hydrogen atom or an alkyl group, and a hydrogen atom is preferred. R 3a and R 4a The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. R 3a and R 4a These may be bonded together to form a ring. The formed ring is preferably a five-membered or six-membered ring, and more preferably a five-membered or six-membered aliphatic hydrocarbon ring.

[0153] Alk in formula (OX-1) 1 and Alk 2Each of these independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have substituents, but is preferably an unsubstituted alkyl group. Alk 1 and Alk 2 The elements may be bonded together to form a ring, and it is preferable that a ring is formed. The formed ring is preferably a 5-membered or 6-membered ring, more preferably a 5-membered or 6-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.

[0154] In formula (OX-1), n ​​represents either 0 or 1, and is preferably 0.

[0155] Specific examples of compounds represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of Japanese Patent Publication No. 2012-113104 and the compounds described in paragraph 0041 of Japanese Patent Publication No. 2012-189997.

[0156] A compound represented by formula (OX-2) can also be used as a photopolymerization initiator.

[0157] [ka]

[0158] In formula (OX-2), R 1b and R 2b Each of these independently represents a substituent, R 3b ~R 7b Each of these independently represents a hydrogen atom or substituent, and Ar 1b n represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and n represents 0 or 1.

[0159] R 1b and R 2b The substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups.

[0160] R 3b ~R 7b The substituents represented by include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl groups and aryl groups are those mentioned above. R 3b ~R 7b It is preferable that it is a hydrogen atom.

[0161] Ar 1b represents an optionally substituted aryl group or an optionally substituted heteroaryl group, and Ar 1b It is preferable that the group is an aryl group which may have substituents. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, with acyl groups being preferred.

[0162] A compound represented by formula (OX-3) can also be used as a photopolymerization initiator.

[0163] [ka]

[0164] In formula (OX-3), Ar 1c represents an aromatic ring group with (k+m+1) valency or a heterocyclic ring group with (k+m+1) valency. Ar 2c represents a (k+2) valent aromatic ring group or a (k+2) valent heterocyclic ring group, R 1c ~R 3c Each of these independently represents a substituent, L 1c is a single bond or CR 11c R 12c Represents R 11c and R 12c Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group. X 1c -CH2-, -N-, -O-, or -S- k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.

[0165] R 1c and R 2c The substituents represented by include alkyl groups and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heteroaryl groups. R 2c It is preferable that the alkyl group has a branched or cyclic structure.

[0166] R 3cExamples of the substituent represented by [the relevant symbol] include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group, and it is preferably an acyl group.

[0167] L 1c represents a single bond or CR 11c R 12c where R 11c and R 12c each independently represent a hydrogen atom, an alkyl group, or an aryl group. The alkyl group and aryl group in R 11c and R 12c are synonymous with the alkyl group and aryl group in R[[ID=1^]] 1c and R 2c When k is 1, L 1c is preferably a single bond.

[0168] X 1c represents -CH2-, -N-, -O-, or -S-, and -O- or -S- is preferred.

[0169] Ar 1c represents a (k + m + 1)-valent aromatic ring group or a (k + m + 1)-valent heterocyclic group, and it is preferably a (k + m + 1)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0170] Ar 2c represents a (k + 2)-valent aromatic ring group or a (k + 2)-valent heterocyclic group, and it is preferably a (k + 2)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0171] k represents 0 or 1, and 0 is preferred. m represents an integer from [0] to 4, and 0 or 1 is preferred, and 1 is more preferred. n represents 0 or 1, and 0 is preferred.

[0172] Note: In the translation of "mは0~4の整数を表し", "from [0]" is added in the translation to make the meaning more explicit as the original might be a bit ambiguous in this regard. Also, some tags like etc. are just preserved as they are as per the instruction.The photoinitiator can also preferably use a ketooxime ester compound having an allyloxy group at the ortho position represented by the formula (OX-4). Examples of such compounds include those described in the specification of Chinese Patent Application Publication No. 117342977.

Chemical formula

[0173] In formula (OX-4), R 1d and R 2d each independently represents an alkyl group, an aryl group or a heterocyclic group; R 3d , R 4d , R 5d , R 6d each independently represents a hydrogen atom, a halogen atom, CN, NO2, CF3, R, OR, SR, SOR, SO2R or NRR‘, R and R‘ each independently represents an alkyl group or an aryl group. When R and R‘ exist simultaneously, R and R‘ may be bonded to form a ring, and one or more -CH2- in the alkyl group or aryl group represented by R and R‘ may each independently be substituted by -O-, -N-, -S-, -CO-, -COO-, -OCO- or a benzene ring; R 7d , R 8d and R 9d each independently represents a hydrogen atom or a methyl group.

[0174] The photoinitiator can also preferably use a compound represented by the formula (OX-5). Examples of such compounds include those described in International Publication No. 2024 / 101219. [[ID=​​​​​​​​​​​Each of these independently represents a hydrocarbon group which may have substituents, and n represents an integer from 0 to 4.

[0176] Specific examples of oxime compounds include the following compounds.

[0177] [ka] [ka] [ka] [ka] [ka]

[0178] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, even more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferable to measure it using a spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0179] As the photopolymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and the solubility in solvents, etc., is improved, making precipitation less likely over time and improving the long-term stability of the composition. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include the compounds described in paragraph 0148 of International Publication No. 2022 / 065215.

[0180] The content of the photopolymerization initiator in the total solid content of the composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The composition may contain only one type of photopolymerization initiator, or it may contain two or more types. If it contains two or more types, it is preferable that their total amount is within the above range.

[0181] <<Hardening agent>> If the composition of the present invention contains a compound having a cyclic ether group, it is preferable that the composition of the present invention further contains a curing agent. Examples of curing agents include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polycarboxylic acids, and thiol compounds. Specific examples of curing agents include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, and pentaerythritol tetrakis(3-mercaptopropionate). The curing agent may also be a compound described in paragraphs 0072 to 0078 of Japanese Patent Publication No. 2016-075720 or a compound described in Japanese Patent Publication No. 2017-036379. The content of the curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 6.0 parts by mass, per 100 parts by mass of the compound having a cyclic ether group.

[0182] <<Surfactants>> The composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a silicone surfactant or a fluorosurfactant. Regarding the surfactant, reference can be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, and this content is incorporated herein.

[0183] As the fluorosurfactant, the compounds described in paragraphs 0167 to 0173 of International Publication No. 2022 / 085485 can be used.

[0184] Examples of the nonionic surfactant include the compounds described in paragraph 0174 of International Publication No. 2022 / 085485.

[0185] Examples of the silicone surfactant include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), 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-3760, BYK-UV3510 (manufactured by BYK Chemie GmbH), etc. Compounds having the following structure can also be used as the silicone surfactant.

Chemical formula

[0186] The surfactant content in the total solids of the composition is preferably 0.001 to 5% by mass. The lower limit is preferably 0.005% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less. The composition may contain only one type of surfactant or two or more types. If two or more types are included, it is preferable that their total amount falls within the above range.

