Composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, and compound

Abstract

The present invention provides a composition containing a compound represented by formula (1), a curable compound, and a solvent. Also provided are a film, an optical filter, a solid-state imaging element, an image display device, an infrared sensor, and a camera module using the composition.

Description

Technical Field

[0001] This invention relates to an indigo compound and a composition containing the indigo compound. Furthermore, this invention relates to a membrane, filter, solid-state imaging element, image display device, infrared sensor, and camera module using a composition containing the indigo compound. Background Technology

[0002] Solid-state imaging elements, namely CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor), are used in video cameras, digital cameras, and mobile phones with camera functions to produce color images. These solid-state imaging elements use silicon photodiodes, which are sensitive to infrared light, in their light-receiving parts. Therefore, infrared cutoff filters are sometimes used for visibility correction.

[0003] Infrared cutoff filters are manufactured using compositions containing infrared absorbers. Indigo compounds are known as infrared absorbers.

[0004] Patent Document 1 describes the use of a composition containing a specific indigo compound to manufacture an infrared cutoff filter, etc.

[0005] Previous technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2012-224593 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] In recent years, there has been a demand for further improvements in lightfastness for films obtained using compositions containing infrared absorbers.

[0010] According to the inventor's research, the lightfastness of the indigo compound disclosed in Patent Document 1 is insufficient and has room for further improvement.

[0011] Therefore, the object of the present invention is to provide a composition capable of forming a film with excellent lightfastness. Furthermore, the object of the present invention is to provide a film, a filter, a solid-state imaging element, an image display device, an infrared sensor, a camera module, and a compound.

[0012] means for solving technical problems

[0013] The present invention provides the following.

[0014] <1> A composition comprising a compound represented by formula (1), a curable compound, and a solvent;

[0015] [Chemical Formula 1]

[0016]

[0017] In equation (1), A 1 and A 2 Each can be independently represented as aryl, heteroaryl, or alkyl.

[0018] X 1 ~X 4 Each can independently represent an aryl, heteroaryl, alkoxy, aryloxy, or halogen atom.

[0019] R 1 ~R 8 Each can be used independently to represent a hydrogen atom or a substituent.

[0020] X 1 With X 2 X 3 With X 4 They can be connected to form a ring.

[0021] Among them, A 1 A 2 X 1 X 2 X 3 and X 4 At least one of them represents a heteroaryl group.

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

[0023] A in the above formula (1) 1 A 2 X 1 X 2 X 3 and X 4 At least one of them is a group represented by any one of formulas (A-1) to (A-3).

[0024] [Chemical Formula 2]

[0025]

[0026] In equation (A-1), X A1 Indicates O, S, or NR X1 ,

[0027] X A2 CR X2 Or N,

[0028] X A3 CR X3 Or N,

[0029] X A4 CR X4 Or N,

[0030] R X1 ~R X4 Each can be used independently to represent a hydrogen atom or a substituent.

[0031] In X A2 For CR X2 And X A3 For CR X3 In the case of R X2 With R X3 They can bond together to form a ring.

[0032] In X A3 For CR X3 And X A4 For CR X4 In the case of R X3 With R X4 They can bond together to form a ring.

[0033] * indicates a connection key.

[0034] In equation (A-2), X A5 Indicates O, S, or NR X5 ,

[0035] X A6 CR X6 Or N,

[0036] X A7 CR X7 Or N,

[0037] X A8 CR X8 Or N,

[0038] R X5 ~R X8 Each can be used independently to represent a hydrogen atom or a substituent.

[0039] In X A7 For CR X7 And X A8 For CR X8 In the case of R X7 With R X8 They can bond together to form a ring.

[0040] * indicates a connection key.

[0041] In equation (A-3), Y A1 ~Y A5 Represent N or CR independently, respectively. Y1 R Y1 Represents a hydrogen atom or a substituent.

[0042] YA1 ~Y A5 1 to 3 of them are N.

[0043] In Y A1 ~Y A5 Two or more adjacent ones are CR Y1 In the case of two adjacent CRs Y1 R in Y1 They can bond together to form a ring.

[0044] * indicates a connection key.

[0045] <3> The composition according to <2>, wherein,

[0046] A in the above formula (1) 1 and A 2 At least one of them is a group represented by any of the above formulas (A-1) to (A-3).

[0047] <4> The composition according to <2>, wherein,

[0048] A in the above formula (1) 1 and A 2 At least one of them is a group represented by any of the above formulas (A-1) to (A-2).

[0049] <5> The composition according to any one of <1> to <4>, wherein,

[0050] Curable compounds include polymerizable compounds.

[0051] <6> The composition according to any one of <1> to <5> further comprises a photopolymerization initiator.

[0052] <7> A membrane obtained using any one of <1> to <6>.

[0053] <8> A filter having the membrane described in <7>.

[0054] <9> A solid-state imaging element having the film described in <7>.

[0055] <10> An image display device having the film described in <7>.

[0056] <11> An infrared sensor having the membrane described in <7>.

[0057] <12> A camera module having the membrane described in <7>.

[0058] <13> A compound represented by formula (1),

[0059] [Chemical Formula 3]

[0060]

[0061] In equation (1), A 1 and A 2 Each can be independently represented as aryl, heteroaryl, or alkyl.

[0062] X 1 ~X 4 Each can independently represent an aryl, heteroaryl, alkoxy, aryloxy, or halogen atom.

[0063] R 1 ~R 8 Each can be used independently to represent a hydrogen atom or a substituent.

[0064] X 1 With X 2 X 3 With X 4 They can be connected to form a ring.

[0065] Among them, A 1 A 2 X 1 X 2 X 3 and X 4 At least one of them represents a heteroaryl group.

[0066] Invention Effects

[0067] According to the present invention, a composition capable of forming a film with excellent lightfastness can be provided. Furthermore, the present invention can provide a film, a filter, a solid-state imaging element, an image display device, an infrared sensor, a camera module, and a compound. Attached Figure Description

[0068] Figure 1 A schematic diagram illustrating one embodiment of an infrared sensor. Detailed Implementation

[0069] The present invention will now be described in detail.

[0070] In this specification, “~” is used to imply that the values ​​recorded before and after it are the lower and upper limits.

[0071] In the designation of groups (atomic groups) in this specification, the designations that do not specify substitution and non-substitution include groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0072] In this specification, "exposure" means, unless otherwise specified, not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used in exposure include the bright-line spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other photochemical rays or radiation.

[0073] In this specification, “(meth)acrylate” means either or both of acrylate and methacrylate, “(meth)acrylic acid” means either or both of acrylic acid and methacrylic acid, and “(meth)acryloyl” means either or both of acryloyl and methacryloyl.

[0074] In this specification, weight-average molecular weight and number-average molecular weight are defined as polystyrene conversion values ​​determined by gel permeation chromatography (GPC).

[0075] In this specification, in the chemical formulas, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl.

[0076] In this specification, infrared light refers to light (electromagnetic waves) with a wavelength of 700–2500 nm.

[0077] In this specification, total solids content refers to the total mass of the components after removing the solvent from all components of the composition.

[0078] In this specification, the term "process" includes not only independent processes, but also processes that perform the expected function of a process, even when they cannot be clearly distinguished from other processes.

[0079] <Composition>

[0080] The compositions of the present invention are characterized by containing a compound represented by formula (1), a curable compound, and a solvent.

[0081] The compounds represented by formula (1) contained in the compositions of the present invention exhibit excellent lightfastness, and the compositions of the present invention containing such compounds can form films with minimal variation in spectroscopic properties based on light irradiation. This is presumably because, in the compounds represented by formula (1), A of formula (1)... 1 A 2 X 1 X 2 X 3 and X 4At least one of the compounds is a heteroaryl group, thereby increasing the oxidation potential of the compound, stabilizing it at the HOMO (Highest Occupied Molecular Orbital) level, and improving the compound's resistance to oxidative decomposition.

[0082] Furthermore, in the compound represented by formula (1), A of formula (1) 1 A 2 X 1 X 2 X 3 and X 4 At least one of the groups is a heteroaryl group, thereby shifting the absorption wavelength further to the longer wavelength side, resulting in excellent infrared shielding properties (especially shielding properties of any light in the wavelength range of 1000-2000 nm (short wavelength infrared shielding properties)). Furthermore, it also exhibits excellent visible transparency.

[0083] Furthermore, in the compound represented by formula (1), A of formula (1) 1 A 2 X 1 X 2 X 3 and X 4 At least one of the compounds is a heteroaryl group, thereby, when the compound represented by formula (1) is used as a pigment, the compound represented by formula (1) in the composition is easily adsorbed to resins, etc. through hydrogen bonds, and the aggregation of the compound represented by formula (1) can be suppressed. Therefore, the dispersibility of the composition can also be improved.

[0084] The compositions of the present invention can be used as compositions for optical filters. Examples of optical filters include infrared cut-off filters and infrared transmission filters. The compounds represented by formula (1) have excellent visible light transmittance and infrared shielding properties, therefore, the compositions of the present invention are particularly preferred for use as compositions for infrared cut-off filters.

[0085] The components used in the compositions of the present invention will be described below.

[0086] <<Specific compound (the compound represented by formula (1))>>

[0087] The compositions of the present invention contain compounds represented by formula (1). Hereinafter, compounds represented by formula (1) will also be referred to as specific compounds. Compounds represented by formula (1) are also compounds of the present invention.

[0088] [Chemical Formula 4]

[0089]

[0090] In equation (1), A 1and A 2 Each can be independently represented as aryl, heteroaryl, or alkyl.

[0091] X 1 ~X 4 Each can independently represent an aryl, heteroaryl, alkoxy, aryloxy, or halogen atom.

[0092] R 1 ~R 8 Each can be used independently to represent a hydrogen atom or a substituent.

[0093] X 1 With X 2 X 3 With X 4 They can be connected to form a ring.

[0094] Among them, A 1 A 2 X 1 X 2 X 3 and X 4 At least one of them represents a heteroaryl group.

[0095] A in equation (1) 1 and A 2 The alkyl group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 12. Alkyl groups can be straight-chain, branched, or cyclic, more preferably straight-chain or branched. Alkyl groups can have substituents or be unsubstituted. Substituents can be groups listed in the substituent T section below, as well as groups represented by formula (R-100), preferably alkoxy, aryl, heteroaryl, halogen atoms, or groups represented by formula (R-100).

[0096] A in equation (1) 1 A 2 X 1 X 2 X 3 and X 4 The aryl group represented preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents or may be unsubstituted. Substituents may include groups listed in the substituent T below and groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atom, or groups represented by formula (R-100).

[0097] A in constitutive formula (1) 1 A 2 X 1 X 2 X 3 and X 4The number of carbon atoms in the ring of the heteroaryl group is preferably 1 to 10, more preferably 1 to 5. Nitrogen atoms, oxygen atoms, and sulfur atoms can be listed as types of heteroatoms constituting the ring of the heteroaryl group. The number of heteroatoms in the ring constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group is preferably a monocyclic ring or a fused ring with 2 to 8 fusion numbers, more preferably a monocyclic ring or a fused ring with 2 to 4 fusion numbers. The heteroaryl group may have substituents or may be unsubstituted. Substituents can be groups listed in the substituent T section below and groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atoms, or groups represented by formula (R-100).

[0098] A in equation (1) 1 A 2 X 1 X 2 X 3 and X 4 The heteroaryl group represented is preferably any one of the groups represented by formulas (A-1) to (A-3), and for the sake of obtaining better lightfastness, it is more preferably any one of the groups represented by formulas (A-1) to (A-2).

[0099] [Chemical Formula 5]

[0100]

[0101] In equation (A-1), X A1 Indicates O, S, or NR X1 ,

[0102] X A2 CR X2 Or N,

[0103] X A3 CR X3 Or N,

[0104] X A4 CR X4 Or N,

[0105] R X1 ~R X4 Each can be used independently to represent a hydrogen atom or a substituent.

[0106] In X A2 For CR X2 And X A3 For CR X3 In the case of R X2 With R X3 They can bond together to form a ring.

[0107] In X A3 For CR X3And X A4 For CR X4 In the case of R X3 With R X4 They can bond together to form a ring.

[0108] * indicates a connection key.

[0109] In equation (A-2), X A5 Indicates O, S, or NR X5 ,

[0110] X A6 CR X6 Or N,

[0111] X A7 CR X7 Or N,

[0112] X A8 CR X8 Or N,

[0113] R X5 ~R X8 Each can be used independently to represent a hydrogen atom or a substituent.

[0114] In X A7 For CR X7 And X A8 For CR X8 In the case of R X7 With R X8 They can bond together to form a ring.

[0115] * indicates a connection key.

[0116] In equation (A-3), Y A1 ~Y A5 Represent N or CR independently, respectively. Y1 R Y1 Represents a hydrogen atom or a substituent.

[0117] Y A1 ~Y A5 1 to 3 of them are N.

[0118] In Y A1 ~Y A5 Two or more adjacent ones are CR Y1 In the case of two adjacent CRs Y1 R in Y1 They can bond together to form a ring.

[0119] * indicates a connection key.

[0120] As R X1 ~R X8 RY1 The substituents represented may be groups listed in the substituent T below and groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atom or groups represented by formula (R-100).

[0121] In equation (A-1), at X A2 For CR X2 And X A3 For CR X3 In the case of R X2 With R X3 When the rings are formed by mutual bonding, the formed ring is preferably a 5-membered ring or a 6-membered ring. Furthermore, the formed ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The formed ring may have substituents. Substituents can be groups listed in the substituent T section below, as well as groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atom, or groups represented by formula (R-100).

[0122] In equation (A-1), at X A3 For CR X3 And X A4 For CR X4 In the case of R X3 With R X4 When the rings are formed by mutual bonding, the formed ring is preferably a 5-membered ring or a 6-membered ring. Furthermore, the formed ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The formed ring may have substituents. Substituents can be groups listed in the substituent T section below, as well as groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atom, or groups represented by formula (R-100).

[0123] In equation (A-2), at X A7 For CR X7 And X A8 For CR X8 In the case of R X7 With R X8 When the rings are formed by mutual bonding, the formed ring is preferably a 5-membered ring or a 6-membered ring. Furthermore, the formed ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The formed ring may have substituents. Substituents can be groups listed in the substituent T section below, as well as groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atom, or groups represented by formula (R-100).

[0124] In equation (A-3), in Y A1 ~Y A5 Two or more adjacent ones are CR Y1In the case of two adjacent CRs Y1 R in Y1 When the rings are formed by mutual bonding, the resulting ring is preferably a 5-membered or 6-membered ring. Furthermore, the resulting ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The resulting ring may have substituents. Substituents can be groups listed in the substituent T section below, as well as groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atom, or groups represented by formula (R-100).

[0125] X in equation (1) 1 ~X 4 The alkoxy group represented preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 12. Alkoxy groups can be straight-chain, branched, or cyclic, more preferably straight-chain or branched. Alkoxy groups can have substituents or be unsubstituted. Substituents can be groups listed in the substituent T section below, as well as groups represented by formula (R-100), preferably aryl, heteroaryl, halogen atoms, or groups represented by formula (R-100).

[0126] X in equation (1) 1 ~X 4 The aryloxy group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The aryloxy group may have substituents or may be unsubstituted. Substituents may include groups listed in the substituent T below and groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, heteroaryl, halogen atom or groups represented by formula (R-100).

[0127] X as in equation (1) 1 ~X 4 The halogen atoms represented can include chlorine, fluorine, bromine, and iodine atoms.

[0128] R as in equation (1) 1 ~R 8 The substituents represented may be groups listed in the substituent T below and groups represented by formula (R-100), preferably alkyl, alkoxy, aryl, aryloxy, heteroaryl, halogen atom or groups represented by formula (R-100).

[0129] In equation (1), X 1 With X 2 X 3 With X 4 They can be connected to form a ring. The rings formed are preferably 5-membered or 6-membered rings.