[0187] <<Polymerization inhibitor>> The composition of the present invention may contain a polymerization inhibitor. Examples of 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), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.), with p-methoxyphenol being preferred. The content of the polymerization inhibitor in the total solid content of the composition is preferably 0.0001 to 5% by mass. The composition may contain only one polymerization inhibitor or two or more. If two or more are included, it is preferable that their total amount is within the above range.

[0188] <<Silane coupling agent>> The composition of the present invention may contain a silane coupling agent. The silane coupling agent is preferably a silane compound having a hydrolyzable group, and more preferably a silane compound having a hydrolyzable group and other functional groups. A hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. The silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, styrene groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with (meth)acryloyl groups and epoxy groups being preferred. Examples of silane coupling agents include compounds described in paragraph 0177 of International Publication No. 2022 / 085485 and compounds described in Japanese Patent Publication No. 2019-183020. The content of the silane coupling agent in the total solid content of the composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The composition may contain only one type of silane coupling agent, or it may contain two or more types. If two or more types are included, it is preferable that their total amount is within the above range.

[0189] <<UV absorber>> The compositions of the present invention may contain ultraviolet absorbers. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. The UV absorbers include compounds described in paragraphs 0038-0052 of JP 2009-217221, compounds described in paragraphs 0052-0072 of JP 2012-208374, compounds described in paragraphs 0317-0334 of JP 2013-068814, compounds described in paragraphs 0061-0080 of JP 2016-162946, compounds described in paragraphs 0059-0076 of International Publication No. 2016 / 181987, compounds described in paragraphs 0052 and 0074 of International Publication No. 2021 / 131355, and International Publication No. 2021 / 132247 The compounds described in paragraphs 0022-0024 of the publication, the compound described in paragraph 0179 of International Publication No. 2022 / 085485, the reactive triazine UV absorber described in JP 2021-178918, the UV absorber described in JP 2022-007884, the compound described in Korean Published Patent No. 10-2022-0014454, the compound described in JP 2023-013321, the compounds described in paragraphs 0049-0059 of Japanese Patent No. 6268967, and the compound described in JP 2023-178225 can also be used. Commercially available UV absorbers include the Tinuvin series and Uvinul series from BASF. Furthermore, an example of a benzotriazole compound is the MYUA series manufactured by Miyoshi Oil & Fat Co., Ltd. (Chemical Daily, February 1, 2016). The content of the ultraviolet absorber in the total solid content of the composition is preferably 0.01 to 30% by mass. The lower limit is preferably 0.05% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The composition may contain only one type of ultraviolet absorber, or it may contain two or more types.If two or more types are included, it is preferable that their total amounts fall within the above range.

[0190] <<Antioxidant>> The composition of the present invention may contain an antioxidant. Examples of antioxidants include phenolic antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenol compounds. Phenolic antioxidants are preferably compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group. As for the substituents, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Antioxidants that have both a phenolic group and a phosphite ester group in the same molecule are also preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate, and tris(2,4-di-tert-butylphenyl) phosphite. Examples of commercially available antioxidants include Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330, Adeka Stab AO-412S, Adeka Stab 2112, Adeka Stab PEP-36, Adeka Stab HP-10 (all manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). The antioxidant may also be a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, a compound described in International Publication No. 2017 / 006600, a compound described in International Publication No. 2017 / 164024, or a compound described in Korean Published Patent No. 10-2019-0059371. The antioxidant content in the total solids of the composition is preferably 0.01 to 20% by mass. The lower limit is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 15% by mass or less, and even more preferably 10% by mass or less.The composition may contain only one antioxidant or two or more antioxidants. If it contains two or more antioxidants, it is preferable that their total amount falls within the above range.

[0191] <<Component B>> The composition of the present invention may optionally contain sensitizers, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, latent antioxidants, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be compounds described in paragraph 0182 of International Publication No. 2022 / 085485. Furthermore, thiol compounds described in Japanese Patent Application Publication No. 2020-109068 can be used as chain transfer agents. In addition, compounds having two or more triethoxysilyl groups described in Japanese Patent Application Publication No. 2023-180607 can be used as other components.

[0192] The composition of the present invention preferably has a free metal content of 100 ppm or less, and more preferably 50 ppm or less. Furthermore, the free halogen content is preferably 100 ppm or less, and more preferably 50 ppm or less. Methods for reducing free metals and halogens in the composition include washing with deionized water, filtration, ultrafiltration, purification with ion exchange resin, and purification with inorganic adsorbents such as hydrotalcite.

[0193] From an environmental perspective, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. In the composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solid content of the composition. The composition of the present invention may not substantially contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and compounds that can substitute for perfluoroalkyl carboxylic acid and its salts, a composition that substantially does not contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be selected. Compounds that may substitute for regulated compounds include, for example, compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. The compositions of the present invention may contain perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, to the maximum permissible extent.

[0194] From an environmental regulatory standpoint, the content of fluorine-containing compounds in the composition may be 5% by mass or less, 1% by mass or less, 100 ppm by mass or less, 1 ppm by mass or less, or substantially none at all.

[0195] <container> There are no particular limitations on the container used to contain the composition of the present invention, and any known container can be used. Alternatively, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can be used.

[0196] <Method for preparing the composition> The composition of the present invention can be prepared by mixing the aforementioned components. When preparing the composition, all components may be dissolved or dispersed simultaneously in a solvent, or, if necessary, two or more solutions or dispersions containing the components in appropriate proportions may be prepared in advance and mixed at the time of use (application) to prepare the composition.

[0197] The preparation of the composition may include a process for dispersing the pigment. Examples of mechanical forces used in the pigment dispersion process include compression, squeezing, impact, shearing, and cavitation. 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, and ultrasonic dispersion. Furthermore, in the grinding of pigments using a sand mill (bead mill), it is preferable to process the material under conditions that enhance grinding efficiency, such as by using small-diameter beads or increasing the bead packing density. It is also preferable to remove coarse particles after the grinding process by filtration or centrifugation. Furthermore, the processes and dispersers for dispersing the pigments can suitably be those described in "Complete Collection of Dispersion Technologies, published by Joho Kiko Co., Ltd., July 15, 2005," "Comprehensive Data Collection on Dispersion Technologies and Practical Industrial Applications, Centered on Suspensions (Solid / Liquid Dispersion Systems), published by Keiei Kaihatsu Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Publication No. 2015-157893. In addition, in the process of dispersing the pigments, the pigments may be refined using a salt milling process. For materials, equipment, and processing conditions used in the salt milling process, refer to, for example, Japanese Patent Publication No. 2015-194521 and Japanese Patent Publication No. 2012-046629. Examples of bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Furthermore, inorganic compounds with a Mohs hardness of 2 or higher can be used as beads. The composition may contain 1 to 10,000 ppm of the above-mentioned beads.

[0198] In preparing the composition, it is preferable to filter the composition with a filter for purposes such as removing foreign matter and reducing defects. Examples of filters and filtration methods used for filtration include those described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485.

[0199] <Membrane> Next, the film of the present invention will be described. The film of the present invention is obtained from the composition of the present invention described above. The film of the present invention can preferably be used as an optical filter. The applications of the optical filter are not particularly limited, but include color filters and infrared transmission filters.

[0200] The thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The film thickness can be 200 μm or less, 150 μm or less, 120 μm or less, 20 μm or less, 10 μm or less, or 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, and more preferably 0.2 μm or more.