[0130] In equation (1), A 1 and A2 Preferably, each is an aryl or a heteroaryl group, and for the reasons of good lightfastness and excellent shielding of longer wavelength infrared light, a heteroaryl group is more preferred. Furthermore, the heteroaryl group is preferably a group represented by any of the above formulas (A-1) to (A-3), and more preferably a group represented by any of the formulas (A-1) to (A-2).

[0131] In equation (1), X 1 ~X 4 Preferably, each is an aryl or a heteroaryl group. Furthermore, the heteroaryl group is preferably a group represented by any of the formulas (A-1) to (A-3) above, and more preferably a group represented by any of the formulas (A-1) to (A-2).

[0132] For the reasons of good lightfastness and excellent shielding properties against longer wavelengths of infrared radiation, A of formula (1) is preferred among specific compounds. 1 and A 2 At least one of them is a group represented by any of the above formulas (A-1) to (A-3), more preferably a group represented by any of the above formulas (A-1) to (A-2).

[0133] In a specific compound, A of preferred formula (1) 1 and A 2 Each is independently a heteroaryl group and X 1 ~X 4 Each is independently aryl or heteroaryl, more preferably A of formula (1). 1 and A 2 Each is independently a heteroaryl group and X 1 ~X 4 Each is an aryl group. The heteroaryl group is preferably a group represented by any of the formulas (A-1) to (A-3) above, and more preferably a group represented by any of the formulas (A-1) to (A-2).

[0134] The specific compound can be either a pigment or a dye. When using the specific compound as a dye, R is preferred. 1 ~R 8 At least one of them is a branched alkyl group having 5 to 30 carbon atoms or a group having a group represented by the formula (R-100) described below, or A 1 A 2 X 1 X 2 X 3 and X 4 At least one of them is a branched alkyl group having 5 to 30 carbon atoms or a group having a group represented by the formula (R-100) described below as a substituent.

[0135] -Regarding the substituent T-

[0136] As substituent T, the following groups can be listed: halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably alkyl group with 1 to 30 carbon atoms), cycloalkyl group (preferably cycloalkyl group with 5 to 30 carbon atoms), alkenyl group (preferably alkenyl group with 2 to 30 carbon atoms), alkynyl group (preferably alkynyl group with 2 to 30 carbon atoms), aryl group (preferably aryl group with 6 to 30 carbon atoms), heteroaryl group (preferably heteroaryl group with 1 to 30 carbon atoms), amino group (preferably amino group with 0 to 30 carbon atoms), alkoxy group (preferably alkoxy group with 1 to 30 carbon atoms), aryloxy group (preferably aryloxy group with 6 to 30 carbon atoms), heteroaryloxy group (preferably heteroaryloxy group with 1 to 30 carbon atoms), acyl group (preferably carbon atom). Acyl groups with 2 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups with 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl groups with 7 to 30 carbon atoms), heteroaryloxycarbonyl groups (preferably heteroaryloxycarbonyl groups with 2 to 30 carbon atoms), acyloxy groups (preferably acyloxy groups with 2 to 30 carbon atoms), amide groups (preferably amide groups with 2 to 30 carbon atoms), aminocarbonylamino groups (preferably aminocarbonylamino groups with 2 to 30 carbon atoms), alkoxycarbonylamino groups (preferably alkoxycarbonylamino groups with 2 to 30 carbon atoms), aryloxycarbonylamino groups (preferably aryloxycarbonylamino groups with 7 to 30 carbon atoms), aminosulfonyl groups (preferably aminosulfonyl groups with 0 to 30 carbon atoms), aminosulfonyl groups Amino (preferably aminosulfonylamino with 0-30 carbon atoms), carbamoyl (preferably carbamoyl with 1-30 carbon atoms), alkylthio (preferably alkylthio with 1-30 carbon atoms), arylthio (preferably arylthio with 6-30 carbon atoms), heteroarylthio (preferably heteroarylthio with 1-30 carbon atoms), alkylsulfonyl (preferably alkylsulfonyl with 1-30 carbon atoms), alkylsulfonylamino (preferably alkylsulfonylamino with 1-30 carbon atoms), arylsulfonyl (preferably arylsulfonyl with 6-30 carbon atoms), arylsulfonylamino (preferably arylsulfonylamino with 6-30 carbon atoms), heteroarylsulfonyl (preferably heteroarylsulfonyl with 1-30 carbon atoms). The following groups are permitted: arylsulfonyl, heteroarylsulfonylamino (preferably heteroarylsulfonylamino with 1 to 30 carbon atoms), alkylsulfinyl (preferably alkylsulfinyl with 1 to 30 carbon atoms), arylsulfinyl (preferably arylsulfinyl with 6 to 30 carbon atoms), heteroarylsulfinyl (preferably heteroarylsulfinyl with 1 to 30 carbon atoms), urea (preferably urea with 1 to 30 carbon atoms), hydroxyl, nitro, carboxyl, sulfonic acid, phosphate, carboxylic acid amide, sulfonic acid amide, imide, phosphin, mercapto, cyano, alkylsulfinyl, arylsulfinyl, aryl azo, heteroaryl azo, oxophosphin, oxophosphinyloxy, oxophosphinylamino, silyl, hydrazyl, and imino. When these groups are groups capable of further substitution, substituents may be further included.As substituents, examples include the groups described in the substituent T above and the groups represented by the formula (R-100) shown below.

[0137] -Regarding the group represented by formula (R-100)-

[0138] -O-(R r1 -O) m -R r2 ······(R-100)

[0139] In formula (R-100), R r1 R represents an alkylene group having 1 to 10 carbon atoms. r2 It represents an alkyl group with 1 to 10 hydrogen atoms or an aryl group with 6 to 10 carbon atoms, where m represents an integer from 1 to 30.

[0140] Specific examples of particular compounds include compounds 1-1 to 1-16, which are described in the examples described below.

[0141] The maximum absorption wavelength of a particular compound is more preferably in the wavelength range of 750 to 1500 nm, even more preferably in the wavelength range of 900 to 1200 nm, and especially preferably in the wavelength range of 1000 to 1100 nm.

[0142] Certain compounds are preferably used as infrared absorbers.

[0143] The content of the specific compound (represented by formula (1)) in the total solids 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 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The composition of the present invention may contain only one specific compound or may contain two or more. When containing two or more, their combined amount is preferably within the above-mentioned range.

[0144] The compositions of the present invention may further contain a compound represented by formula (101).

[0145] [Chemical Formula 6]

[0146]

[0147] In equation (101), A 101 Indicates aryl, heteroaryl, or alkyl.

[0148] X 101 ~X 104 Each can independently represent an aryl, heteroaryl, alkoxy, aryloxy, or halogen atom.

[0149] R 101 ~R 108 Each can be used independently to represent a hydrogen atom or a substituent.

[0150] X 101 With X 102 They can be connected to form a ring.

[0151] A in equation (101) 101 X 101 ~X 104 R 101 ~R 108 The meaning of A in equation (1) 1 X 1 ~X 4 R 1 ~R 8 The meanings are the same, and the preferred ranges are also the same.

[0152] The content of the compound represented by formula (101) in the total solids of the preferred composition is 100 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 1 part by mass or less, relative to 100 parts by mass of the particular compound.

[0153] <<Cureable Compounds>>

[0154] The compositions of the present invention contain a curable compound. Examples of curable compounds include polymerizable compounds and resins. The resin can be a non-polymerizable resin (a resin without a polymerizable group) or a polymerizable resin (a resin with a polymerizable group). Examples of polymerizable groups include groups containing olefinic unsaturated bonds, cyclic ether groups, hydroxymethyl groups, alkoxymethyl groups, etc. Examples of groups containing olefinic unsaturated bonds include vinyl, vinylphenyl, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, etc., preferably (meth)allyl, (meth)acryloyl, and (meth)acryloyloxy, more preferably (meth)acryloyloxy. Examples of cyclic ether groups include epoxy groups, oxetyl, etc., preferably epoxy groups.

[0155] As a curing compound, it is preferable to use a curing compound that contains at least a resin. Furthermore, when the composition of the present invention is used as a composition for photolithography, as a curing compound, it is preferable to use a resin and a polymeric compound (preferably a polymeric monomer as a monomer-type polymeric compound), and more preferably a resin and a polymeric monomer having a group containing an olefinic unsaturated bond (a monomer-type polymeric compound).

[0156] (polymeric compounds)

[0157] Examples of polymerizable compounds include compounds having groups containing olefinic unsaturated bonds, compounds having cyclic ether groups, compounds having hydroxymethyl groups, and compounds having alkoxymethyl groups. Compounds having groups containing olefinic unsaturated bonds are preferably used as free radical polymerizable compounds. Furthermore, compounds having cyclic ether groups are preferably used as cationic polymerizable compounds.

[0158] As resin-type polymeric compounds, examples include resins that contain repeating units having polymeric groups.

[0159] The molecular weight of monomer-type polymeric compounds (polymeric monomers) is preferably less than 2000, more preferably less than 1500. The lower limit of the molecular weight of polymeric monomers is preferably 100 or more, more preferably 200 or more. The weight-average molecular weight (Mw) of resin-type polymeric compounds is preferably between 2000 and 2000000. The upper limit of the weight-average molecular weight is preferably less than 1000000, more preferably less than 500000. The lower limit of the weight-average molecular weight is preferably more than 3000, more preferably more than 5000.

[0160] The polymerizable monomer having a group containing an olefinically unsaturated bond is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include compounds described in paragraphs 0075 to 0083 of International Publication No. 2022 / 065215.

[0161] In addition, as a specific example, the compound described in Taiwan Patent Application Publication No. 201832008 can also be cited.

[0162] Examples of compounds containing olefinically unsaturated groups include dinepentylenetetroxide tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dinepentylenetetroxide tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dinepentylenetetroxide 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 Co., Ltd.), as well as compounds in which the (meth)acryloyl group is bonded via ethylene glycol and / or propylene glycol residues (e.g., by SARTOMER). Company, Inc.'s commercially available SR454, SR499, etc. Furthermore, as compounds containing olefinically unsaturated groups, they can also be modified with diglycerol EO (ethylene oxide) to produce (meth)acrylates (commercially available, M-460; manufactured by TOAGOSEI CO.,LTD.), neopentyl terephthalate tetraacrylate (manufactured by Shin-Nakamura Chemical Co.,Ltd., NK ESTER A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co.,Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co.,Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO.,LTD.), NK OLIGO UA-7200 (manufactured by Shin-Nakamura Chemical Co.,Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co.,Ltd.). (manufactured by Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by KYOEISHA CHEMICAL CO.,LTD.), 8UH-1006, 8UH-1012 (manufactured by TAISEI FINE CHEMICAL CO.,LTD.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL CO.,LTD.), etc.

[0163] As compounds having groups containing olefinic unsaturated bonds, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, ethylene oxide isocyanate modified tri(meth)acrylate, and neopentyl tertrol tri(meth)acrylate are also preferred. Commercially available trifunctional (meth)acrylate compounds include ARONIX 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 Co.,Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co.,Ltd.), etc.

[0164] As compounds having groups containing olefinic unsaturated bonds, compounds having both olefinic unsaturated bonds and urethane bonds are also preferred (hereinafter, also referred to as polymerizable compounds having urethane bonds). By using such compounds, the heat resistance of the obtained film can be further improved. The reason presumably for this effect is that the urethane bonds form a physical cross-linking structure based on intermolecular hydrogen bonds.

[0165] Polymerizable compounds having urethane bonds include, for example, urethane (meth)acrylates obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and urethane (meth)acrylates obtained by reacting a polyfunctional isocyanate with a polyol and then further reacting a (meth)acrylate having a hydroxyl group.

[0166] Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl tertrol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dinepentyl tertrol penta(meth)acrylate, dinepentyl tertrol ethylene oxide modified penta(meth)acrylate, dinepentyl tertrol propylene oxide modified penta(meth)acrylate, dinepentyl tertrol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reactants of epoxy-containing compounds and carboxyl (meth)acrylates, and hydroxyl-containing polyol polyacrylates.

[0167] Examples of the aforementioned multifunctional isocyanates include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, aromatic diisocyanates such as toluene diisocyanate, diphenylmethylene diisocyanate, xylene diisocyanate, their biuret bodies, isocyanate ureates, trimethylolpropane adducts, etc.

[0168] Polymerizable compounds having urethane bonds can also include compounds described in paragraphs 0308 to 0315 of Japanese Patent Application Publication No. 2022-173080.

[0169] As compounds containing olefinically unsaturated groups, compounds with acid groups such as carboxyl, sulfonic acid, and phosphoric acid groups can also be used. Commercially available examples of such compounds include ARONIX M-305, M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO.,LTD.).

[0170] As compounds containing olefinically unsaturated groups, compounds with caprolactone structures can also be used. For information on compounds with caprolactone structures, please refer to paragraphs 0042 to 0045 of Japanese Patent Application Publication No. 2013-253224, which is incorporated herein by reference. Examples of compounds with caprolactone structures include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available from Nippon Kayaku Co., Ltd. as part of the KAYARAD DPCA series.

[0171] As compounds having groups containing olefinic unsaturated bonds, compounds having groups containing olefinic unsaturated bonds and alkeneoxy groups can also be used. Such compounds are preferably compounds having groups containing olefinic unsaturated bonds and ethoxy and / or propyleneoxy groups, more preferably compounds having groups containing olefinic unsaturated bonds and ethoxy groups, and even more preferably 3- to 6-functional (meth)acrylate compounds having 4 to 20 ethoxy groups. Examples of commercially available products include, for instance, SR-494, a tetrafunctional (meth)acrylate having 4 ethoxy groups manufactured by SARTOMER Company, Inc., and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd.

[0172] As compounds containing olefinically unsaturated groups, polymerizable compounds with a fluorene skeleton can also be used. Examples of commercially available products include OGSOL EA-0200 and EA-0300 ((meth)acrylate monomers with a fluorene skeleton manufactured by Osaka Gas Chemicals Co., Ltd.).

[0173] As for compounds containing olefinically unsaturated groups, compounds that are substantially free of environmentally regulated substances such as toluene are preferred. Examples of commercially available such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., Ltd.).

[0174] Examples of compounds having a cyclic ether group include compounds having an epoxy group and compounds having an oxacyclobutyl group, with compounds having an epoxy group being preferred. Examples of compounds having an epoxy group include compounds having 1 to 100 epoxy groups per 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.

[0175] Compounds having cyclic ether groups can be low molecular weight compounds (e.g., molecular weight less than 1000) or macromolecules (e.g., molecular weight 1000 or more, or, in the case of polymers, weight-average molecular weight 1000 or more). The weight-average molecular weight of the cyclic ether groups 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.

[0176] As compounds having cyclic ether groups, compounds described in paragraphs 0034 to 0036 of Japanese Patent Application Publication No. 2013-011869, compounds described in paragraphs 0147 to 0156 of Japanese Patent Application Publication No. 2014-043556, compounds described in paragraphs 0085 to 0092 of Japanese Patent Application Publication No. 2014-089408, and compounds described in Japanese Patent Application Publication No. 2017-179172 can also be used.

[0177] 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), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, and CELLOXIDE 2021P. 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (all manufactured by Daicel Corporation), CYCLOMER P ACA200M, 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), ARONE OXETANE OXT-121, OXT-221, OX-SQ, PNOX (all manufactured by TOAGOSEI CO.,LTD.), ADEKA GLYCIROL ED-505 (an epoxy-containing monomer manufactured by ADEKA CORPORATION), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (NOF CORPORATION's epoxy-containing polymers), OXT-101, OXT-121, OXT-212, OXT-221 (TOAGOSEI CO.,LTD.'s oxygen-containing heterocyclic butyl monomers), OXE-10, OXE-30 (OSAKA ORGANICCHEMICAL INDUSTRY LTD.'s oxygen-containing heterocyclic butyl monomers), etc.

[0178] As compounds containing a hydroxymethyl group (hereinafter also referred to as hydroxymethyl compounds), examples include compounds in which the hydroxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Furthermore, as compounds containing an alkoxymethyl group (hereinafter also referred to as alkoxymethyl compounds), examples include compounds in which the alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Preferably, as compounds in which the alkoxymethyl or hydroxymethyl group is bonded to a nitrogen atom, alkoxymethylated melamine, hydroxymethylated melamine, alkoxymethylated benzoguanamine, hydroxymethylated benzoguanamine, alkoxymethylated glycourea, hydroxymethylated glycourea, alkoxymethylated urea, and hydroxymethylated urea are preferred. Furthermore, compounds described in paragraphs 0134 to 0147 of Japanese Patent Application Publication No. 2004-295116 and paragraphs 0095 to 0126 of Japanese Patent Application Publication No. 2014-089408 can also be used.

[0179] (Resin)

[0180] The compositions of the present invention can use resin as a curing compound. Preferably, the curing compound is a curing compound containing at least a resin. The resin is used, for example, for dispersing pigments or the like in the composition or for use as an adhesive. Furthermore, resins used primarily for dispersing pigments or the like in the composition are also referred to as dispersants. However, this use of resin is one example; resins can also be used for purposes other than this. Additionally, resins having polymerizable groups also correspond to polymerizable compounds.

[0181] The weight-average molecular weight of the resin is preferably between 3,000 and 2,000,000. The upper limit is preferably below 1,000,000, more preferably below 500,000. The lower limit is preferably above 4,000, more preferably above 5,000.

[0182] Examples of resins include (meth)acrylic resins, epoxy resins, olefin-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polystyrene resins, polyarylene ether phosphine 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 can be used alone, or two or more can be used in combination. From the viewpoint of improving heat resistance, norbornene resins are preferred as cyclic olefin resins. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (e.g., ARTON F4520). Furthermore, as a resin, the following resins can also be used: the resin described in paragraphs 0091 to 0099 of International Publication No. 2022 / 065215; the end-capped polyisocyanate resin described in Japanese Patent Application Publication No. 2016-222891; the resin described in Japanese Patent Application Publication No. 2020-122052; the resin described in Japanese Patent Application Publication No. 2020-111656; the resin described in Japanese Patent Application Publication No. 2020-139021; the resin described in Japanese Patent Application Publication No. 2017-138503 that includes structural units having a ring structure on the main chain and structural units having biphenyl structures on the side chains; the resin described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373; and the resin described in Japanese Patent Application Publication No. 2020. The following resins are described: the alkali-soluble resin disclosed in Japanese Patent Application Publication No. 2020-186325; the resin represented by Formula 1 disclosed in Korean Patent Application Publication No. 10-2020-0078339; the copolymer containing epoxy and acid groups disclosed in International Patent Application Publication No. 2022 / 030445; the resins described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373; the alkali-soluble resin disclosed in Japanese Patent Application Publication No. 2020-186325; the resin represented by Formula 1 disclosed in Korean Patent Application Publication No. 10-2020-0078339; the resin disclosed in Japanese Patent Application Publication No. 2021-134350; and the copolymer disclosed in Japanese Patent Application Publication No. 2020-041046. Furthermore, a resin having a fluorene backbone can be preferably used as the resin. As resins having a fluorene skeleton, examples include those described in U.S. Patent Application Publication No. 2017 / 0102610.Furthermore, as a resin, the resin described in paragraphs 0199 to 0233 of Japanese Patent Application Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Application Publication No. 2020-186325, the resin represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339, the resin described in Japanese Patent Application Publication No. 2021-134350, and the resin described in Japanese Patent Application Publication No. 2022-174597 can also be used.

[0183] As the resin, a resin having acid groups is preferred. Examples of acid groups include carboxyl groups, phosphate groups, sulfonyl groups, and phenolic hydroxyl groups. There may be only one type of acid group or two or more types. The resin having acid groups can also be used as a dispersant. The acid value of the resin having acid groups is preferably 30 to 500 mg KOH / g. The lower limit is preferably 50 mg KOH / g or more, more preferably 70 mg KOH / g or more. The upper limit is preferably 400 mg KOH / g or less, more preferably 200 mg KOH / g or less, further preferably 150 mg KOH / g or less, and most preferably 120 mg KOH / g or less.

[0184] As a resin, a resin having a polymerizable group is preferred. The polymerizable group is preferably a group containing an olefinic unsaturated bond or a cyclic ether group, and more preferably a group containing an olefinic unsaturated bond.

[0185] The resin preferably includes 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 acid groups exceeds the amount of base groups. As an acidic dispersant (acidic resin), it is preferable that, when the total amount of acid groups and base groups is set to 100 mol%, the amount of acid groups is 70 mol% or more. The acid groups in the acidic dispersant (acidic resin) are preferably carboxyl groups. 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 base groups exceeds the amount of acid groups. As a basic dispersant (basic resin), it is preferable that, when the total amount of acid groups and base groups is set to 100 mol%, the amount of base groups exceeds 50 mol%. The base groups in the basic dispersant are preferably amino groups.

[0186] The resin used as a dispersant is preferably a grafted resin. For details regarding grafted resins, please refer to paragraphs 0025 to 0094 of Japanese Patent Application Publication No. 2012-255128, which is incorporated herein by reference.

[0187] The resin used as a dispersant is preferably a polyimide dispersant containing a nitrogen atom at least once in the main chain and side chains. As a polyimide dispersant, a resin having a main chain and side chains, and having a basic nitrogen atom at least once in the main chain and side chains, is preferred. The main chain contains a partial structure with functional groups having a pKa of 14 or less, and the side chains have 40 to 10,000 atoms. There are no particular limitations as long as the basic nitrogen atom is a nitrogen atom exhibiting basicity. For information on polyimide dispersants, please refer to paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, which is incorporated herein by reference.

[0188] 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 dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymers C-1 to C-31 as described in paragraphs 0196 to 0209 of Japanese Patent Application Publication No. 2013-043962.

[0189] The resin used as a dispersant is preferably a resin containing repeating units with olefinically unsaturated groups on the side chains. Preferably, the content of repeating units with olefinically unsaturated groups on the side chains is 10 mol% or more in all repeating units of the resin, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol%.

[0190] As a dispersant, the resin described in Japanese Patent Application Publication No. 2018-087939, the end-capped copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Application Publication No. 6432077, the polyethyleneimine with polyester side chains described in International Publication No. 2016 / 104803, the end-capped copolymers described in International Publication No. 2019 / 125940, the end-capped polymers with acrylamide structural units described in Japanese Patent Application Publication No. 2020-066687, the end-capped polymers with acrylamide structural units described in Japanese Patent Application Publication No. 2020-066688, and the dispersant described in International Publication No. 2016 / 104803, etc., can also be used.

[0191] Dispersants are also available as commercially available products. Specific examples include the DISPERBYK series manufactured by BYK-Chemie GmbH, the SOLSPERSE series manufactured by Japan Lubrizol Corporation, the Efka series manufactured by BASF Corporation, and the Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc. Furthermore, the products described in paragraph 0129 of Japanese Patent Application Publication No. 2012-137564 and paragraph 0235 of Japanese Patent Application Publication No. 2017-194662 can also be used as dispersants.

[0192] The content of the curable compound in the total solids component 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, further preferably 7% by mass or more, and especially preferably 10% by mass or more. The upper limit is preferably 94% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, and especially preferably 80% by mass or less.

[0193] When the composition of the present invention contains a polymeric compound as a curing compound, the content of the polymeric compound in the total solids component of the composition is preferably 1 to 85% 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.

[0194] When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer in the total solids component of the composition is preferably 1 to 50% 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 30% by mass or less, more preferably 20% by mass or less.

[0195] When the composition of the present invention contains a compound having a group containing an olefinic unsaturated bond as a curing compound, the content of the compound having a group containing an olefinic unsaturated bond in the total solids component of the composition is preferably 1 to 70% 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 65% ​​by mass or less, more preferably 60% by mass or less.

[0196] When the composition of the present invention contains a compound having a cyclic ether group as a curing compound, the content of the compound having a cyclic ether group in the total solids component 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, and even more preferably 60% by mass or less.

[0197] When the composition of the present invention contains a resin as a curing compound, the resin content in the total solids component of the composition is preferably 1 to 85% by mass. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and especially preferably 10% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, and especially preferably 40% by mass or less.

[0198] When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant in the total solids of the composition is preferably 0.1 to 40% by mass. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Furthermore, the content of the resin as a dispersant is preferably 1 to 100 parts by mass relative to 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, more preferably 5 parts by mass or more.

[0199] The compositions of the present invention may contain only one curing compound or two or more. When containing two or more curing compounds, their combined amount is preferably within the range described above.

[0200] <<Solvent>>

[0201] 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 details regarding these solvents, please refer to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. Furthermore, ester solvents with cyclic alkyl substituted structures and ketone solvents with cyclic alkyl substituted structures are preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, 3-ethoxymethyl propionate, ethyl 3-ethoxypropionate, ethyl cellulose 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, and propylene glycol monomethyl ether. Alcohol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, diacetate butane-1,3-diyl, dipropylene glycol methyl ether acetate, diacetone alcohol (as an alternative name, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropanol, etc. However, sometimes for environmental reasons, it is preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents (for example, relative to the total amount of organic solvents, it can be set to 50 ppm by mass (parts per million or less), 10 ppm by mass or less, or 1 ppm by mass or less).

[0202] The preferred organic solvent has a low metal content. For example, the metal content of the organic solvent is preferably below 10 parts per billion (ppb). Organic solvents with metal content at the ppt (parts per trillion) level can be used as needed; these organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0203] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation or membrane distillation) or filtration using a filter. The pore size of the filter used in filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0204] Organic solvents can contain isomers (compounds with the same number of atoms but different structures). Furthermore, they can contain only one isomer or multiple isomers.

[0205] The peroxide content in the organic solvent is preferably less than 0.8 mmol / L, and more preferably substantially free of peroxide.

[0206] The solvent content in the composition is preferably 10-97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further 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, more preferably 95% by mass or less. The composition may contain only one solvent or two or more solvents. When two or more solvents are contained, their combined amount is preferably within the above-mentioned range.

[0207] <<Other Infrared Absorbers>>

[0208] The compositions of the present invention can contain infrared absorbers other than the specific compounds described above (other infrared absorbers). By further containing other infrared absorbers, a film capable of blocking a wider range of infrared wavelengths can be formed. Other infrared absorbers can be dyes or pigments (particles). Examples of other infrared absorbers include pyrrolopyrrole compounds, polymethyl compounds, squaric acid compounds, phthalocyanine compounds, naphthylphthalocyanine compounds, quaterrylene compounds, benzocyanine compounds, oxocyanate compounds, imine compounds, dithiol compounds, triarylmethane compounds, pyrrole methylene compounds, methylimine compounds, anthraquinone compounds, dibenzofuranone compounds, dithioene metal complexes, metal oxides, metal borides, etc., preferably at least one selected from squaric acid compounds and phthalocyanine compounds.

[0209] Examples of pyrrolopyrrole compounds include those described in paragraphs 0016 to 0058 of Japanese Patent Application Publication No. 2009-263614, those described in paragraphs 0037 to 0052 of Japanese Patent Application Publication No. 2011-068731, and those described in paragraphs 0010 to 0033 of International Patent Application Publication No. 2015 / 166873. Examples of compounds that can be identified as squaric acid compounds include those described in paragraphs 0044-0049 of Japanese Patent Application Publication No. 2011-208101, those described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 6065169, those described in paragraph 0040 of International Publication No. 2016 / 181987, those described in Japanese Patent Application Publication No. 2015-176046, those described in paragraph 0072 of International Publication No. 2016 / 190162, and those described in Japanese Patent Application Publication No. 2016-074. The compounds described in paragraphs 0196 to 0228 of Japanese Patent Application Publication No. 649, the compounds described in paragraph 0124 of Japanese Patent Application Publication No. 2017-067963, the compounds described in International Publication No. 2017 / 135359, the compounds described in Japanese Patent Application Publication No. 2017-114956, the compounds described in Japanese Patent Application Publication No. 6197940, the compounds described in International Publication No. 2016 / 120166, and the compounds described in Table 1 of US Patent Application Publication No. 11261172, etc. Examples of polymethyl compounds include those described in paragraphs 0044-0045 of Japanese Patent Application Publication No. 2009-108267, those described in paragraphs 0026-0030 of Japanese Patent Application Publication No. 2002-194040, those described in Japanese Patent Application Publication No. 2015-172004, those described in Japanese Patent Application Publication No. 2015-172102, and those described in Japanese Patent Application Publication No. 2008-088426. Compounds described in the following publications: compounds described in paragraph 0090 of International Publication No. 2016 / 190162, compounds described in Japanese Patent Application Publication No. 2017-031394, compounds described in Japanese Patent Application Publication No. 2021-134350, compounds described in International Publication No. 2021 / 085372, and compounds described in paragraphs 0188 to 0192 of International Patent Application Publication No. 2022 / 181422. Examples of ketone acid compounds include compounds described in Japanese Patent Application Publication No. 2017-082029 and compounds described in Japanese Patent Application Publication No. 2016-079331. Examples of imine compounds include those described in Japanese Patent Application Publication No. 2008-528706, Japanese Patent Application Publication No. 2012-012399, Japanese Patent Application Publication No. 2007-092060, and those described in paragraphs 0048 to 0063 of International Publication No. 2018 / 043564.Examples of phthalocyanine compounds include those described in paragraph 0093 of Japanese Patent Application Publication No. 2012-077153, titanium phthalocyanine described in Japanese Patent Application Publication No. 2006-343631, compounds described in paragraphs 0013 to 0029 of Japanese Patent Application Publication No. 2013-195480, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, and compounds described in International Publication No. 2020 / 071470. Examples of naphthyl phthalocyanine compounds include those described in paragraph 0093 of Japanese Patent Application Publication No. 2012-077153 and those described in Japanese Patent Application Publication No. 2022-173080. Examples of dithioene metal complexes include those described in Japanese Patent No. 5733804. Examples of metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details on tungsten oxide, please refer to paragraph 0080 of Japanese Patent Application Publication No. 2016-006476, which is incorporated herein by reference. Examples of metal borides include lanthanum boride. Commercially available lanthanum boride products include LaB6-F (manufactured by Japan New Metals Co., Ltd.). Furthermore, compounds described in International Publication No. 2017 / 119394 can also be used as metal borides. Commercially available indium tin oxide products include F-ITO (manufactured by DOWA HOLDINGS CO.,LTD).

[0210] As an infrared absorber, it can also use the squaric acid compound described in Japanese Patent Application Publication No. 2017-197437, Japanese Patent Application Publication No. 2017-025311, International Publication No. 2016 / 154782, Japanese Patent No. 5884953, Japanese Patent No. 6036689, Japanese Patent No. 5810604, and International Publication No. 2017 / 21304. The following compounds contain aromatic compounds: squaric acid compounds described in paragraphs 0090-0107 of Japanese Patent Application Publication No. 7; pyrrole ring-containing compounds described in paragraphs 0019-0075 of Japanese Patent Application Publication No. 2018-054760; pyrrole ring-containing compounds described in paragraphs 0078-0082 of Japanese Patent Application Publication No. 2018-002773; and compounds with aromaticity at the α-position of the amide described in paragraphs 0024-0086 of Japanese Patent Application Publication No. 2018-041047. Squamous acid compounds with rings, amide-linked squamous acid compounds described in Japanese Patent Application Publication No. 2017-179131, compounds having a pyrrole bimorphic squamous acid skeleton or a ketone acid skeleton described in Japanese Patent Application Publication No. 2017-141215, dihydrocarbazole bimorphic squamous acid compounds described in Japanese Patent Application Publication No. 2017-082029, asymmetric compounds described in paragraphs 0027 to 0114 of Japanese Patent Application Publication No. 2017-068120, and compounds containing pyrrole rings described in Japanese Patent Application Publication No. 2017-067963. (Carbazole type), phthalocyanine compounds described in Japanese Patent No. 6251530, compounds described in Japanese Unexamined Patent Application Publication No. 2019-127549, compounds described in International Publication No. 2022 / 059619, compounds described in Japanese Unexamined Patent Application Publication No. 2022-151682, compounds described in Japanese Unexamined Patent Application Publication No. 2022-188858, compounds described in Japanese Unexamined Patent Application Publication No. 2022-184710, compounds described in Japanese Unexamined Patent Application Publication No. 2022-189736, etc.