[0201] When the film of the present invention is used as a color filter, it is preferable that the film has a hue of green, red, blue, cyan, magenta, or yellow. Furthermore, the film of the present invention 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.

[0202] When the film of the present invention is used as an infrared transmission filter, it is preferable that the film of the present invention has any of the following spectral characteristics (i1) to (i3). (i1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 850 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 850 nm and transmit light with a wavelength greater than 950 nm. (i2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength greater than 1050 nm. (i3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm. A film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light with a wavelength greater than 1150 nm.

[0203] <Memory manufacturing method> The film of the present invention can be manufactured by a process of applying the composition of the present invention. The manufacturing process of the film may further include a step to form a pattern (pixel). Examples of methods for forming the pattern (pixel) include photolithography and dry etching, with photolithography being preferred.

[0204] The pattern formation by photolithography preferably includes the steps of forming a composition layer on a support using the composition of the present invention, exposing the composition layer in a pattern, and developing and removing the unexposed parts of the composition layer to form a pattern (pixels). If necessary, a step of baking the composition layer (pre-bake step) and a step of baking the developed pattern (pixels) (post-bake step) may be provided.

[0205] In the step of forming the composition layer, the composition layer is formed on a support using the composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. Examples include glass substrates and silicon substrates, with silicon substrates being preferred. Charge-coupled devices (CCDs), complementary metal-oxide-semiconductor (CMOS) elements, transparent conductive films, etc., may be formed on the silicon substrate. A black matrix that isolates each pixel may also be formed on the silicon substrate. Furthermore, a base layer may be provided on the silicon substrate to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.

[0206] Known methods can be used for coating the composition. For example, drop casting; slit coating; spray coating; roll coating; spin coating; casting; slit and spin coating; pre-wetting (e.g., the method described in Japanese Patent Publication No. 2009-145395); various printing methods such as inkjet (e.g., on-demand, piezo, thermal), nozzle jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; transfer methods using molds, etc.; and nanoimprint methods. In addition, the coating method described in paragraph 0207 of International Publication No. 2022 / 085485 can also be used.

[0207] The composition layer formed on the support may be dried (pre-baked). Pre-baking is not necessary when manufacturing the film by a low-temperature process. If pre-baking is performed, 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 also 80°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, oven, etc.

[0208] Next, the composition layer is exposed in a pattern (exposure step). For example, the composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine to expose it through a mask having a predetermined mask pattern. This allows the exposed areas to be cured.

[0209] Examples of radiation (light) that can be used during exposure include g-rays and i-rays. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Long-wave light sources with wavelengths of 300 nm or more can also be used.

[0210] Furthermore, exposure may be performed by continuously irradiating with light, or by irradiating in pulses (pulsed exposure). Pulsed exposure is an exposure method that involves repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less).

[0211] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm². 2 Preferably, 0.05 to 1.0 J / cm² 2 This is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in air, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21 vol% (e.g., 22 vol%, 30 vol%, or 50 vol%). Furthermore, the exposure intensity can be appropriately set, usually 1000 W / m². 2 ~100,000 W / m 2 (For example, 5000W / m 2 , 15000W / m 2 , or 35000W / m 2The oxygen concentration and exposure intensity can be combined as appropriate; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m². 2 At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². 2 This can be done as follows.

[0212] Next, the unexposed areas of the composition layer are developed and removed to form a pattern (pixels). The development and removal of the unexposed areas of the composition layer can be done using a developer. This causes the unexposed areas of the composition layer in the exposure process to dissolve in the developer, leaving only the photocured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve the ability to remove residue, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.

[0213] Examples of developing solutions include organic solvents and alkaline developers, with alkaline developers being preferred. For the developing solution and the rinsing method after development, the developing solution and rinsing method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0214] After development and drying, it is preferable to perform additional exposure or heat treatment (post-bake). Additional exposure and post-bake are curing treatments after development to ensure complete hardening. The heating temperature in post-bake is preferably 100 to 300°C, and more preferably 100 to 270°C. Post-bake can be performed continuously or in batches using heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions. When performing additional exposure, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure may also be performed using the method described in Korean Published Patent No. 10-2017-0122130.

[0215] The dry etching method for pattern formation preferably includes the steps of: forming a composition layer on a support using the composition of the present invention; curing the entire composition layer to form a cured layer; forming a photoresist layer on the cured layer; exposing the photoresist layer in a patterned manner, then developing it to form a resist pattern; and using the resist pattern as a mask to dry etch the cured layer using an etching gas. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, the photoresist layer formation process is preferably one in which a heat treatment after exposure and a heat treatment after development (post-bake treatment) are performed. For the dry etching method for pattern formation, refer to paragraphs 0010 to 0067 of Japanese Patent Application Publication No. 2013-064993, and this content is incorporated herein by reference.

[0216] <Solid-state image sensor> The film of the present invention can be used in solid-state image sensors. The configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configurations can be considered.

[0217] The imaging device has a support on which a plurality of photodiodes constituting the light-receiving area of ​​a solid-state image sensor and a transfer electrode made of polysilicon or the like are provided. The photodiodes and transfer electrode have a light-shielding film made of tungsten or the like with an opening only for the light-receiving portion of the photodiode. The light-shielding film has a device protection film made of silicon nitride or the like formed to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode. The device protection film has the film of the present invention. Furthermore, the device protection film may have a configuration in which a light-gathering means (e.g., a microlens; the same applies hereinafter) is provided below the film of the present invention (on the side closer to the support), or a configuration in which the light-gathering means is provided on the film of the present invention. The color filter may also have a structure in which a film forming each pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a lower refractive index than each pixel. Examples of imaging devices having such a structure include the devices described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577.

[0218] <Image display device> The film of the present invention can be used in image display devices. Examples of image display devices include liquid crystal displays and organic electroluminescent (organic EL) displays. Definitions and details of image display devices are described, for example, in "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal displays are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular limitations on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology". The image display device may also have white organic EL elements. The white organic EL elements are preferably in a tandem structure. The tandem structure of organic EL elements is described in Japanese Patent Publication No. 2003-045676, supervised by Akiyoshi Mikami, "The Cutting Edge of Organic EL Technology Development - High Brightness, High Precision, Long Lifespan, and Know-how Collection," Technical Information Association, pp. 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), the green region (530-580 nm), and the yellow region (580-620 nm). In addition to these emission peaks, it is even more preferable to have a maximum emission peak in the red region (650-700 nm). The film of the present invention can also be used as an infrared-transmitting film provided in an infrared communication opening formed in the frame portion of a protective plate for a display device.

[0219] <Compound> The compound of the present invention is the compound represented by formula (1) described above. The compounds of the present invention have a high color value and can be preferably used as colorants. Furthermore, the compounds of the present invention can also be used in semiconductor materials, organic thin-film transistors, organic photoelectric conversion elements (solid-state image sensors for optical sensor applications, solar cells for energy conversion applications, etc.), gas sensors, organic rectifier elements, organic inverters, information recording elements, and the like. [Examples]

[0220] The present invention will be further described in detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. In the following structural formulas, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, i-Pr represents an isopropyl group, and TIPS represents a triisopropylsilyl group.