[0211] As another infrared absorber, tungsten oxide represented by the following formula as described in paragraph 0025 of European Patent No. 3628645 can also be used.

[0212] M 1 a M 2 b W c O d (P(O)) n R m ) e

[0213] M 1 M 2 The values ​​represent ammonium cations or metal cations, where a is 0.01–0.5, b is 0–0.5, c is 1, d is 2.5–3, e is 0.01–0.75, n is 1, 2, or 3, m is 1, 2, or 3, and R represents a hydrocarbon group that may have substituents.

[0214] Preferably, the content of other infrared absorbers is 1 to 100 parts by mass relative to 100 parts by mass of the specific compound mentioned above, more preferably 3 to 60 parts by mass, and even more preferably 5 to 40 parts by mass.

[0215] The total content of the aforementioned specific compound and other infrared absorbers is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more in the total solids content of the composition. The upper limit of the total content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0216] <<Pigment Derivatives>>

[0217] The compositions of the present invention can contain pigment derivatives. Pigment derivatives can be used as dispersing agents. Dispersing agents are materials used to improve the dispersibility of pigments in a composition.

[0218] As pigment derivatives, compounds having at least one structure selected from pigment structures and triazine structures and an acid group or a base group can be listed.

[0219] Examples of pigment structures include squaric acid pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacrine pigment structure, anthraquinone pigment structure, dianthraquinone pigment structure, benzisoindole pigment structure, thiazine indigo pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, naphthyl phthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, violet ketone pigment structure, benzimidazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure, and benzoxazole pigment structure. Preferably, squaric acid pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, phthalocyanine pigment structure, quinacrine pigment structure, and benzimidazolone pigment structure are preferred, and squaric acid pigment structure and pyrrolopyrrole pigment structure are more preferred.

[0220] Acid groups present in pigment derivatives can include carboxyl, sulfonyl, phosphate, boric acid, carboxylic acid amide, sulfonic acid amide, imide, and their salts. Atoms or groups constituting salts can include alkali metal ions (Li...). + Na + K + (etc.), alkaline earth metal ions (Ca 2+Mg 2+ (etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ions, etc. As a carboxylic acid amide group, -NHCOR is preferred. X1 The indicated group. As a sulfonic acid amide group, -NHSO2R is preferred. X2 The indicated group. As an imide group, -SO2NHSO2R is preferred. X3 -CONHSO2R X4 -CONHCOR X5 or -SO2NHCOR X6 The indicated group is more preferably -SO2NHSO2R X3 R X1 ~R X6 Each can be represented independently as either alkyl or aryl. R X1 ~R X6 The alkyl and aryl groups may have substituents. Preferably, a halogen atom is used as a substituent, and more preferably a fluorine atom.

[0221] Examples of bases present in pigment derivatives include amino, pyridyl and their salts, ammonium salts, and phthaliminomethyl. Examples of atoms or groups constituting salts include hydroxide ions, halide ions, carboxylic acid ions, sulfonic acid ions, and phenoxide ions.

[0222] Specific examples of pigment derivatives include compounds described in paragraphs 0037 to 0054 of International Publication No. 2016 / 035695, compounds described in paragraphs 0061 to 0086 of International Publication No. 2017 / 146092, compounds described in paragraphs 0017 to 0068 of International Publication No. 2018 / 230387, compounds described in paragraphs 0085 to 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 their salts described in Japanese Patent Application Publication No. 2018-168244, and compounds having the isoindoline skeleton described in general formula (1) in Japanese Patent No. 6996282.

[0223] The content of the pigment derivative relative to 100 parts by weight of the pigment is preferably 1 to 50 parts by weight. The lower limit is preferably 3 parts by weight or more, more preferably 5 parts by weight or more. The upper limit is preferably 40 parts by weight or less, more preferably 30 parts by weight 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, the total amount is preferably within the above range.

[0224] <<Photopolymerization Initiator>>

[0225] When 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. There are no particular limitations on the photopolymerization initiator, and it can be suitably selected from known photopolymerization initiators. For example, compounds that are photosensitizing to light in the ultraviolet to visible regions are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0226] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaaryl biimidazole compounds, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, and α-amino ketone compounds. From the viewpoint of exposure sensitivity, photopolymerization initiators are preferably trihalomethane triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaaryl biimidazole compounds, onium compounds, benzothiazole compounds, diphenyl ketone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferably, compounds selected from oxime compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and acylphosphine compounds are preferred, and oxime compounds are even more preferred.Furthermore, examples of photopolymerization initiators include compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, and compounds with oxalic properties described in Japanese Patent Application Publication No. 2020-055992. Zolazolidinyl aminoacetophenone initiators, oxime photopolymerization initiators described in Japanese Patent Application Publication No. 2013-190459, polymers described in Japanese Patent Application Publication No. 2020-172619, compounds represented by formula (1) described in International Publication No. 2020 / 152120, compounds described in Japanese Patent Application Publication No. 2021-181406, photopolymerization initiators described in Japanese Patent Application Publication No. 2022-013379, compounds represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, and compounds represented by formula (1) described in Japanese Patent Application Publication No. 2021-507058. The following are described as fluorinated fluorenoxime ester photoinitiators: initiators described in Chinese Patent Application Publication No. 110764367, initiators described in Japanese Patent Application Publication No. 2022-518535, initiators described in International Patent Publication No. 2021 / 175855, compounds described in Japanese Patent Application Publication No. 2022-078550, compounds described in Korean Patent Publication No. 10-2017-0087330, compounds described in International Patent Publication No. 2022 / 075452, and oxime ester compounds described in Chinese Patent Application Publication No. 110066225. Compounds disclosed in Korean Patent Publication No. 10-2022-0076157, compounds disclosed in paragraphs 0042 to 0062 of International Publication No. 2019 / 013112 having a triarylamine or N-arylcarbazole skeleton, oxime ester photopolymerization initiators disclosed in Japanese Patent Publication No. 7219378, photopolymerization initiators disclosed in Korean Patent Publication No. 10-2021-0146174, photopolymerization initiators disclosed in International Publication No. 2019 / 013112, and photopolymerization initiators disclosed in Japanese Patent Application Publication No. 2023-033731, etc.

[0227] In addition, compounds described in Taiwan Patent Application Publication No. 202200534 can also be listed as photopolymerization initiators.

[0228] Specific examples of hexaaryl diimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-diimidazole, etc.

[0229] Commercially available α-hydroxy ketone 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-amino ketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (both manufactured by IGMresins BV), Irgacure 819, and Irgacure TPO (both manufactured by BASF).

[0230] Examples of oxime compounds include those described in paragraph 0142 of International Publication No. 2022 / 085485, those described in Japanese Patent No. 5430746, those described in Japanese Patent No. 5647738, those represented by general formula (1) in Japanese Patent Application Publication No. 2021-173858, or those described in paragraphs 0022-0024, and those described in Japanese Patent Application Publication No. 2021-170089. Compounds represented by the general formula (1) or compounds described in paragraphs 0117 to 0120, oxime ester compounds described in Chinese Patent Application Publication No. 110066225, compounds described in Korean Patent Publication No. 10-2022-0076157, compounds described in paragraphs 0042 to 0062 of International Publication No. 2019 / 013112 having a triarylamine or N-arylcarbazole skeleton, etc. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), etc. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-327 (manufactured by TRONLY), and Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 as described in Japanese Patent Application Publication No. 2012-014052). Furthermore, as oxime compounds, compounds that are colorless or highly transparent and resistant to discoloration are preferred. Commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0231] As photopolymerization initiators, oxime compounds having a fluorene ring, oxime compounds having at least one benzene ring in a carbazole ring forming a naphthalene ring skeleton, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 can also be used.

[0232] As a photopolymerization initiator, compounds represented by formula (OX-1) can also be used.

[0233] [Chemical Formula 7]

[0234]

[0235] In equation (OX-1), X 1a This indicates that it contains a divalent linker selected from at least one of aromatic rings and heterocycles.

[0236] R 1a Represents a hydrogen atom or an acyl group.

[0237] R 2a Indicates alkyl or aryl.

[0238] R 3a and R 4a Each can be used independently to represent a hydrogen atom or an alkyl group.

[0239] Alk 1 and Alk 2 Each can be used independently to represent an alkyl group.

[0240] R 3a With R 4a They can bond together to form a ring.

[0241] Alk 1 With Alk 2 They can bond together to form a ring.

[0242] n represents 0 or 1.

[0243] X as in equation (OX-1) 1a The divalent linker referred to may include divalent aromatic ring groups, divalent heterocyclic groups, divalent groups that bond two or more aromatic rings via single bonds or linkers, divalent groups that bond two or more heterocyclic rings via single bonds or linkers, and divalent groups that bond aromatic rings and heterocyclic rings via single bonds or linkers. Examples of linkers that bond the aforementioned aromatic rings to each other, heterocyclic groups to each other, or aromatic rings to heterocyclic rings include -CH2-, -O-, -CO-, -S-, and -NR. x - and groups formed by combining them, etc. R x It represents a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or heterocyclic group.

[0244] X in equation (OX-1) 1aPreferably, it is a group represented by any of the formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and even more preferably a group represented by formula (X-2) or formula (X-6).

[0245] [Chemical Formula 8]

[0246]

[0247] In the formula, R X1 ~R X9 Each can be independently represented by a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, or heterocyclic group.

[0248] R X1 ~R X9 The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0249] R X1 ~R X9 The alkenyl group preferably has 2 to 15 carbon atoms, more preferably 2 to 10. The alkenyl group can be straight-chain, branched, or cyclic. The alkenyl group may have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0250] R X1 ~R X9 The number of carbon atoms in the represented alkynyl group is preferably 2 to 15, more preferably 2 to 10. The alkynyl group can be straight-chain, branched, or cyclic. The alkynyl group can have substituents. Examples of substituents include halogen atoms, aryl groups, and heterocyclic groups.

[0251] R X1 ~R X9 The aryl group preferably has 6 to 20 carbon atoms, 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 heterocyclic groups.

[0252] R X1 ~R X9 The heterocyclic group represented is preferably a 5-membered or 6-membered ring. The heteroatoms in the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0253] R in equation (OX-1) 1aIt represents a hydrogen atom or an acyl group, preferably an acyl group.

[0254] R 1a The acyl group represented is preferably -C(O)-R 101 The group represented. R 101 It represents an aryl or heterocyclic group, preferably an aryl group.

[0255] R 101 The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12. The aryl group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and heterocyclic groups. 101 The aryl group represented is preferably phenyl, methylphenyl, or naphthyl, more preferably methylphenyl or naphthyl.

[0256] R 101 The heterocyclic group represented is preferably a 5-membered or 6-membered ring. The heteroatoms in the heterocyclic group are preferably oxygen, nitrogen, and sulfur atoms. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have substituents. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0257] R in equation (OX-1) 2a The group is alkyl or aryl, and alkyl is preferred for the reason that it has high reactivity in generating free radicals.

[0258] R 2a The alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10, even more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted. 2a The alkyl group represented is preferably an unsubstituted straight-chain or branched alkyl group, and more preferably an unsubstituted straight-chain alkyl group.

[0259] R 2a The aryl group represented preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents, preferably unsubstituted aryl groups.

[0260] R in equation (OX-1) 3a and R 4a Each can be represented independently as a hydrogen atom or an alkyl group, preferably a hydrogen atom.

[0261] R 3a and R 4aThe alkyl group represented preferably has 1 to 15 carbon atoms, more preferably 1 to 10, even more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted.

[0262] R 3a With R 4a They can bond together to form a ring. The formed ring is preferably a 5-membered or 6-membered ring, more preferably a 5-membered or 6-membered aliphatic hydrocarbon ring.

[0263] Alk of formula (OX-1) 1 and Alk 2 Alkyl groups are represented independently. The number of carbon atoms in an alkyl group is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and even more preferably 1 to 3. The alkyl group can be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, more preferably straight-chain. The alkyl group may have substituents, but is preferably unsubstituted.

[0264] Alk 1 With Alk 2 They can bond together to form a ring, preferably a ring. 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.

[0265] In formula (OX-1), n ​​represents 0 or 1, preferably 0.

[0266] Specific examples of compounds represented by formula (OX-1) include compounds described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2012-113104 and compounds described in paragraph 0041 of Japanese Patent Application Publication No. 2012-189997.

[0267] As a photopolymerization initiator, compounds represented by formula (OX-2) can also be used.

[0268] [Chemical Formula 9]

[0269]

[0270] In equation (OX-2), R 1b and R 2b Each substituent is represented independently, R 3b ~R 7b Each can be independently represented by a hydrogen atom or a substituent, Ar 1b This indicates an aromatic cyclic or heterocyclic group that can have substituents, and n represents 0 or 1.

[0271] As R1b and R 2b The substituents represented may include alkyl and aryl groups, preferably alkyl. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Substituents may include halogen atoms, aryl, alkenyl, ynyl, heterocyclic groups, etc. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Substituents may include halogen atoms, alkyl, alkenyl, ynyl, heterocyclic groups, etc.

[0272] As R 3b ~R 7b The substituents represented can include halogen atoms, alkyl groups, and aryl groups. Examples of alkyl and aryl groups include those mentioned above.

[0273] R 3b ~R 7b Hydrogen atoms are preferred.

[0274] Preferred Ar 1b Ar indicates an aromatic cyclic or heterocyclic group that can have substituents. 1b It can be an aromatic cyclic group that has substituents. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, and acyl groups, preferably acyl groups. Examples of acyl groups include the acyl groups mentioned above.

[0275] As a photopolymerization initiator, compounds represented by formula (OX-3) can also be used.

[0276] [Chemical Formula 10]

[0277]

[0278] In formula (OX-3), Ar 1c This indicates a (k+m+1) valence aromatic cyclic group or a (k+m+1) valence heterocyclic group.

[0279] Ar 2c This indicates a (k+2) valence aromatic cyclic group or a (k+2) valence heterocyclic group.

[0280] R 1c ~R 3c Substituents are represented independently.

[0281] L 1c Indicates a single key or CR 11c R 12c R 11c and R 12cEach can independently represent a hydrogen atom, alkyl group, or aryl group.

[0282] X 1c Indicates -O- or -S-,

[0283] k represents 0 or 1, m represents an integer from 0 to 4, and n represents 0 or 1.

[0284] As R 1c and R 2c The substituents represented may include alkyl and aryl groups, preferably alkyl. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10. The alkyl group can be straight-chain, branched, or cyclic. The alkyl group may have substituents. Substituents may include halogen atoms, aryl, alkenyl, ynyl, heterocyclic groups, etc. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have substituents. Substituents may include halogen atoms, alkyl, alkenyl, ynyl, heterocyclic groups, etc.

[0285] R 2c Preferably, it is an alkyl group having a branched or cyclic structure.

[0286] As R 3c The substituents represented may include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and acyl groups, with acyl groups being preferred. The acyl groups mentioned above may be used as examples of acyl groups.

[0287] Ar 1c This indicates a (k+m+1) valent aromatic cyclic group or a (k+m+1) valent heterocyclic group, preferably a (k+m+1) valent aromatic cyclic group. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group.

[0288] Ar 2c The term represents a (k+2) valent aromatic cyclic group or a (k+2) valent heterocyclic group, preferably a (k+2) valent aromatic cyclic group. The aromatic cyclic group is preferably a benzene cyclic group or a naphthyl cyclic group, more preferably a benzene cyclic group.

[0289] k represents 0 or 1, preferably 0.

[0290] m represents an integer from 0 to 4, preferably 0 or 1, and more preferably 1.

[0291] The following are specific examples of oxime compounds that are preferably used in this invention, but the invention is not limited to these.