[0221] <Example of synthesis> (Synthesis Example 1) Synthesis of Compound 1-1 Compound 1-1 is synthesized according to the following scheme. [ka] [ka]

[0222] -Synthesis process for compound A-1- Add 86.5 mL of diethyl ether (Et2O) to a three-necked flask under a nitrogen atmosphere. While cooling the internal temperature to below -60°C using a dry ice-acetone bath, add 54.0 mL of n-butyllithium (n-BuLi) (1.6 mol / L; 86.5 mmol; 1.05 eq). Add a solution of 20.0 g (82.3 mmol) of 2,4-dibromothiazole dissolved in 123.5 mL of Et2O dropwise at an internal temperature of below -72°C and stir for 1.5 hours. Add 17.5 g (90.6 mmol; 1.1 eq) of triisopropylsilyl chloride (TIPSCl) dropwise at an internal temperature of -76°C or below, wash with 20 mL of Et2O, remove the dry ice from the bath, and slowly raise the temperature to room temperature. Add 200 mL of saturated sodium bicarbonate (NaHCO3) solution, add ethyl acetate (siRNA), separate the solution, wash with a brine, dry with magnesium sulfate (MgSO4), and concentrate under reduced pressure to obtain a dark yellowish-brown oil. Compound A-1 (light brown oil) 12.7 g was obtained by purification using a Universal Premium 3L automated column (manufactured by Yamazen Corporation, eluent: hexane). 1H NMR (CDCl3) δ1.13(d, J=7.6Hz, 18H), 1.45(m, J=4.0Hz, 3H), 7.40(s, 1H). 13 C NMR (CDCl3) δ11.55, 18.42, 119.10, 127.97, 172.07.

[0223] -Synthesis process for compound A-2- Add 59.2 mL of Et2O to a 300 mL three-necked flask under a nitrogen atmosphere. While cooling the internal temperature to below -60°C using a dry ice-acetone bath, add 37.0 mL of n-BuLi (1.6 mol / L; 59.2 mmol; 1.5 eq). Add a solution of 12.7 g (39.5 mmol) of compound A-1 dissolved in 59.2 mL of Et2O dropwise at an internal temperature of below -73°C and stir for 1 hour. Add 14.1 g (43.4 mmol; 1.1 eq) of tributyltin chloride (Bu3SnCl) dropwise at an internal temperature of below -73°C and wash with 12.7 mL of Et2O. Stir for 1 hour and raise to room temperature. Add 200 mL of saturated NaHCO3 water, add hexane and separate, wash with brine, dry over MgSO4, and concentrate under reduced pressure to obtain approximately 30 g of yellowish-brown oil. The compound A-2 (pale yellow oil) was purified using a Q-PACK NH60 SIZE400 automated column (manufactured by Fuji Silysia Chemical Co., Ltd., eluent: hexane) to obtain 19.3 g. 1 H NMR(CDCl3) δ7.52(t,J=5.6Hz, 1H).

[0224] -Synthesis process for compound A-3- 20.0 g (61.7 mmol) of 2,5-dibromoterephthalic acid, 100 mL (1.37 mol) of thionyl chloride, and 0.06 mL (0.78 mmol) of N,N-dimethylformamide (DMF) were placed in a round-bottom flask and suspended. The mixture was reacted in an oil bath at 80°C for 2 hours. After cooling, the mixture was removed by distillation under reduced pressure (40°C, 100 mmHg to 50 mmHg) to obtain 23.1 g of compound A-3 (pale cream-colored solid). Compound A-3 was used directly in the synthesis of compound A-4. 1¹H NMR (CDCl3) δ 8.21 (s, 2H). 13 C NMR(CDCl3) δ119.34, 137.15, 139.68, 164.35.

[0225] -Synthesis process for compound A-4- A calcium chloride tube is attached to a three-necked flask, and compound A-3 obtained in the above step is added to 400 mL of dichloromethane (CH2Cl2) and dissolved completely. In an ice bath, 51.6 mL (370 mmol; 6.0 eq) of triethylamine (Et3N) is added, and 36.6 mL (370 mmol; 6.0 eq) of piperidine is added dropwise at an internal temperature of 13°C or lower, and the mixture is reacted overnight at room temperature. 200 mL of water is added to the reaction mixture and separated, washed with water, dried with MgSO4, concentrated under reduced pressure, suspended in methanol, filtered, washed with methanol, and then dried under reduced pressure (60°C) to obtain 26.5 g of compound A-4 (cream-colored powder). 1 H NMR (CDCl3) δ1.47-1.68(m, 12H), 3.17-3.24(m, 4H), 3.69-3.77(m, 4H), 7.44(s, 2H). 13 C NMR (CDCl3) δ24.34, 25.43, 26.20, 42.70, 47.97, 118.60, 131.54, 140.22, 165.53.

[0226] -Synthesis process for compound A-5- 4.00 g (8.73 mmol) of compound A-4, 10.2 g (19.2 mmol; 2.2 eq) of compound A-2, and 40 mL of DMF (super-dehydrated) are placed in a round-bottom flask and suspended. Degassing under reduced pressure and nitrogen purging are repeated three times, and 0.40 g (0.44 mmol; 5 mol%) of XPhos Pd G4 is added. Degassing under reduced pressure and nitrogen purging are repeated three times, and the mixture is reacted under nitrogen flow in an oil bath set to 110°C for 26 hours. After cooling, 80 mL of water and 10 mL of siRNA are added, the mixture is stirred at room temperature, filtered, rinsed with water, and rinsed with siRNA. The resulting solid is suspended in CH2Cl2, filtered by Celite filtration, rinsed with CH2Cl2, and the filtrate is concentrated to obtain 1.8 g of compound A-5 (gray solid). 1 H NMR (CDCl3) δ0.59-0.65(m, 2H), 1.14-1.17(m, 36H), 1.43-1.60(m, 16H), 2.94-3.05(m, 4H), 3.44-3.51(m, 2H), 3.83-3.88(m, 2H), 7.83(s, 2H), 7.95(s, 2H). 13 C NMR (CDCl3) δ11.61, 18.52, 18.54, 24.32, 25.32, 25.61, 42.53, 47.93, 119.71, 127.88, 131.61, 135.61, 155.07, 169.52, 169.63.

[0227] -Synthesis process for compounds A-6 and A-7- In a three-necked flask, 2.50 g (3.21 mmol) of compound A-5 and 225 mL of tetrahydrofuran (THF) are placed under a nitrogen atmosphere and suspended. The mixture is cooled to below -40°C using a dry ice-water-methanol bath, and 35.1 mL (2 mol / L; 70 mmol; 22 eq) of lithium diisopropylamide (LDA) is added dropwise at an internal temperature of -47 to -43°C. The mixture is stirred at an internal temperature of -40°C for 3.5 hours. 75 mL of water is added, Â is added and the mixture is separated. The mixture is washed with a brine filter, dried over MgSO4, and concentrated under reduced pressure to obtain a yellowish-brown solid. The resulting yellowish-brown solid was purified by silica gel column chromatography (eluent: hexane-dichloromethane = 1:1), and the reddish-purple band was recovered to obtain 0.8 g of compound A-6. To the residue after purification of compound A-6, the eluent was changed to hexane-siRNA = 1:1, and the yellowish-brown band was recovered to obtain approximately 1.5 g of compound A-7. Compound A-7 was converted back to compound A-6 using LDA under the same reaction conditions as above. Compound A-6 R f =0.85 (Hexane-SiO = 2:1) 1 H NMR (CDCl3) δ1.18(d, J=7.2Hz, 36H), 1.48(hept, J=7.2Hz, 6H), 7.73(s, 2H). 13 C NMR (CDCl3) δ11.63, 18.45, 115.79, 132.04, 140.42, 143.39, 176.35, 182.22, 187.76. Compound A-7 R f =0.52 (Hexane-SiO = 2:1) 1 H NMR (CDCl3) δ0.60-0.65(m, 1H), 1.15-1.20(m, 36H), 1.46-1.50(m, 11H), 2.96-3.10(m, 2H), 3.39-3.45(m, 1H), 3.82-3.88(m, 1H), 7.49(s, 1H), 7.80(s, 1H), 8.09(s, 1H).

[0228] -Synthesis process for compound 1-1- Dissolve 0.68 g (1.1 mmol) of compound A-6 in 110 mL of THF in a three-necked flask under a nitrogen atmosphere. Cool in a dry ice-acetone bath, add 11 mL of mesitylmagnesium bromide (1 mol / L in Et2O; 11 mmol; 10 eq) dropwise at an internal temperature of -72°C or lower, stir for 1 hour, then stir at room temperature for 15 hours. Add 100 mL of saturated ammonium chloride solution, separate, extract the aqueous layer with siRNA, wash with brine, dry over MgSO4, and concentrate under reduced pressure to obtain a yellowish-brown oil. Add 88 mL of toluene (deoxygenated), repeat vacuum degassing and nitrogen purging three times, add 0.85 g (4.5 mmol; 4 eq) of tin chloride (SnCl2), repeat vacuum degassing and nitrogen purging three times, and react under nitrogen flow in an oil bath set to 70°C for 1.5 hours. After cooling, the mixture is filtered with Celite, washed with ethyl acetate, and the filtrate is concentrated under reduced pressure to obtain a reddish-purple crude compound. It is purified by silica gel column chromatography (eluent: hexane-CH2Cl2 = 5:1~5:2) to obtain 0.35 g of compound 1-1 (reddish-purple solid). 1 H NMR (CDCl3) δ1.10(d, J=7.2Hz, 36H), 1.48(hept, J=7.2Hz, 6H), 2.31(s, 12H), 2.32(s, 6H), 6.45(s, 2H), 6.92(s, 4H). 13 C NMR (CDCl3) δ11.62, 18.51, 20.58, 21.13, 124.94, 128.31, 129.93, 131.55, 135.83, 136.42, 137.97, 142.56, 144.15, 166.12, 175.78.

[0229] (Synthesis Example 2) Synthesis of Compound 1-2 Compound 1-2 is synthesized in the same manner as the synthesis of compound 1-1 in Synthesis Example 1, except that mesitylmagnesium bromide (1 mol / L in Et2O) is replaced with 2-thienylmagnesium bromide (1 mol / L in THF).

[0230] (Synthesis Example 3) Synthesis of Compounds 1-3 Compound 1-3 is synthesized in the same manner as the synthesis of compound 1-1 in Synthesis Example 1, except that mesitylmagnesium bromide (1 mol / L in Et2O) is replaced with methylmagnesium bromide (1 mol / L in THF).

[0231] (Synthesis Example 4) Synthesis of Compounds 1-4 Compounds 1-4 are synthesized in the same manner as in Synthesis Example 1, except that a compound with the following structure is used instead of compound A-1. [ka]

[0232] (Synthesis Example 5) Synthesis of Compounds 1-5 Dissolve 0.56 g (0.7 mmol) of compound 1-1 in 20 mL of toluene (super-dehydrated) in a three-necked flask under a nitrogen atmosphere. Cool in an ice bath, and add 2.1 mL of tetrabutylammonium fluoride (approximately 1 mol / L tetrahydrofuran solution) dropwise at an internal temperature of 5°C or below, stirring for 1 hour. After adding 40 mL of methanol, stir at room temperature, filter, rinse with water, and rinse with ethyl acetate. Dry the resulting solid under reduced pressure at 50°C for 1 hour to obtain 0.25 g of compound 1-5.

[0233] (Synthesis Example 6) Synthesis of Compounds 1-6 Compounds 1-6 are synthesized in the same manner as in Synthesis Example 1, except that a compound with the following structure is used instead of compound A-1. [ka]

[0234] (Synthesis Example 7) Synthesis of Compounds 1-7 Compounds 1-7 are synthesized in the same manner as in Synthesis Example 1, except that a compound with the following structure is used instead of compound A-1. [ka]

[0235] (Synthesis Example 8) Synthesis of Compounds 1-8 Compound 1-8 is synthesized in the same manner as in Synthesis Example 1, except that a compound with the following structure is used instead of compound A-1, and in the synthesis step of compound 1-1 in Synthesis Example 1, mesitylmagnesium bromide (1 mol / L in Et2O) is changed to methylmagnesium bromide (1 mol / L in THF). [ka]

[0236] <Manufacturing of resin solutions> (Manufacturing Example 1-1): Manufacturing of resin solution B-1 Prepare a separable flask with a condenser as the reaction vessel, and prepare a monomer dropping vessel by thoroughly stirring and mixing 162.38 parts by mass of benzyl methacrylate (hereinafter referred to as "BzMA"), 34.00 parts by mass of methacrylic acid (hereinafter referred to as "MAA"), 6.06 parts by mass of 2,2'-azobis(2-methylpropionic acid)dimethyl (low metal grade) (referred to as "V-601HP" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 435 parts by mass of cyclohexanone, and 5.33 parts by mass of n-dodecanethiol (hereinafter referred to as "n-DM"). Charge 49 parts by mass of cyclohexanone into the reaction vessel, purge with nitrogen, and then heat in an oil bath while stirring to raise the temperature of the reaction vessel to 75°C. Once the temperature of the reaction vessel has stabilized at 75°C, begin dropping from the monomer dropping vessel into the reaction vessel. The dropwise addition is carried out over 150 minutes while maintaining the temperature at 75°C. After 120 minutes have passed since the dropwise addition was completed, the temperature is raised to 90°C in the reaction vessel. After maintaining 90°C for 2 hours, the reaction solution is cooled to room temperature. After the polymerization reaction is complete, 3.09 parts by mass of N,N-dimethyldodecylamine as an amine compound and 0.5 parts by mass of p-methoxyphenol as a polymerization inhibitor are added under air. Then, 37.43 parts by mass of glycidyl methacrylate (hereinafter referred to as "GMA") and 96 parts by mass of cyclohexanone are added. Subsequently, the temperature of the reaction solution is raised to 90°C in the reaction vessel. After maintaining 90°C for 6 hours, the reaction solution is cooled to room temperature. The cooled reaction solution is discharged into a mixture of 10,000 parts by mass of methanol and 2,500 parts by mass of water. The precipitated solid (polymer) is filtered off, and the filtered solid is washed twice with 500 parts by mass of water. The washed solid is air-dried at 50°C for 18 hours to obtain resin B-1 with the following structure. The weight-average molecular weight (Mw) of resin B-1 is 12000, the acid value is 32 mgKOH / g, and the C=C value is 1.13 mmol / g. [ka]

[0237] The resin B-1 obtained by the above procedure is added to propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") to produce resin solution B-1 such that the final resin concentration (solid content concentration) of the resin solution obtained is 30% by mass.