[0292] [Chemical Formula 11]

[0293]

[0294] [Chemical Formula 12]

[0295]

[0296] [Chemical Formula 13]

[0297]

[0298] [Chemical Formula 14]

[0299]

[0300] The oxime compound is preferably a compound having a maximum absorption wavelength in the range of 350–500 nm, more preferably a compound having a maximum absorption wavelength in the range of 360–480 nm. Furthermore, from the viewpoint of sensitivity, the oxime compound preferably has a high molar absorptivity at wavelengths of 365 nm or 405 nm, more preferably 1,000–300,000, even more preferably 2,000–300,000, and particularly preferably 5,000–200,000. The molar absorptivity of the compound can be determined using known methods. For example, it is preferably determined using a spectrophotometer (a Cary-5 spectrophotometer manufactured by Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0301] As photopolymerization initiators, photoradical polymerization initiators with two or more functionalities can be used. By using these photoradical polymerization initiators, two or more free radicals are generated from one molecule of the initiator, thus achieving good sensitivity. Furthermore, in the case of using compounds with asymmetric structures, crystallinity decreases while solubility in solvents increases, making precipitation more difficult over time, thereby improving the long-term stability of the composition. Specific examples of photoradical polymerization initiators with two or more functionalities include the compounds described in paragraph 0148 of International Publication No. 2022 / 065215.

[0302] The content of photopolymerization initiator in the total solids component of the composition is preferably 0.1% to 30% by mass. The lower limit is preferably 0.5% by mass or more, 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 two or more types. When two or more types are contained, their combined amount is preferably within the above-mentioned range.

[0303] <<Curing Agent>>

[0304] When 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 anhydrides, amide compounds, phenolic compounds, polycarboxylic acids, and thiols. Specific examples of curing agents include succinic acid, trimellitic acid, pyrolithic acid, N,N-dimethyl-4-aminopyridine, and neopentyltetra(3-mercaptopropionate). The curing agent can also be the compounds described in paragraphs 0072 to 0078 of Japanese Patent Application Publication No. 2016-075720 and the compounds described in Japanese Patent Application Publication No. 2017-036379. Preferably, the content of the curing agent is 0.01 to 20 parts by mass relative to 100 parts by mass of the compound having a cyclic ether group, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 6.0 parts by mass.

[0305] <<Coloring Agents>>

[0306] The compositions of the present invention can contain colorants. Examples of colorants include red, green, blue, yellow, purple, and orange colorants. The colorant can be a pigment or a dye. Pigments and dyes can be used simultaneously. Furthermore, the pigment can be either inorganic or organic. The pigment can also be a material in which a portion of an inorganic pigment or an organic-inorganic pigment is replaced by an organic chromophore. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be easily achieved.

[0307] The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, 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. Furthermore, in this specification, the primary particle size of the pigment can be determined by observing the primary particles of the pigment using a transmission electron microscope and based on the obtained photographs. Specifically, the projected area of ​​the primary particles of the pigment is calculated, and the corresponding circular equivalent diameter is taken as the primary particle size of the pigment. Moreover, the average primary particle size in this specification is set as the arithmetic mean of the primary particle sizes of 400 pigment particles. Furthermore, the primary particles of the pigment refer to unaggregated independent particles.

[0308] The crystallite size, derived from the half-width of the peak of any crystal plane in the X-ray diffraction spectrum when CuKα rays are used as the X-ray source, is preferably 0.1–100 nm, more preferably 0.5–50 nm, even more preferably 1–30 nm, and particularly preferably 5–25 nm.

[0309] The specific surface area of ​​the pigment is preferably 1 to 300 m². 2 / g. The lower limit is preferably 10m. 2 / g or more, preferably 30m 2 / g or more. The upper limit is preferably 250m. 2 / g or less, more preferably 200m 2 / g or less. The specific surface area value can be determined according to the BET (Brunauer, Emmett and Teller) method and according to DIN 66131: determination of the specific surface area of ​​solids by gas adsorption.

[0310] The colorant preferably contains pigment. The pigment content in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Examples of pigments include those listed below.

[0311] Colorimetric Index (CI) for 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, 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 (methylene derivatives), 233 (quinoline derivatives), 234 (aminoketone derivatives), 235 (aminoketone derivatives), 236 (aminoketone derivatives), etc. (the above are yellow pigments).

[0312] 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, 73, etc. (the above are orange pigments)

[0313] CI 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, 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 (Xanton type, Organic Ultramarine, Bluish Red), 295 (Monoazo type), 296 (Diazo type), 297 (Aminoketone type), etc. (the above are red pigments)

[0314] CI pigments green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine), 65 (phthalocyanine), 66 (phthalocyanine), etc. (the above are green pigments).

[0315] CI pigments include purple 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane), 61 (xanthine), etc. (the above are purple pigments).

[0316] 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 (monoazo), 88 (methylene), etc. (the above are blue pigments).

[0317] As a green colorant, zinc halide phthalocyanine pigments with an average of 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms per molecule can also be used. Specific examples include the compound described in International Patent Publication No. 2015 / 118720. Furthermore, as a green colorant, compounds described in paragraph 0029 of International Patent Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Application Publication No. 2020-070426, and diarylmethane compounds described in Japanese Patent Application Publication No. 2020-504758, etc., can also be used.

[0318] As a blue coloring agent, aluminum phthalocyanine compounds having phosphorus atoms can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Application Publication No. 2011-157478.

[0319] As a yellow coloring agent, compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485, methylene dyes described in Japanese Patent Application Publication No. 2019-073695, and methylene dyes described in Japanese Patent Application Publication No. 2019-073696 can be used.

[0320] As a red coloring agent, compounds described in paragraph 0034 of International Publication No. 2022 / 085485 and brominated dione pyrrolopyrrole compounds described in Japanese Patent Application Publication No. 2020-085947 can also be used.

[0321] Coloring agents can also use dyes. There are no particular restrictions on the dyes used; well-known dyes can be used. Examples include pyrazole azo dyes, aniline azo dyes, triarylmethane dyes, anthraquinone dyes, anthraquinone dyes, benzylene dyes, oxacyanine dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthocyanin dyes, phenazine dyes, pyrrolopyrazole methylimine dyes, xanthan dyes, phthalocyanine dyes, benzopiperanium dyes, indigo dyes, and pyrrole methylene dyes. Furthermore, dyes can also include thiazole compounds described in Japanese Patent Application Publication No. 2012-158649, azo compounds described in Japanese Patent Application Publication No. 2011-184493, and azo compounds described in Japanese Patent Application Publication No. 2011-145540.

[0322] As a coloring agent, it is also possible to use the triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, the xanthones compound described in Japanese Patent Application Publication No. 2020-117638, the phthalocyanine compound described in International Patent Publication No. 2020 / 174991, the isoindoline compound or its salts described in Japanese Patent Application Publication No. 2020-160279, the compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442, the compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730, and the compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070. The compounds represented by Formula 1 as described herein, the compounds represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0069067, the compounds represented by Formula 1 as described in Korean Patent Publication No. 10-2020-0069062, the zinc halide phthalocyanine pigment described in Japanese Patent No. 6809649, the isoindoline compounds described in Japanese Unexamined Patent Publication No. 2020-180176, the phenazine compounds described in Japanese Unexamined Patent Publication No. 2021-187913, the zinc halide phthalocyanine pigment described in International Publication No. 2022 / 004261, the zinc halide phthalocyanine pigment described in International Publication No. 2021 / 250883, and Korean Patent Publication No. 10-2020-0030 The following compounds are included: the quinoline yellow compound represented by Formula 1 in Japanese Patent Publication No. 759; the polymer dye described in Korean Patent Publication No. 10-2020-0061793; the colorant described in Japanese Patent Application Publication No. 2022-029701; the isoindoline compound described in International Patent Publication No. 2022 / 014635; the aluminum phthalocyanine compound described in International Patent Publication No. 2022 / 024926; the compound described in Japanese Patent Application Publication No. 2022-045895; the compound described in International Patent Publication No. 2022 / 050051; the compound described in Japanese Patent Application Publication No. 2020-090676; the compound described in Japanese Patent Application Publication No. 2020-055956; and the compound described in Japanese Patent Application Publication No. 202... The compounds described in Japanese Patent Application Publication No. 1-031681, Japanese Patent Application Publication No. 2022-056354, U.S. Patent Application Publication No. 2021 / 0355327, International Patent Application Publication No. 2022 / 065357, Japanese Patent Application Publication No. 2020-045436, Korean Patent Publication No. 10-2021-0146726, Japanese Patent Application Publication No. 2018-178039, Chinese Patent Application Publication No. 113881244, and Chinese Patent Application Publication No. 113881245.The compounds described in Chinese Patent Application Publication No. 113881246, Japanese Patent Application Publication No. 2022-104822, Japanese Patent Application Publication No. 2022-096701, Japanese Patent Application Publication No. 2020-023652, the green pigment described on pages 80-84 of the Journal of the Japan Society for Color Materials (published in 2022), the compounds described in Japanese Patent Application Publication No. 2022-143135, Japanese Patent Application Publication No. 2022-140287, the compound described in International Publication No. 2022 / 136308, the perylene compound described in Chinese Patent Application Publication No. 113061349, the cyanide pigment described in Korean Patent Publication No. 10-2017-0018993, and Japanese Patent Application Publication No. 2020-180176... The compounds described in the report, the compounds described in Japanese Patent Application Publication No. 2023-013209, the compounds described in Japanese Patent Application Publication No. 2023-013166, the xaton compound described in International Publication No. 2023 / 286526, the compounds described in Japanese Patent Application Publication No. 2021-155746, the compounds described in Japanese Patent Application Publication No. 2021-155747, and Japanese Patent Application Publication No. 2 The compounds described in Japanese Patent Application Publication No. 021-155748, Japanese Patent Application Publication No. 2021-155749, Japanese Patent Publication No. 2018 / 051876, Japanese Patent Application Publication No. 2020-083981, Japanese Patent Application Publication No. 2023-056463, and Japanese Patent Publication No. 2023-515473. The colorant can be rotaxane, and the pigment skeleton can be used for cyclic structures, rod-shaped structures, or both of these structures.

[0323] When the composition of the present invention contains a colorant, the content of the colorant in the total solids of the composition is preferably 1 to 50% by mass. When the composition of the present invention contains two or more colorants, their combined amount is preferably within the above range.

[0324] When using the composition of the present invention as an infrared cutoff filter, it is preferable that the composition of the present invention substantially does not contain colorant. Furthermore, "substantially does not contain colorant" means that the content of colorant in the total solids of the composition is 0.5% by mass or less, preferably 0.1% by mass or less, and more preferably, it contains no colorant.

[0325] <<Colorants that transmit infrared light and block visible light>>

[0326] The compositions of the present invention may also contain colorants that transmit infrared light and block visible light (hereinafter also referred to as visible light-blocking colorants). Compositions containing visible light-blocking colorants are preferably used as compositions for forming infrared transmission filters.

[0327] The colorant used to block visible light is preferably a colorant that absorbs light in the violet to red wavelength range. Furthermore, the colorant used to block visible light is preferably a colorant that blocks light in the wavelength range of 450–650 nm. Moreover, the colorant used to block visible light is preferably a colorant that allows light in the wavelength range of 900–1500 nm to pass through. The colorant used to block visible light preferably satisfies at least one of the following requirements (A) and (B).

[0328] (A): Contains two or more colorants, and black is formed by the combination of two or more colorants.

[0329] (B): Contains organic black coloring agents.

[0330] As colorants, the aforementioned colorants can be listed. As organic black colorants, examples include bisbenzofuranone compounds, imine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. As bisbenzofuranone compounds, compounds described in Japanese Patent Application Publication Nos. 2010-534726, 2012-515233, and 2012-515234 can be listed, for example, and can be obtained as "Irgaphor Black" manufactured by BASF. As perylene compounds, compounds described in paragraphs 0016 to 0020 of Japanese Patent Application Publication No. 2017-226821, CI Pigment Black 31, 32, etc., can be listed. As a methylimine compound, examples include compounds described in Japanese Patent Application Publication No. 01-170601 and Japanese Patent Application Publication No. 02-034664, which can be obtained, for example, as “CHROMO FINE BLACK A1103” manufactured by Dainichiseika Color & Chemicals Mfg.Co.,Ltd.

[0331] As a combination of colorants that forms black by combining two or more colorants, the following (1) to (8) can be listed as examples.

[0332] (1) A method containing yellow colorant, blue colorant, purple colorant and red colorant.

[0333] (2) A method containing yellow colorant, blue colorant and red colorant.

[0334] (3) The method of containing yellow colorant, purple colorant and red colorant.

[0335] (4) Methods containing yellow and purple colorants.

[0336] (5) A method containing green colorant, blue colorant, purple colorant and red colorant.

[0337] (6) Methods containing purple and orange colorants.

[0338] (7) A method containing green colorant, purple colorant and red colorant.

[0339] (8) Methods containing green and red colorants.

[0340] When the composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light in the total solids of the composition is preferably 1 to 50% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and especially preferably 30% by mass or more.

[0341] When using the composition of the present invention as an infrared cutoff filter, it is preferable that the composition of the present invention substantially does not contain colorants that block visible light. Furthermore, "substantially does not contain colorants that block visible light" means that the content of colorants that block visible light in the total solids component of the composition is 0.5% by mass or less, preferably 0.1% by mass or less, and more preferably, it contains no colorants that block visible light.

[0342] <<Surfactants>>

[0343] The compositions of the present invention can contain surfactants. Various surfactants, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants, can be used as surfactants. Silicone surfactants or fluorinated surfactants are preferred. Regarding surfactants, reference can be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, the contents of which are incorporated herein by reference.

[0344] As a fluorinated surfactant, the compounds described in paragraphs 0167 to 0173 of International Publication No. 2022 / 085485 can be used.

[0345] As nonionic surfactants, compounds described in paragraph 0174 of International Publication No. 2022 / 085485 can be cited as examples.

[0346] Examples of polysiloxane surfactants 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, and BYK-UV3510 (manufactured by BYK-Chemie). (Made by GmbH), etc. Compounds with the following structures can also be used in polysiloxane surfactants.

[0347] [Chemical Formula 15]

[0348]

[0349] The surfactant content in the total solids component 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, further preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less. The composition may contain only one surfactant or two or more surfactants. When two or more surfactants are contained, their combined amount is preferably within the above-mentioned range.

[0350] <<Polymerization Inhibitor>>

[0351] The compositions of the present invention can contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallnut phenol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine salts (ammonium salts, cerium salts, etc.), with p-methoxyphenol being preferred. The content of the polymerization inhibitor in the total solids component of the composition is preferably 0.0001 to 5% by mass. The composition may contain only one polymerization inhibitor or two or more. When two or more are contained, their combined amount is preferably within the above-mentioned range.

[0352] <<Silane Coupling Agents>>

[0353] The compositions of the present invention can contain a silane coupling agent. The silane coupling agent is preferably a silane compound having a hydrolyzable group, more preferably a silane compound having a hydrolyzable group and other functional groups. A hydrolyzable group refers to a substituent that directly bonds to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a fusion reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, etc., with alkoxy groups being preferred. The silane coupling agent is preferably a compound having an alkoxysilyl group. Furthermore, examples of functional groups other than the hydrolyzable group include vinyl, styryl, (meth)acryloyl, mercapto, epoxy, oxetyl, amino, urea, thioether, isocyanate, phenyl, etc., with (meth)acryloyl and epoxy groups being preferred. Examples of silane coupling agents include compounds described in International Publication No. 2022 / 085485, paragraph 0177, and compounds described in Japanese Patent Application Publication No. 2019-183020. The content of the silane coupling agent in the total solids component of the composition is preferably 0.1% to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The composition may contain only one type of silane coupling agent or two or more types. When two or more types are contained, their combined amount is preferably within the above-mentioned range.