[0238] (Manufacturing Example 1-2) Manufacturing of Resin Solution B-2 Prepare a separable flask with a condenser as the reaction vessel. Meanwhile, prepare a monomer dropping vessel containing 30.7 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 43.1 parts by mass of MAA, 14.3 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), 113.5 parts by mass of BzMA, 4 parts by mass of PBO, and 60 parts by mass of diethylene glycol dimethyl ether (hereinafter referred to as "DMDG"), mixed with stirring. Prepare a chain transfer agent dropping vessel containing 8 parts by mass of n-DM and 32 parts by mass of DMDG, mixed with stirring. Charge 375 parts by mass of DMDG into the reaction vessel, purge with nitrogen, and then heat in an oil bath while stirring to raise the temperature of the reaction vessel to 90°C. Once the temperature of the reaction vessel has stabilized at 90°C, begin dropping from the monomer dropping vessel and the chain transfer agent dropping vessel into the reaction vessel. The dripping process is carried out over 135 minutes each, while maintaining a temperature of 90°C. Sixty minutes after the dropwise addition is complete, start raising the temperature to 110°C in the reaction vessel. After maintaining 110°C for 3 hours, attach a gas inlet tube to the separable flask and start bubbling with an oxygen / nitrogen = 5 / 95 (v / v) mixed gas. Next, add 50.9 parts by mass of GMA, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol) (hereinafter referred to as "MBMTB"), and 0.8 parts by mass of triethylamine (hereinafter referred to as "TEA") to the reaction vessel and allow to react at 110°C for 3 hours. After confirming the completion of the reaction by measuring the acid value of the reaction solution, add 155 parts by mass of DMDG to the reaction solution and cool to room temperature. 1000 parts by mass of water are added to the cooled reaction solution, and the precipitated solid (polymer) is filtered off. The filtered solid is washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water to obtain resin B-2 with the following structure. The weight-average molecular weight (Mw) of resin B-2 is 18000, the acid value is 32 mgKOH / g, and the C=C value is 1.42 mmol / g. [ka]

[0239] The resin B-2 obtained by the above procedure is added to PGMEA to produce resin solution B-2 such that the final resin solution has a resin concentration (solid content concentration) of 30% by mass.

[0240] (Manufacturing Example 1-3) Manufacturing of Resin Solution B-3 In a three-necked flask, 30.4 parts by mass of a macromonomer represented by the following formula (MM), 51 parts by mass of ω-carboxy-polycaprolactone monoacrylate (manufactured by Toagosei Co., Ltd., Aronics M-5300), and PGMEA are introduced to obtain a mixture. The mixture is stirred while blowing nitrogen into it. [ka]

[0241] Next, the mixture is heated to 75°C while flowing nitrogen gas through the flask. Then, 0.82 parts by mass of n-DM and then 0.43 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, V-601) are added to the mixture to start the polymerization reaction. After heating the mixture at 75°C for 2 hours, another 0.43 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) are added to the mixture. After 2 hours, another 0.43 parts by mass of 2,2'-azobis(methyl 2-methylpropionate) are added to the mixture. After reacting for another 2 hours, the mixture is heated to 90°C and stirred for 3 hours. The polymerization reaction is completed by the above procedure. After the polymerization reaction is complete, 9.6 parts by mass of dimethyldodecylamine as an amine compound and 0.3 parts by mass of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a polymerization inhibitor are added under air, and then 9 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) are added dropwise. After the dropwise addition is complete, the reaction is continued for 24 hours at 90°C under air. The completion of the reaction is confirmed by measuring the acid value, and the reaction solution is cooled to room temperature. 1000 parts by mass of water are added to the cooled reaction solution, and the precipitated solid (polymer) is filtered off. The filtered solid is washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water to obtain resin B-3 with the following structure. The weight-average molecular weight (Mw) of resin B-3 is 17200, the acid value is 70 mgKOH / g, and the C=C value is 0.50 mmol / g. [ka]

[0242] The resin B-3 obtained by the above procedure is added to PGMEA to produce resin solution B-3 such that the final resin solution has a resin concentration (solid content concentration) of 30% by mass.

[0243] (Manufacturing Example 1-4) Manufacturing of Resin Solution B-4 In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 8 parts by mass of 3-mercapto-1,2-propanediol, 12 parts by mass of pyromellitic anhydride, 80 parts by mass of PGMEA, and 0.2 parts by mass of monobutyltin oxide as a catalyst are charged, the mixture is purged with nitrogen gas, and the reaction is carried out at 120°C for 5 hours (first step). Next, 30 parts by mass of methyl methacrylate, 10 parts by mass of t-butyl acrylate, 10 parts by mass of ethyl acrylate, 5 parts by mass of methacrylic acid, 10 parts by mass of benzyl methacrylate, and 35 parts by mass of 2-hydroxyethyl methacrylate are charged, the reaction vessel is heated to 80°C, and 1 part by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) is added and the reaction is carried out for 12 hours (second step). Next, the flask is purged with air, and 35.0 parts by mass of 2-methacryloyloxyethyl isocyanate and 0.1 parts by mass of hydroquinone are added and the mixture is reacted at 70°C for 4 hours (third step). After confirming that the 2270 cm-1 peak based on the isocyanate group has disappeared by infrared absorption spectroscopy, the reaction solution is cooled to obtain resin B-4 with the following structure. The acid value of resin B-4 is 40 mg KOH / g, the weight-average molecular weight is 12000, and the C=C value is 1.44 mmol / g. [ka]

[0244] In formula (B-4), one of *1 and *2 is bonded to either *5 or *6 to form a polyester main chain, and the other is bonded to either *3 or *4 to form a polyester main chain. One of *3 and *4 is bonded to either *1 or *2 to form a polyester main chain, and the other is integrated with an OH group to form a carboxylic acid. One of *5 and *6 is bonded to either *1 or *2 to form a polyester main chain, and the other is integrated with an OH group to form a carboxylic acid.

[0245] The resin B-4 obtained by the above procedure is added to PGMEA to produce resin solution B-4 such that the final resin solution has a resin concentration (solid content concentration) of 30% by mass.

[0246] <Manufacturing of micronized pigments> (Manufacturing Example 2-1) 100 parts by mass of compound 1-5, 1200 parts by mass of sodium chloride, and 120 parts by mass of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 4 hours. The resulting kneaded composition was added to 3000 parts by mass of hot water and stirred for 1 hour to form a slurry. After removing sodium chloride and diethylene glycol by repeated filtration and washing, the mixture was dried at 80°C overnight to produce fine pigment 1-5M.