[0354] <<Ultraviolet Absorber>>

[0355] The compositions of the present invention can contain ultraviolet absorbers. Examples of ultraviolet absorbers include conjugated diene compounds, amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, triazine compounds, and benzoyl compounds. The ultraviolet absorber can also include compounds described in paragraphs 0038 to 0052 of Japanese Patent Application Publication No. 2009-217221, compounds described in paragraphs 0052 to 0072 of Japanese Patent Application Publication No. 2012-208374, compounds described in paragraphs 0317 to 0334 of Japanese Patent Application Publication No. 2013-068814, compounds described in paragraphs 0061 to 0080 of Japanese Patent Application Publication No. 2016-162946, compounds described in paragraphs 0059 to 0076 of International Publication No. 2016 / 181987, and compounds described in paragraphs 0052 and 0074 of International Publication No. 2021 / 131355. Compounds described in paragraphs 0022-0024 of International Publication No. 2021 / 132247, compounds described in paragraph 0179 of International Publication No. 2022 / 085485, reactive triazine UV absorbers described in Japanese Patent Application Publication No. 2021-178918, UV absorbers described in Japanese Patent Application Publication No. 2022-007884, compounds described in Korean Patent Publication No. 10-2022-0014454, compounds described in Japanese Patent Application Publication No. 2023-013321, and compounds described in paragraphs 0049-0059 of Japanese Patent Application No. 6268967. Commercially available UV absorbers include the Tinuvin series and Uvinul series manufactured by BASF. Furthermore, examples of benzotriazole compounds include the MYUA series manufactured by MIYOSHI OIL & FAT CO.,LTD. (Chemical Industry Daily, February 1, 2016). The content of the ultraviolet absorber in the total solids component 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, further 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 two or more types. When two or more types are contained, their combined amount is preferably within the above-mentioned range.

[0356] <<Antioxidants>>

[0357] The compositions of the present invention can contain antioxidants. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. Examples of hindered phenolic compounds are examples of phenolic antioxidants. Phenolic antioxidants are preferably compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Antioxidants are also preferably compounds having a phenolic group and a phosphite group within the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-2-yl)oxy]ethyl]amine, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, and tris(2,4-di-tert-butylphenyl) phosphite. Commercially available antioxidants include, for example, 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 CO.,LTD.). The antioxidant can also be the compounds described in paragraphs 0023-0048 of Japanese Patent No. 6268967, the compounds described in International Publication No. 2017 / 006600, the compounds described in International Publication No. 2017 / 164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371. The 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, more preferably 0.5% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The composition may contain only one antioxidant or two or more. When containing two or more antioxidants, their combined amount is preferably within the above range.

[0358] <<Other Ingredients>>

[0359] The compositions of the present invention may also contain, as needed, sensitizers, fillers, thermosetting accelerators, plasticizers, and other additives (e.g., conductive particles, defoamers, flame retardants, leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, potential antioxidants, etc.). By appropriately including these components, the physical properties of the film can be adjusted. These components can be compounds described in paragraph 0182 of International Publication No. 2022 / 085485. Furthermore, the chain transfer agent can be a thiol compound described in Japanese Patent Application Publication No. 2020-109068.

[0360] The free metal content of the composition of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less. Furthermore, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing free metals or halogens in the composition include washing with ion-exchanged water, filtration, ultrafiltration, purification based on ion-exchange resins, and purification based on inorganic adsorbents such as hydrotalcite.

[0361] From an environmental regulatory perspective, the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, is sometimes regulated. In the compositions of the present invention, when reducing the content of the aforementioned compounds, it is preferable that the content of perfluoroalkyl sulfonic acids (especially perfluoroalkyl sulfonic acids with 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts, and perfluoroalkyl carboxylic acids (especially perfluoroalkyl carboxylic acids with 6 to 8 carbon atoms in the perfluoroalkyl group) and their salts is in the range of 0.01 ppb to 1,000 ppb relative to the total solids content of the composition, 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. The compositions of the present invention may also be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using compounds that can replace perfluoroalkyl sulfonic acids and their salts, and compounds that can replace perfluoroalkyl carboxylic acids and their salts, compositions that are substantially free of perfluoroalkyl sulfonic acids and their salts can also be selected. As alternatives to regulated compounds, examples include compounds excluded from regulation based on differences in the number of carbon atoms in the perfluoroalkyl group. However, the foregoing does not preclude the use of perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts. The compositions of the present invention may also contain perfluoroalkyl sulfonic acids and their salts, as well as perfluoroalkyl carboxylic acids and their salts, to the maximum permissible extent.

[0362] From an environmental regulatory perspective, the content of fluorinated compounds in the composition can be set to less than 5% by mass, less than 1% by mass, less than 100 ppm by mass, less than 1 ppm by mass, or substantially non-existent.

[0363] <Containment Container>

[0364] There are no particular limitations on the container used for the composition of the present invention, and known containers can be used. Furthermore, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can be used as the container.

[0365] <Preparation method of the composition>

[0366] The compositions of the present invention can be prepared by mixing the said components. In preparing the composition, all components can be simultaneously dissolved or dispersed in a solvent, or, as needed, two or more solutions or dispersions appropriately formulated with each component can be prepared in advance and mixed together before use (during coating) to prepare the composition.

[0367] The preparation of the composition may include a process for dispersing pigments. Examples of mechanical forces used to disperse pigments in this process include compression, extrusion, impact, shearing, and pitting. Specific examples of these processes include bead milling, sand milling, roller milling, ball milling, coating agitation, microjet milling, high-speed impeller milling, sand mixing, jet mixing, high-pressure wet microparticle formation, and ultrasonic dispersion. Furthermore, in the pulverization of pigments in sand mixing (bead milling), it is preferable to perform the process under conditions that improve pulverization efficiency by using small-diameter beads and increasing the bead filling rate. Moreover, it is preferable to remove coarse particles after pulverization by filtration, centrifugation, or the like. Furthermore, the pigment dispersion process and disperser can preferably use the processes and dispersers described in "Complete Collection of Dispersion Technology, JOHOKIKO CO.,LTD., July 15, 2005" or "Comprehensive Collection of Practical Data on Dispersion Technology and Industrial Applications Centered on Suspension (Solid / Liquid Dispersion Systems), Business Development Center Publishing Department, October 10, 1978", and paragraph 0022 of Japanese Patent Application Publication No. 2015-157893. In addition, the pigment dispersion process can be achieved by a salt milling step to refine the pigment. The materials, equipment, and processing conditions used in the salt milling step can be referenced, for example, in Japanese Patent Application Publication Nos. 2015-194521 and 2012-046629. Examples of microsphere materials used for dispersion include zirconium dioxide, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Furthermore, the microspheres can also be made from inorganic compounds with a Mohs hardness of 2 or higher. The composition may contain 1 to 10,000 ppm of the aforementioned microspheres.

[0368] When preparing the composition, it is preferable to filter the composition using a filter for the purpose of removing foreign matter and reducing defects. Examples of filters and filtration methods described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485 can be cited as examples of filters and filtration methods used for filtration.

[0369] <Membrane>

[0370] Next, the membrane of the present invention will be described. The membrane of the present invention is a membrane obtained from the composition of the present invention described above. The membrane of the present invention can preferably be used as a filter. The application of the filter is not particularly limited, and examples include infrared cut-off filters, infrared transmission filters, etc. Examples of infrared cut-off filters include infrared cut-off filters on the light-receiving side of a solid-state imaging element (e.g., infrared cut-off filters for wafer-level lenses), infrared cut-off filters on the back side (the side opposite to the light-receiving side) of a solid-state imaging element, and infrared cut-off filters for ambient light sensors (e.g., illuminance sensors that sense the illuminance and hue of the environment in which an information terminal device is placed and adjust the hue of the display, color correction sensors that adjust the hue). In particular, it can preferably be used as an infrared cut-off filter on the light-receiving side of a solid-state imaging element. Examples of infrared transmission filters include filters that block visible light and selectively transmit infrared light above a certain wavelength.

[0371] The film of the present invention can be patterned or unpatterned (flat film). Furthermore, the film of the present invention can be used by laminating it onto a support or by peeling it off from the support. Examples of supports include semiconductor substrates such as silicon substrates or transparent substrates.

[0372] Charge-coupled devices (CCDs), complementary metal-oxide-semiconductor (CMOS) layers, photoelectric conversion layers, transparent conductive films, and other components can be formed on the semiconductor substrate used as a support. Furthermore, partitions is sometimes formed on the semiconductor substrate to isolate each pixel. Examples of partitions include metals, metal oxides, and black matrices. Additionally, to improve adhesion to the upper layer, prevent material diffusion, or achieve substrate surface planarization, an undercoat layer can be applied to the semiconductor substrate as needed.

[0373] As a transparent substrate used as a support, there are no particular limitations as long as it is made of a material capable of transmitting at least visible light. Examples of substrates include glass and resin. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, norbornene resin, polyacrylate, acrylic resins such as polymethyl methacrylate, urethane resin, vinyl chloride resin, fluoropolymer resin, polycarbonate resin, polyvinyl butyral resin, and polyvinyl alcohol resin. Examples of glass include soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, and copper-containing glass. Examples of copper-containing glass include copper phosphate glass and copper fluorophosphate glass. Commercially available copper-containing glass can also be used. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC TECHNO GLASS Co., Ltd.).

[0374] The thickness of the membrane of the present invention can be appropriately adjusted according to the purpose. The membrane thickness can be set to 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 membrane thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more.

[0375] When the membrane of the present invention is used as an infrared cutoff filter, the membrane of the present invention preferably has a maximum absorption wavelength in the wavelength range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm).

[0376] Furthermore, the average transmittance in the wavelength range of 700 to 720 nm is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and especially preferably 2% or less.

[0377] Furthermore, the average transmittance in the wavelength range of 400–550 nm is preferably 86% or higher, more preferably 89% or higher, even more preferably 92% or higher, and particularly preferably 95% or higher. Moreover, the transmittance in all wavelength ranges from 420 to 550 nm is preferably 50% or higher, more preferably 70% or higher, and even more preferably 80% or higher.

[0378] Furthermore, the transmittance at at least one location within the wavelength range of 650–1500 nm (preferably 660–1200 nm, more preferably 660–1000 nm) is preferably 10% or less, more preferably 7% or less, even more preferably 4% or less, and particularly preferably 2% or less.

[0379] Furthermore, when the absorbance at the maximum absorption wavelength is set to 1, it is preferable that the average absorbance of the film of the present invention is less than 0.030 in the wavelength range of 400 to 550 nm, more preferably less than 0.025.

[0380] When the membrane of the present invention is used as an infrared transmission filter, the membrane of the present invention preferably has any of the following (i1) to (i3) spectral characteristics.

[0381] (i1): A filter with 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 with this spectral dispersive characteristic can block light in the wavelength range of 400 to 850 nm while allowing light exceeding 950 nm to pass through.

[0382] (i2): A filter with 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 with this spectral dispersive characteristic can block light in the wavelength range of 400 to 950 nm while allowing light exceeding wavelength 1050 nm to pass through.

[0383] (i3): A filter with 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 with this spectral dispersive characteristic can block light in the wavelength range of 400 to 1050 nm while allowing light exceeding wavelength 1150 nm to pass through.

[0384] The membrane of the present invention can also be used in combination with a color filter containing a colorant. The color filter can be manufactured using a coloring composition containing a colorant. When the membrane of the present invention is used as an infrared cutoff filter and the membrane of the present invention is used in combination with a color filter, it is preferable that the color filter is disposed on the optical path of the membrane of the present invention. For example, it is preferable to laminate the membrane of the present invention and the color filter to use as a laminate. In the laminate, the membrane of the present invention and the color filter may be adjacent or not adjacent in the thickness direction. When the membrane of the present invention and the color filter are not adjacent in the thickness direction, the membrane of the present invention may be formed on a different support than the support on which the color filter is formed, or other components constituting a solid-state imaging element (e.g., microlenses, planarization layers, etc.) may be interposed between the membrane of the present invention and the color filter.

[0385] The film of the present invention can be used in various devices such as CCD (charge-coupled device), CMOS (complementary metal oxide semiconductor) and other solid-state imaging elements (in addition to Si, the imaging part can also use compound semiconductors such as InGaAs, organic semiconductors, quantum dots, etc.), infrared sensors, light-emitting elements, optical communication elements (including transceivers), image display devices, etc.

[0386] <Membrane Manufacturing Method>

[0387] The film of the present invention can be manufactured by coating the composition of the present invention.

[0388] The aforementioned supports can be used as examples of supports. As for the coating method of the composition, known methods such as spin coating can be used. For example, the coating method described in paragraph 0207 of International Publication No. 2022 / 085485 can be used.

[0389] The coating layer formed by applying the composition can be dried (pre-baked). When pre-baking, the pre-baking temperature is preferably below 150°C, more preferably below 120°C, and even more preferably below 110°C. The lower limit can be, for example, set to 50°C or higher, and also to 80°C or higher. The pre-baking time is preferably from 10 seconds to 3000 seconds, more preferably from 40 to 2500 seconds, and even more preferably from 80 to 220 seconds. Drying can be performed using a heating plate, oven, or the like.

[0390] The method for manufacturing the film may further include a pattern-forming step. Examples of pattern-forming methods include those using photolithography and those using dry etching; the photolithography method is preferred. Furthermore, when the film of the present invention is used as a planarization film, the pattern-forming step may be omitted. The pattern-forming step will be described in detail below.

[0391] (The case of creating patterns using photolithography)

[0392] The pattern forming method using photolithography preferably includes a step of exposing a composition layer formed by coating the composition of the present invention in a patterned manner (exposure step) and a step of developing to remove unexposed portions of the composition layer to form a pattern (development step). A step of baking the developed pattern (post-baking step) may be provided as needed. Each step will be described below.

[0393] In the exposure process, the composition layer is exposed in a patterned manner. For example, using a stepper or scanning exposure machine, the composition layer is exposed through a mask with a predetermined mask pattern, thereby enabling patterned exposure. This allows the exposed portion to be cured.

[0394] Examples of radiation (light) that can be used during exposure include gamma rays and i-rays. Furthermore, light with wavelengths below 300 nm can also be used (preferably light with wavelengths of 180–300 nm). Examples of light with wavelengths below 300 nm include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Moreover, light sources with wavelengths above 300 nm can also be used.

[0395] Furthermore, during exposure, exposure can be performed by continuous illumination or by pulsed illumination (pulse exposure). In addition, pulse exposure refers to an exposure method that involves repeatedly illuminating and pausing light in short cycles (e.g., less than milliseconds).

[0396] The irradiation dose (exposure dose) is preferably 0.03 to 2.5 J / cm. 2 More preferably, it is 0.05–1.0 J / cm³. 2 The oxygen concentration during exposure can be appropriately selected. Besides exposure in the atmosphere, it can be performed in a low-oxygen atmosphere (e.g., 15% or 5% by volume, or virtually oxygen-free) or in a high-oxygen atmosphere (e.g., 22%, 30%, or 50% by volume) with an oxygen concentration exceeding 21% by volume. Furthermore, the exposure illuminance can be appropriately set, typically from 1000 W / m². 2 ~100000W / m 2 (For example, 5000W / m) 2 15000W / m 2 Or 35000W / m 2 The range of oxygen concentration and exposure illuminance can be selected. These conditions can be appropriately combined; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m² can be set. 2 Oxygen concentration 35% by volume and illuminance 20000 W / m² 2 wait.

[0397] Next, the unexposed portions of the composition layer after exposure are removed by development to form a pattern. The removal of the unexposed portions of the composition layer can be performed using a developing solution. Here, the unexposed portions of the composition layer from the exposure process dissolve into the developing solution, leaving only the photocured portion on the support. The temperature of the developing solution is preferably, for example, 20–30°C. The development time is preferably 20–180 seconds. Furthermore, to improve residue removal, the process of repeatedly discarding the developing solution every 60 seconds and then supplying new developing solution can be repeated multiple times.

[0398] Developers may include organic solvents, alkaline developers, etc., and alkaline developers are preferred. Regarding the developer and the post-development cleaning (rinsing) method, the developer or cleaning method described in paragraph 0214 of International Publication No. 2022 / 085485 may be used.

[0399] After development, it is preferable to perform additional exposure and heating treatment (post-baking) after drying. The additional exposure and post-baking are post-development curing treatments for complete curing. The heating temperature during post-baking is preferably 100–240°C, more preferably 200–240°C. The developed film can be post-baked continuously or intermittently using heating mechanisms such as heating plates, convection ovens (hot air circulating dryers), or high-frequency heaters, in accordance with the above conditions. When performing additional exposure, the light used for exposure is preferably light with a wavelength of 400 nm or less. Furthermore, the additional exposure can be performed using the method described in Korean Patent Publication No. 10-2017-0122130.

[0400] (The case of forming a pattern using dry etching)

[0401] When forming a pattern using dry etching, the following method can be used: a composite layer formed by coating the above-described composition onto a support is cured to form a cured layer; a patterned photoresist layer is then formed on the cured layer; the patterned photoresist layer is then used as a mask, and the cured layer is dry-etched using an etching gas. Pre-baking is preferably performed when forming the photoresist layer. For details on forming patterns using dry etching, please refer to paragraphs 0010 to 0067 of Japanese Patent Application Publication No. 2013-064993, which is incorporated herein by reference.

[0402] <Filter>

[0403] The filter of the present invention has the membrane described above. Examples of filters include infrared cut-off filters and infrared transmission filters.

[0404] In addition to the film described above, the filter of the present invention may further include a copper-containing layer, a dielectric multilayer film, and an ultraviolet-absorbing layer. For example, the ultraviolet-absorbing layer described in paragraphs 0040-0070 and 0119-0145 of International Publication No. 2015 / 099060 can be used as an absorption layer. For example, the dielectric multilayer film described in paragraphs 0255-0259 of Japanese Patent Application Publication No. 2014-041318 can be used as a dielectric multilayer film. For the copper-containing layer, a glass substrate made of copper-containing glass (copper-containing glass substrate) or a layer containing a copper complex (copper-containing complex layer) can also be used. Examples of copper-containing glass substrates include copper phosphate glass and copper fluorophosphate glass. Commercially available copper-containing glass products include NF-50 (manufactured by AGC TECHNO GLASS Co., Ltd.), BG-60, BG-61 (manufactured by Schott AG), and CD5000 (manufactured by HOYACORPORATION).

[0405] The filter of the present invention can be formed on a support. Examples of supports include those described above. Preferred substrates include transparent substrates made of materials such as glass and resin. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, norbornene resin, polyacrylate, acrylic resins such as polymethyl methacrylate, urethane resin, vinyl chloride resin, fluoropolymer resin, polycarbonate resin, polyvinyl butyral resin, and polyvinyl alcohol resin. Examples of glass include soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, and copper-containing glass. Furthermore, the filter can be directly deposited onto various components.

[0406] Solid-state imaging element

[0407] The solid-state imaging element of the present invention has the film of the present invention described above. As for the structure of the solid-state imaging element, there are no particular limitations as long as it has the structure of the film of the present invention and functions as a solid-state imaging element. Examples include the following structures.

[0408] The structure is as follows: a support has multiple photodiodes constituting the light-receiving area of ​​a solid-state imaging element and a transmission electrode made of polysilicon or the like; a light-shielding film made of tungsten or the like has an opening only in the light-receiving portion of the photodiodes on the photodiodes and the transmission electrode; a device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire light-shielding film and the light-receiving portion of the photodiodes; and the film of the present invention is on the device protective film. Furthermore, it can also be a structure with a light-gathering mechanism (e.g., a microlens, etc. The same applies hereinafter) on the device protective film and below the film of the present invention (near the support side), or a structure with a light-gathering mechanism on the film of the present invention, etc. Furthermore, the color filter can also have a structure in which, for example, a film forming each pixel is embedded in a grid-like space divided by partitions. In this case, the partitions preferably have a low refractive index compared to each pixel. Examples of imaging devices with this structure include those described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577.

[0409] <Image display device>

[0410] The image display device of the present invention incorporates the film of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescent (organic EL) display devices. Definitions and details regarding image display devices are described, for example, in "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Publishing Co., Ltd., 1989). Furthermore, liquid crystal display devices are described, for example, in "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994). There are no particular limitations on the liquid crystal display devices to which the present invention can be applied; for example, liquid crystal display devices of various types described in the aforementioned "Next-Generation Liquid Crystal Display Technology" can be applied. The image display device may be an image display device having a white organic EL element. A series structure is preferred as the white organic EL element. Regarding the series structure of organic EL elements, it is described in Japanese Patent Application Publication No. 2003-045676, supervised by Akiyoshi Mikami, "The Forefront of Organic EL Technology Development - High Brightness, High Precision, Long Lifespan Technology Collection -", TECHNICALINFORMATION INSTITUTE CO.,LTD., 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 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 transmission film disposed in an infrared communication opening formed on the frame portion of a protective plate for a display device.

[0411] <Infrared Sensor>

[0412] The infrared sensor of the present invention has the membrane described above. There are no particular limitations on the structure of the infrared sensor, as long as it functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to the accompanying drawings.

[0413] exist Figure 1In the image, 110 represents a solid-state imaging element. An infrared cutoff filter 111 and an infrared transmission filter 114 are disposed on the imaging area of ​​the solid-state imaging element 110. Furthermore, a color filter 112 is disposed on the infrared cutoff filter 111. A microlens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlens 115.

[0414] The infrared cutoff filter 111 can be formed using the composition of the present invention. The color filter 112 is not particularly limited to a color filter that forms pixels that transmit and absorb light of a specific wavelength in the visible region; conventionally known pixel-forming color filters can be used. For example, color filters that form pixels of red (R), green (G), and blue (B) can be used. For example, reference can be made to paragraphs 0214 to 0263 of Japanese Patent Application Publication No. 2014-043556, the contents of which are incorporated herein by reference. The infrared transmission filter 114 can be selected according to the emission wavelength of the infrared LED used. The infrared transmission filter 114 can be formed using the composition of the present invention.

[0415] exist Figure 1 In the infrared sensor shown, an infrared cutoff filter (other infrared cutoff filter) different from the infrared cutoff filter 111 can be further configured on the planarization layer 116. Examples of other infrared cutoff filters include infrared cutoff filters having copper layers and / or dielectric multilayer films. Details about these filters are provided above. Furthermore, a dual bandpass filter can be used as another infrared cutoff filter.

[0416] <Camera Module>

[0417] The camera module of the present invention has the membrane of the present invention described above. As for the structure of the camera module, there is no particular limitation as long as it has the structure of the membrane of the present invention and functions as a camera module. For example, a camera module may include a structure having a solid-state imaging element, a lens, and a circuit for processing images obtained from the solid-state imaging element. Known lenses and circuits can be used as the lens used in the camera module and the circuit for processing images obtained from the solid-state imaging element. Examples of camera modules can be found in Japanese Patent Application Publication Nos. 2016-006476 and 2014-197190, the contents of which are incorporated herein by reference.

[0418] <Light-emitting element>

[0419] The film of the present invention can also be used in light-emitting elements. As for the structure of the light-emitting element, there is no particular limitation as long as it can function as a light-emitting element; examples include light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), quantum dot light-emitting diodes (QLEDs), and vertical-cavity surface-emitting lasers (VICSELs). The film of the present invention can be formed directly on the light-emitting element, and can also be disposed in the light-emitting path.

[0420] <Optical Communication Components>

[0421] The film of the present invention can also be used in optical communication elements. As for the structure of the optical communication element, there is no particular limitation as long as it can function as an optical communication element; it can be a transmitting element or a receiving element. Examples of optical communication elements include infrared remote controls, infrared transceivers, optical interposers, and optical interconnects. The film of the present invention can be formed directly on the receiving element, and can also be formed directly on the transmitting element, and can also be disposed on the transceiver path.

[0422] Example

[0423] The present invention will be further described in detail below with examples. The materials, amounts, proportions, processing contents, and processing order shown in the following examples can be appropriately modified without departing from the spirit of the invention. In the structural formulas shown below, Me represents methyl and Ph represents phenyl.

[0424] <About specific compounds>

[0425] The compounds 1-1 to 1-16 used in the examples shown below are as follows.

[0426] [Chemical Formula 16]

[0427]

[0428] [Chemical Formula 17]

[0429]

[0430] [Chemical Formula 18]

[0431]

[0432] <Synthesis example>

[0433] (Synthetic Example 1) Synthesis of Compound 1-1

[0434] Compound (1-1) was synthesized according to the following scheme.

[0435] [Chemical Formula 19]

[0436]

[0437] -Synthesis process of intermediate a-

[0438] 9.9 g (65.9 mmol) of 2-aminobenzothiazole, 400 ml of bromobenzene, and 21.3 g (190 mmol) of diazabicyclooctane (DABCO) were added to a 3 L three-necked flask and stirred under nitrogen atmosphere. Then, 48.1 ml (48.1 mmol) of a 1 mol / L toluene solution of titanium tetrachloride was added dropwise. After the addition was complete, 5.51 g (21.0 mmol) of indigo was added, and the reaction was carried out under reflux for 21 hours. After the reaction was complete, 2100 ml of acetone was added, the mixture was filtered, and the filtrate was concentrated to obtain a green powder. This powder was separated from the water using dichloromethane and water, and the organic phase was concentrated to obtain 3 g of intermediate a.

[0439] -Synthetic Procedure of Compound 1-1-

[0440] In a reaction vessel, 6.2 g (27.6 mmol) of 2-aminoethyl diphenylboronic acid (DPBA) was stirred with 44 ml of 1,2-dichlorobenzene. At an external temperature of 40°C, 7.84 g (41.3 mmol) of titanium tetrachloride was added dropwise over 10 minutes, followed by stirring for 30 minutes. Then, 2.0 g (3.4 mmol) of intermediate a was added, and the temperature was raised to an external temperature of 125°C and heated for 60 minutes. The mixture was then cooled to an internal temperature of 30°C, and 50 ml of methanol was added dropwise while maintaining the internal temperature below 30°C. After the addition, the mixture was stirred for 30 minutes, and the crystals were filtered off and washed with 70 ml of methanol. 50 ml of dimethylacetamide was added to the obtained crystals, and the mixture was heated and stirred at 100°C for 30 minutes. The mixture was then cooled to 30°C, and the crystals were filtered off. Finally, 50 ml of methanol was added to the obtained crystals, and the mixture was heated under reflux for 30 minutes. The mixture was then cooled to 30°C, and the crystals were filtered off. The obtained crystals were dried by air drying at 50°C, thereby obtaining 1.2 g of compound 1-1.

[0441] Identification data of compound 1-1

[0442] MALDI (Matrix Assisted Laser Desorption / Ionization) TOF-MS (Time of Flight Mass Spectrometry): Calc. for [M+H]+855.3, found 855.3.

[0443] <Preparation of Dispersions>

[0444] The infrared absorber, pigment derivative, dispersion resin, and solvent of the types listed in the table below were mixed in the amounts specified below by mass. Then, 117 parts by mass of 0.3 mm diameter zirconia beads were added, and the mixture was dispersed using a paint mixer for 5 hours. The microbeads were then separated by filtration to produce a dispersion. Additionally, the infrared absorber used was an infrared absorber that underwent the following mixing and grinding process.

[0445] (Mixing and grinding conditions)

[0446] 10.6 parts by weight of infrared absorber, 149.4 parts by weight of grinding agent, and 28 parts by weight of binder were added to a Labplastomill (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and the temperature was controlled until the temperature of the mixture in the apparatus reached 70°C and the mixture was kneaded for 2 hours. The grinding agent used was neutral anhydrous Glauber's salt E (average particle size (50% diameter on a volume basis (D50)) = 20 μm, manufactured by MITAJIRI Chemical Industry Co., Ltd.), and the binder used was diethylene glycol. The kneaded and ground mixture was washed with 20 L of water at 24°C to remove the grinding agent and binder, and then treated in a heated oven at 80°C for 24 hours.

[0447] [Table 1]

[0448]

[0449] The materials recorded in the table above are as follows.

[0450] (Infrared absorber)

[0451] 1-1 to 1-13: The above-mentioned compounds 1-1 to 1-13

[0452] 1-r: Compounds with the following structures (comparative compounds)

[0453] [Chemical Formula 20]

[0454]

[0455] IR-1~IR-5: Compounds with the following structures

[0456] [Chemical Formula 21]

[0457]

[0458] (Pigment derivatives)

[0459] F-1~F-5: Compounds with the following structures

[0460] [Chemical Formula 22]

[0461]

[0462] (Dispersion resin)

[0463] E-1: Resins with the following structure (acid value = 99.1 mg KOH / g, weight-average molecular weight = 38000). The values ​​noted on the main chain indicate the molar ratio of repeating units, and the values ​​noted on the side chains indicate the number of repeating units.

[0464] E-2: Resin with the following structure (acid value = 87.0 mg KOH / g, weight-average molecular weight = 18000). The values ​​noted on the main chain indicate the molar ratio of repeating units, and the values ​​noted on the side chains indicate the number of repeating units.

[0465] E-3: Resins with the following structure (acid value = 85.0 mg KOH / g, weight-average molecular weight = 22000). The values ​​noted on the main chain indicate the molar ratio of repeating units, and the values ​​noted on the side chains indicate the number of repeating units.

[0466] E-4: Resins with the following structure (acid value = 43 mg KOH / g, weight-average molecular weight = 9000). The values ​​noted on the side chains indicate the molar ratio of repeating units.

[0467] E-5: End-capped resins with the following structure (amine value = 90 mg KOH / g, quaternary ammonium salt value = 30 mg KOH / g, weight-average molecular weight = 9800). The values ​​in the main chain indicate the molar ratio of repeating units.

[0468] E-6: Resins with the following structure (acid value = 32.3 mg KOH / g, amine value = 45.0 mg KOH / g, weight-average molecular weight = 22900). The values ​​noted on the main chain indicate the molar ratio of repeating units, and the values ​​noted on the side chains indicate the number of repeating units.

[0469] [Chemical Formula 23]

[0470]

[0471] (solvent)

[0472] D-1: Propylene glycol monomethyl ether acetate

[0473] <Preparation of the Composition>

[0474] (Examples 1-66, Comparative Example 1)

[0475] The compositions were prepared by mixing the materials listed in the table below in the indicated mass fractions and filtering them through a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm.

[0476] [Table 2]

[0477]

[0478] [Table 3]

[0479]

[0480] [Table 4]

[0481]

[0482] [Table 5]

[0483]

[0484] [Table 6]

[0485]

[0486] [Table 7]

[0487]

[0488] (Dispersion)

[0489] Dispersions 1-27, Comparative Dispersion 1: The above-mentioned dispersions 1-27, comparative dispersion 1

[0490] (Alkali-soluble resin)

[0491] G-1: Resin with the following structure (acid value = 69.2 mg KOH / g, weight-average molecular weight = 10000). The values ​​noted on the main chain indicate the molar ratio of repeating units.

[0492] G-2: Resin with the following structure (acid value = 91.3 mg KOH / g, weight-average molecular weight = 41000). The values ​​noted on the main chain indicate the molar ratio of repeating units.

[0493] G-3: Resin with the following structure (acid value = 76.8 mg KOH / g, weight-average molecular weight = 17000). The values ​​noted on the main chain indicate the molar ratio of repeating units.

[0494] G-4: Resins with the following structure (acid value = 110 mg KOH / g, weight-average molecular weight = 10000). The values ​​noted on the main chain indicate the molar ratio of repeating units.

[0495] G-5: Resins with the following structure (acid value = 184 mg KOH / g, weight-average molecular weight = 9700). The values ​​noted on the main chain indicate the molar ratio of repeating units.

[0496] [Chemical Formula 24]

[0497]

[0498] (polymeric compounds)

[0499] B-1: A mixture of compounds with the following structures (the molar ratio of the compound on the left to the compound on the right is 7:3).

[0500] B-2: Compounds with the following structures

[0501] B-3: A mixture of compounds with the following structures (containing 55–63 mol% of the compound on the left).

[0502] B-4: Compounds with the following structures

[0503] [Chemical Formula 25]

[0504]

[0505] (Photopolymerization initiator)

[0506] C-7~C-8, C-13, C-22, C-23: Compounds with the following structures

[0507] [Chemical Formula 26]

[0508]

[0509] (UV absorber)

[0510] H-1~H-6: Compounds with the following structures

[0511] [Chemical Formula 27]

[0512]

[0513] (Antioxidants)

[0514] I-1~I-6: Compounds with the following structures

[0515] [Chemical Formula 28]

[0516]

[0517] (additive)

[0518] L-1~L-3: Compounds with the following structures

[0519] [Chemical Formula 29]

[0520]

[0521] (surfactant)

[0522] J-1: Compounds with the following structure (weight-average molecular weight = 14000, in the following formulas, the percentage of repeating units is in molar percentage).