[0247] (Manufacturing examples 2-2 to 2-8) In manufacturing example 2-1, the same process as in manufacturing example 2-1 is performed, except that the pigment used is changed to the pigment shown in the table below, to produce the finely milled pigments in manufacturing examples 2-2 to 2-8.

[0248] [Table 1]

[0249] Compounds 1-5 to 1-8, compound 2-3, and compound 2-4 in the table above are the same compounds 1-5 to 1-8, compound 2-3, and compound 2-4 shown as specific examples of the particular compounds mentioned above.

[0250] <Manufacturing of Pigment Dispersion> After mixing the materials listed in the table below, disperse them for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"). Then, filter the resulting mixture through a 5.0 μm pore size filter to produce each pigment dispersion.

[0251] [Table 2]

[0252] The details of the materials indicated by the abbreviations in the table above are as follows:

[0253] (Finely milled pigments) 1-5M, 1-6M, 1-7M, 1-8M, 2-3M, 2-4M, PB15:6M, PB15:4M: Finely milled pigments 1-5M, 1-6M, 1-7M, 1-8M, 2-3M, 2-4M, PB15:6M, PB15:4M produced in the above-mentioned manufacturing examples 2-1 to 2-8.

[0254] (Pigment derivatives) Derivatives 1-3: Compounds with the following structure [ka]

[0255] (Resin solution) B-3: Resin solution B-3 manufactured in manufacturing example 1-3 B-4: Resin solution B-4 manufactured in manufacturing example 1-4 B-5: A 30% PGMEA solution of a resin with the following structure (acid value 32.3 mgKOH / g, amine value 45.0 mgKOH / g, weight-average molecular weight 22900; the values ​​attached to the main chain represent the molar ratio of repeating units, and the values ​​attached to the side chain represent the number of repeating units) with a solid content of 30% by mass. [ka]

[0256] (solvent) S-2: Propylene glycol monomethyl ether acetate (PGMEA)

[0257] <Production of the composition> Each composition is manufactured by mixing the materials listed in the table below.

[0258] [Table 3]

[0259] [Table 4]

[0260] (Colorants, pigment dispersions) 1-1, 1-2, 1-3, 1-4, 2-1, 2-2: Compounds 1-1, 1-2, 1-3, 1-4, 2-1, and 2-2 are specific examples of the particular compounds mentioned above. Dis01~Dis06, DisB01, DisB02: Pigment dispersions as described above Dye001: Compound with the following structure (xanthene dye, m=3, n=3, k=70%, l=30%, weight-average molecular weight 15000) [ka] X-1: Compound with the following structure (xanthene dye) [ka]

[0261] (Resin solution) B-1: Resin solution B-1 manufactured in manufacturing example 1-1 B-2: Resin solution B-2 manufactured in manufacturing example 1-2

[0262] (polymerizable compound) M-1: Aronics M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The pentaerythritol triacrylate content is 55% to 63% by mass.) M-2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified pentaerythritol tetraacrylate) M-3: Aronics M-510 (manufactured by Toagosei Co., Ltd., polybasic acid modified acrylic oligomer)

[0263] (Photopolymerization initiator) C-1: Compound with the following structure [ka] C-2: ADEKA Arclus NCI-730 (manufactured by ADEKA Corporation) C-3: Irgacure OXE03 (BASF) C-4: Compounds with the following structure [ka]

[0264] <UV absorber> U-1: Uvinul3050 (BASF)

[0265] <Polymerization inhibitor> IN-1: p-methoxyphenol

[0266] <Surfactants> W-1: Compound with the following structure (number-average molecular weight 1800) [ka]

[0267] <Solvent> S-1: Cyclopentanone S-2: Propylene glycol monomethyl ether acetate (PGMEA) S-3: 1-Methoxy-2-propanol (PGME)

[0268] <Membrane manufacturing> Each composition is applied to a glass substrate by spin coating, and the composition layer is formed by heating it at 100°C for 2 minutes using a hot plate. The resulting composition layer is exposed to 1000 mJ / cm using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Corporation). 2 The entire surface is exposed with the specified exposure dose. Then, using a hot plate, it is heated at 180°C for 5 minutes to produce a film with a thickness of 1.0 μm.

[0269] <Heat resistance evaluation> The transmittance of the glass substrate on which the above film has been deposited is measured in the wavelength range of 400 to 1000 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Tech Corporation). Next, the glass substrate on which the above film has been deposited is heated at 265°C for 5 minutes using a hot plate. The change in transmittance (ΔT) in the wavelength range of 400 to 1000 nm for the film before and after heating is calculated using the following formula, and the heat resistance is evaluated based on the value at the wavelength where ΔT is largest across the entire measurement wavelength range, according to the following criteria. A smaller ΔT value indicates better heat resistance. Transmittance change (ΔT) = |Transmittance of the film before heating - Transmittance of the film after heating| A: ΔT < 5% B: 5 ≤ ΔT < 10% C: 10 ≤ ΔT%

[0270] <Evaluation of color transfer properties> (Regarding compositions for evaluating color transfer properties) A pigment dispersion (p-1) is prepared by processing the following ingredients using a bead mill: 9.6 parts by mass of CI Pigment Green 58 as a coloring agent, 3.4 parts by mass of CI Pigment Yellow 138, 10.0 parts by mass of BYK-LPN21116 (manufactured by BYK) as a dispersant (solid content concentration 40% by mass), 12.0 parts by mass of binder resin (D1) solution (solid content concentration 33% by mass), and 65.0 parts by mass of propylene glycol monomethyl ether acetate.

[0271] 68.3 parts by mass of pigment dispersion (p-1), 6.3 parts by mass of binder resin (D2) solution (solid content concentration 33% by mass), 8.5 parts by mass of Aronics M-450 (pentaerythritol tetraacrylate, manufactured by Toagosei Co., Ltd.), 2.1 parts by mass of Aronics M-520 (polybasic acid modified acrylic oligomer, manufactured by Toagosei Co., Ltd.), 1.1 parts by mass of Omnirad 369 (manufactured by IGM Resins BV), 0.5 parts by mass of 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Industry Co., Ltd., trade name B-CIM), 0.5 parts by mass of 2,4-diethylthioxanthone, 0.2 parts by mass of 2-mercaptobenzothiazole, Omnirad 907 (IGM Resins A composition for evaluating color transfer properties (solid content concentration 18% by mass) is prepared by mixing 0.3 parts by mass of BV (manufactured by BV), 0.05 parts by mass of Megafac F-554 (manufactured by DIC Corporation), and propylene glycol monomethyl ether acetate.

[0272] The binder resin (D1) solution and binder resin (D2) solution are as follows: -Regarding the binder resin (D1) solution- 100 parts by mass of propylene glycol monomethyl ether acetate is charged into a flask equipped with a condenser and a stirrer, and nitrogen is purged. The mixture is heated to 80°C, and at the same temperature, a mixed solution of 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-acryloyloxyethyl) succinate, and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) is added dropwise over 1 hour, and polymerization is carried out while maintaining this temperature for 2 hours. After that, the temperature of the reaction solution is raised to 100°C, and polymerization is carried out for a further 1 hour to produce the binder resin (D1) solution.

[0273] -Regarding the binder resin (D2) solution- 80 parts by mass of propylene glycol monomethyl ether acetate is charged into a flask equipped with a condenser and a stirrer, and nitrogen is purged. The mixture is heated to 80°C, and at the same temperature, a mixture of 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate, 28 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-acryloyloxyethyl) succinate, and 20 parts by mass of propylene glycol monomethyl ether acetate and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) is added dropwise over 2 hours, and polymerization is carried out while maintaining this temperature for 1 hour. After that, the temperature of the reaction solution is raised to 90°C, and polymerization is carried out for another hour to produce a binder resin (D2) solution.

[0274] (Method for evaluating color transfer properties) A color transfer evaluation composition is applied to a soda glass substrate with an SiO2 film formed on its surface using a spin coater. The substrate is then pre-baked on a 90°C hot plate for 2 minutes to form a 2.4 μm thick coating. After the substrate is cooled to room temperature, a high-pressure mercury lamp is used to expose the coating to radiation at 400 J / m², without a photomask, including wavelengths of 365 nm, 405 nm, and 436 nm. 2 The entire substrate is exposed to light. Then, a developer consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23°C is applied to the substrate at a developing pressure of 1 kgf / cm². 2 The material is extruded using a nozzle with a diameter of 1 mm. After that, the substrate is washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes to produce a monochromatic filter. The resulting monochromatic filter is measured using a color analyzer (LCF-1100A, manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view to measure the stimulus value (Y), i.e., luminance, in the CIE color system. This luminance is denoted as "YR".

[0275] The compositions of each example and comparative example are applied to a soda glass substrate with an SiO2 film formed on its surface using a spin coater, and then pre-baked on a 90°C hot plate for 2 minutes to form a coating with a thickness of 2.4 μm. After the substrate is cooled to room temperature, radiation including wavelengths of 365 nm, 405 nm, and 436 nm is applied to the coating using a high-pressure mercury lamp via a photomask at a rate of 400 J / m². 2 The substrate is exposed to light at the specified exposure level. Next, a developer solution consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23°C is applied to the substrate at a developing pressure of 1 kgf / cm². 2 The substrate is extruded using a nozzle with a diameter of 1 mm and shower-developed for 90 seconds. After that, the substrate is washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes to produce a substrate with a first filter having a roughly square shape of 3 cm x 3 cm. Next, the color transfer evaluation composition is applied to the substrate on which the first filter is formed using a spin coater, and then pre-baked on a 90°C hot plate for 2 minutes to form a coating film with a thickness of 2.4 μm. After the substrate is cooled to room temperature, radiation including wavelengths of 365 nm, 405 nm, and 436 nm is applied to the coating film at a rate of 400 J / m² using a high-pressure mercury lamp without a photomask. 2 The entire substrate is exposed to light. A developer consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23°C is then applied to the substrate at a developing pressure of 1 kgf / cm². 2 The material is extruded using a nozzle with a diameter of 1 mm. After that, the substrate is washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230°C for 30 minutes to produce a substrate with a second filter on top of the first filter.

[0276] At a point 200 μm away from the interface where the first and second filters of the above substrate overlap, in the direction of non-overlap, a color analyzer (LCF-1100A, manufactured by Otsuka Electronics Co., Ltd.) is used to measure the stimulus value (Y) of the second filter in the CIE color system, i.e., luminance, using a C light source and a 2-degree field of view. This luminance is denoted as "Y1". The rate of change in brightness is calculated using the following formula, and the color transfer properties are evaluated. Rate of change in brightness (%) = ((YR - Y1) / YR) × 100 A: Brightness change rate is less than 2.0% B: Luminance change rate is 2.0% or more and less than 4.0% C: Brightness change rate is 4.0% or higher

[0277] [Table 5]

[0278] As shown in the table above, the examples are superior to the comparative examples in terms of heat resistance and color transfer resistance.

[0279] <Evaluation of coloring properties> For films obtained using the compositions of Examples 1-6 and Comparative Example 1, the absorption spectra in the wavelength range of 400-700 nm were measured using a spectrophotometer (U-4100, Hitachi High-Tech Corporation), and the average transmittance in the range of the maximum absorption wavelength λmax ± 25 nm was calculated. The coloring power was then evaluated according to the following criteria: A lower average transmittance in the range of the maximum absorption wavelength λmax ± 25 nm indicates higher coloring power. A: Average transmittance ≤ 10% in the range of maximum absorption wavelength λmax ± 25 nm B: 10% < Average transmittance in the range of maximum absorption wavelength λmax ± 25nm ≤ 20% C: 20% < Average transmittance in the range of maximum absorption wavelength λmax ± 25 nm

[0280] [Table 6]

[0281] Although Examples 1-6 and Comparative Example 1 are compositions with the same colorant content, Examples 1-4 show superior coloring power compared to Examples 5, 6, and Comparative Example 1.

[0282] (Example 301) Each material is mixed in the proportions shown below, and the mixture is filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to produce the composition of Example 301 (composition for forming an infrared transmission filter). Composition of Example 7: 36.99 parts by mass Pigment dispersion 1-1: 46.5 parts by mass Pigment dispersion DisB01: 37.1 parts by mass When the composition of Example 301 is used and the performance evaluations are performed in the same manner as in Example 1, the same effects as in Example 1 are obtained. Furthermore, the film obtained using the composition of Example 301 can block light of visible wavelengths and transmit at least a portion of light of infrared wavelengths.

[0283] (Example 302) The materials are mixed in the proportions shown below and filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to produce the composition of Example 302 (composition for forming an infrared transmission filter). Composition of Example 11: 36.99 parts by mass Pigment dispersion 1-1: 46.5 parts by mass Pigment dispersion DisB01: 37.1 parts by mass When the composition of Example 302 is used and the performance evaluations are performed in the same manner as in Example 3, the same effects as in Example 3 are obtained. Furthermore, the film obtained using the composition of Example 302 can block light in the visible region and transmit at least a portion of light in the infrared region.

[0284] Pigment dispersion 1-1 Pigment dispersion 1-1 is prepared by mixing and dispersing the following mixture using 0.3 mm diameter zirconia beads in a bead mill (high-pressure disperser with vacuum mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) for 3 hours. Mixed pigment of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139): 11.8 parts by mass Dispersant (Disperbyk-111, manufactured by BYKChemie): 9.1 parts by mass Propylene glycol monomethyl ether acetate: 79.1 parts by mass

Claims

1. A composition comprising a compound represented by formula (1) or formula (2), a curable compound, and a solvent; 【Chemistry 1】 In formula (1), R １ ~R ６ Each of these independently represents a hydrogen atom or a substituent; In formula (2), R １１ ~R １６ Each of these independently represents a hydrogen atom or a substituent.

2. The composition according to claim 1, wherein the curable compound comprises a polymerizable compound.

3. The composition according to claim 1 or 2, further comprising a photopolymerization initiator.

4. A film obtained using the composition described in claim 1 or 2.

5. An optical filter comprising the film described in claim 4.

6. A solid-state image sensor comprising the film described in claim 4.

7. Compounds represented by formula (1); 【Chemistry 2】 In formula (1), R １ ~R ６ Each of these independently represents a hydrogen atom or a substituent.

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