[0523] [Chemical Formula 30]

[0524]

[0525] J-2: FTX-218D (manufactured by Neos Corporation, a fluorinated surfactant).

[0526] J-3: MEGAFACE F-554 (manufactured by DIC Corporation, a fluorinated surfactant).

[0527] (Polymerization inhibitor)

[0528] K-1: p-Methoxyphenol

[0529] (solvent)

[0530] D-1: Propylene glycol monomethyl ether acetate

[0531] D-2: Propylene glycol monomethyl ether

[0532] D-3: Cyclopentanone

[0533] D-4: 3-Methoxy-N,N-Dimethylpropionamide

[0534] D-5: 3-Butoxy-N,N-Dimethylpropionamide

[0535] D-6: Methyl 3-methoxypropionate

[0536] (Examples 101-108, Comparative Example 101)

[0537] The various materials were mixed in the proportions shown below and filtered using a nylon filter (made by Nihon Pall Ltd.) with a pore size of 0.45 μm to produce the compositions.

[0538] The following table lists infrared absorbers or dispersions...parts by mass as listed in the table.

[0539] The following table lists 95.0 parts by weight of epoxy compounds.

[0540] The curing agent listed in the table below (if listed in the table) is 1.5 parts by weight.

[0541] The surfactants listed in the table below are 0.01 parts by weight.

[0542] The antioxidants listed in the table below... 3.3 parts by weight

[0543] The solvents listed in the table below are in quantities of 200.0 parts by mass.

[0544] [Table 8]

[0545]

[0546] (Dispersion)

[0547] Dispersions 2, 12, 19, 25, and Comparative Dispersion 1: The above dispersions 2, 12, 19, 25, and Comparative Dispersion 1

[0548] (Infrared absorber)

[0549] 1-14 to 1-16: Compounds 1-14 to 1-16 mentioned above

[0550] (Epoxy compounds)

[0551] Ep-1: Resins with the following structure (the values ​​of repeating units are mass ratios, weight-average molecular weight 20000, number-average molecular weight 8300, epoxy equivalent 284 g / eq, acid value 130 mg KOH / g, glass transition temperature 136℃)

[0552] [Chemical Formula 31]

[0553]

[0554] Ep-2: Resins with the following structure (the values ​​of the repeating units are mass ratios, weight-average molecular weight 26100, number-average molecular weight 8600, epoxy equivalent 355 g / eq, acid value 163 mg KOH / g, glass transition temperature 133℃)

[0555] [Chemical Formula 32]

[0556]

[0557] Ep-3: Resins with the following structure (the values ​​of the repeating units are mass ratios, weight-average molecular weight 21100, number-average molecular weight 8500, epoxy equivalent 355 g / eq, acid value 130 mg KOH / g, glass transition temperature 157℃)

[0558] [Chemical Formula 33]

[0559]

[0560] Ep-4: Resins with the following structure (the values ​​of the repeating units are mass ratios, weight-average molecular weight 18300, number-average molecular weight 9100, epoxy equivalent 284 g / eq, acid value 98 mg KOH / g, glass transition temperature 134℃)

[0561] [Chemical Formula 34]

[0562]

[0563] Ep-5: Resins with the following structure (the values ​​of the repeating units are mass ratios, weight-average molecular weight 22900, number-average molecular weight 8800, epoxy equivalent 316 g / eq, acid value 130 mg KOH / g, glass transition temperature 124℃)

[0564] [Chemical Formula 35]

[0565]

[0566] (Curing agent)

[0567] P-1: Trimethicone

[0568] P-2: 2-Ethyl-4-methylimidazolium

[0569] P-3: Methyltetrahydrophthalic anhydride

[0570] (surfactant)

[0571] J-1~J-3: The surfactants J-1~J-3 mentioned above

[0572] (solvent)

[0573] D-1, D-3: The solvents D-1 and D-3 mentioned above.

[0574] (Examples 201-207, Comparative Example 201)

[0575] The various materials were mixed in the proportions shown below and filtered using a nylon filter (made by Nihon Pall Ltd.) with a pore size of 0.45 μm to produce the compositions.

[0576] The following table lists infrared absorbers or dispersions...parts by mass as listed in the table.

[0577] The resin listed in the table below is 95.0 parts by weight.

[0578] The antioxidants listed in the table below... 3.3 parts by weight

[0579] The solvents listed in the table below are in quantities of 200.0 parts by mass.

[0580] [Table 9]

[0581]

[0582] (Dispersion)

[0583] Dispersion 1, Comparative Dispersion 1: The above-mentioned Dispersion 1, Comparative Dispersion 1

[0584] (Infrared absorber)

[0585] 1-14 to 1-16: Compounds 1-14 to 1-16 mentioned above

[0586] (Resin)

[0587] G-6: Resins with the following structure (weight average molecular weight 137,000, number average molecular weight 32,000, glass transition temperature 165℃)

[0588] [Chemical Formula 36]

[0589]

[0590] G-7: Resins with the following structure (weight average molecular weight 188,000, number average molecular weight 75,000, glass transition temperature 285℃)

[0591] [Chemical Formula 37]

[0592]

[0593] G-8: Resin with the following structure (glass transition temperature 310℃, logarithmic viscosity 0.87)

[0594] [Chemical Formula 38]

[0595]

[0596] (Antioxidants)

[0597] I-1, I-2, I-4, I-5: the above-mentioned antioxidants I-1, I-2, I-4, I-5

[0598] (solvent)

[0599] D-7: Dichloromethane

[0600] D-8: Dimethylacetamide

[0601] <Membrane Manufacturing>

[0602] (Manufacturing Example 1) Method for manufacturing a membrane using the compositions of Examples 1 to 66 and Comparative Example 1

[0603] Each composition was coated onto a glass substrate using a spin coating method, and the substrate was heated at 100°C for 2 minutes using a heating plate to obtain a composition layer. The obtained composition layer was then subjected to i-ray stepper exposure using an FPA-3000i5+ (manufactured by Canon Inc.) at 1000 mJ / cm². 2The entire surface was exposed using the specified exposure level. Then, a film with a thickness of 1.0 μm was fabricated by heating at 180°C for 5 minutes using a heating plate.

[0604] (Manufacturing Example 2) A method for manufacturing a membrane using the compositions of Examples 101-108 and Comparative Example 101.

[0605] The compositions were coated onto a glass substrate by spin coating, and then cured by heating at 100°C for 2 minutes and then at 200°C for 8 minutes, thereby obtaining a film with a thickness of 1.0 μm.

[0606] (Manufacturing Example 3) A method for manufacturing a membrane using the compositions of Examples 201-208 and Comparative Example 201.

[0607] Each composition was cast onto a glass substrate and dried at 20°C for 8 hours, then peeled off from the glass substrate. The peeled coating was further dried at 100°C under reduced pressure for 8 hours to obtain a film with a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

[0608] <Evaluation of Short-Wavelength Infrared Shielding>

[0609] Regarding the membrane obtained above, the absorption spectrum in the wavelength range of 1000–2000 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Tech Corporation). The average transmittance in the wavelength range of 1000–1100 nm was calculated, and the short-wavelength infrared shielding was evaluated using the following criteria.

[0610] The results are shown in the table below. It can be said that the lower the average transmittance in the above range, the higher the short-wavelength infrared shielding.

[0611] -Evaluation Criteria-

[0612] A: Average transmittance in the wavelength range of 1000–1100 nm ≤ 15%

[0613] B: 15% < average transmittance in the wavelength range of 1000-1100 nm ≤ 30%

[0614] C: 30% < average transmittance in the wavelength range of 1000-1100 nm

[0615] <Evaluation of lightfastness>

[0616] The film obtained above was placed in a fading tester equipped with a 200,000 Lux xenon lamp and irradiated with 200,000 Lux light for 48 hours without using an ultraviolet cutoff filter. Then, the transmittance spectrum of the film after light irradiation was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Tech Corporation). Within the wavelength range of 400 nm to 2000 nm, the transmittance change at the wavelength with the largest change before and after light irradiation was calculated according to the following formula, and the lightfastness was evaluated using the following criteria.

[0617] Transmittance change = |(Transmittance of the film after light irradiation - Transmittance of the film before light irradiation)|

[0618] -Evaluation Criteria-

[0619] A: Transmittance change is less than 5%.

[0620] B: Transmittance change is greater than 5% but less than 10%.

[0621] C: Transmittance change is greater than 10%

[0622] <Evaluation of Dispersion>

[0623] The dispersibility was evaluated by measuring the volume average particle size of the infrared absorber particles in each composition using the following method. However, for Examples 101-104 and 201-207, the infrared absorber was dissolved in a solvent, therefore dispersibility was not evaluated. The volume average particle size of the infrared absorber in the composition was measured using a NANOTRAC UPA particle size analyzer (UPA-EX150, manufactured by Nikkiso Co., Ltd.), and dispersibility was evaluated according to the following criteria. It can be said that the smaller the volume average particle size of the infrared absorber particles in the composition, the better the dispersibility.

[0624] -Evaluation Criteria-

[0625] A: Volume average particle size is greater than 10nm and less than 100nm

[0626] B: Volume average particle size is greater than 100nm and less than 300nm

[0627] C: Volume average particle size exceeds 300 nm.

[0628] [Table 10]

[0629]

[0630] [Table 11]

[0631]

[0632] [Table 12]

[0633]

[0634] [Table 13]

[0635]

[0636] As shown in the table above, the examples exhibit superior lightfastness compared to the comparative examples.

[0637] -Manufacturing of a composition for forming an infrared transmission filter-

[0638] (Example 301)

[0639] The materials were mixed in the proportions shown below and filtered through a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm to produce the composition of Example 301 (composition for forming an infrared transmission filter).

[0640] Composition of Example 1: 36.99 parts by weight

[0641] Pigment dispersion 1-1: 46.5 parts by weight

[0642] Pigment dispersion 1-2: 37.1 parts by weight

[0643] Using the composition of Example 301, the evaluation of lightfastness, short-wavelength infrared shielding, and dispersibility was conducted in the same manner as in Example 1, and the same effects as in Example 1 were obtained. Furthermore, the film obtained using the composition of Example 301 is able to shield light of visible wavelengths while allowing at least a portion of light of near-infrared wavelengths (near-infrared rays) and short-wavelength infrared wavelengths (short-wavelength infrared rays) to pass through.

[0644] (Example 302)

[0645] The materials were mixed in the proportions shown below and filtered through a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm to produce the composition of Example 302 (composition for forming an infrared transmission filter).

[0646] Composition of Example 9: 36.99 parts by weight

[0647] Pigment dispersion 1-1: 46.5 parts by weight

[0648] Pigment dispersion 1-2: 37.1 parts by weight

[0649] Using the composition of Example 302, the evaluation of lightfastness, short-wavelength infrared shielding, and dispersibility was conducted in the same manner as in Example 9, and the same effects as in Example 9 were obtained. Furthermore, the film obtained using the composition of Example 302 is able to shield light of visible wavelengths while allowing at least a portion of light of near-infrared wavelengths (near-infrared rays) and short-wavelength infrared wavelengths (short-wavelength infrared rays) to pass through.

[0650] (Example 303)

[0651] The materials were mixed in the proportions shown below and filtered through a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm to produce the composition of Example 303 (composition for forming an infrared transmission filter).

[0652] Composition of Example 26: 22.67 parts by weight

[0653] Pigment dispersion 2-1: 51.23 parts by weight

[0654] Using the composition of Example 303, the evaluation of lightfastness, short-wavelength infrared shielding, and dispersibility was conducted in the same manner as in Example 26, and the same effects as in Example 26 were obtained. Furthermore, the film obtained using the composition of Example 303 is able to shield light of visible wavelengths and near-infrared wavelengths (near-infrared rays), while allowing at least a portion of light of short-wavelength infrared wavelengths (short-wavelength infrared rays) to pass through.

[0655] (Example 304)

[0656] The materials were mixed in the proportions shown below and filtered through a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm to produce the composition of Example 304 (composition for forming an infrared transmission filter).

[0657] Composition of Example 18: 22.67 parts by weight

[0658] Pigment dispersion 2-1: 51.23 parts by weight

[0659] Using the composition of Example 304, the evaluation of lightfastness, short-wavelength infrared shielding, and dispersibility was conducted in the same manner as in Example 18, and the same effects as in Example 18 were obtained. Furthermore, the film obtained using the composition of Example 304 is able to shield light of visible wavelengths while allowing at least a portion of light of near-infrared wavelengths (near-infrared rays) and short-wavelength infrared wavelengths (short-wavelength infrared rays) to pass through.

[0660] Pigment dispersion 1-1

[0661] Pigment dispersion 1-1 was prepared by mixing and dispersing the following mixture for 3 hours using zirconia beads with a diameter of 0.3 mm in a bead mill (NANO-3000-10 high-pressure disperser with decompression mechanism (manufactured by Nippon Bee Chemical Co., Ltd.)).

[0662] A mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139): 11.8 parts by weight

[0663] Dispersant (Disperbyk-111, manufactured by BYKChemie GmbH): 9.1 parts by weight

[0664] Propylene glycol monomethyl ether acetate: 79.1 parts by weight

[0665] Pigment dispersion 1-2

[0666] Pigment dispersions 1-2 were prepared by mixing and dispersing the following mixture for 3 hours using zirconia beads with a diameter of 0.3 mm in a bead mill (NANO-3000-10 high-pressure disperser with a pressure reduction mechanism (manufactured by Nippon Bee Chemical Co., Ltd.)).

[0667] A mixed pigment consisting of blue pigment (CI Pigment Blue 15:6) and purple pigment (CI Pigment Violet 23): 12.6 parts by weight

[0668] Dispersant (Disperbyk-111, manufactured by BYKChemie GmbH): 2.0 parts by weight

[0669] The above-mentioned alkali-soluble resin G-3: 3.3 parts by weight

[0670] Cyclohexanone: 31.2 parts by weight

[0671] Propylene glycol monomethyl ether acetate: 50.9 parts by weight

[0672] Pigment dispersion 2-1

[0673] 60 parts by weight of CI Pigment Black 32, 20 parts by weight of CI Pigment Blue 15:6, 20 parts by weight of CI Pigment Yellow 139, 80 parts by weight of dispersant (manufactured by Lubrizol Japan Limited, SOLSPERSE 76500, solid content concentration of 50% by weight), 120 parts by weight of a solution containing the above-mentioned alkali-soluble resin G-5 (solid content concentration of 35% by weight), and 700 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed using a paint mixer for 8 hours to prepare pigment dispersion 2-1.

[0674] Symbol Explanation

[0675] 110 - Solid-state imaging element, 111 - Infrared cutoff filter, 112 - Color filter, 114 - Infrared transmission filter, 115 - Microlens, 116 - Planarization layer.

Claims

1. A composition comprising a compound represented by formula (1), a curing compound, and a solvent, In equation (1), A 1 and A 2 Each can be independently represented as aryl, heteroaryl, or alkyl. X 1 ~X 4 Each can independently represent an aryl, heteroaryl, alkoxy, aryloxy, or halogen atom. R 1 ~R 8 Each can be used independently to represent a hydrogen atom or a substituent. X 1 With X 2 X 3 With X 4 They can be arbitrarily connected to form a ring. in, A 1 A 2 X 1 X 2 X 3 and X 4 At least one of them represents a heteroaryl group.

2. The composition according to claim 1, wherein, A in equation (1) 1 A 2 X 1 X 2 X 3 and X 4 At least one of them is a group represented by any one of formulas (A-1) to (A-3). In equation (A-1), X A1 Indicates O, S or NR X1 , X A2 CR X2 Or N, X A3 CR X3 Or N, X A4 CR X4 Or N, R X1 ~R X4 Each can be used independently to represent a hydrogen atom or a substituent. In X A2 For CR X2 And X A3 For CR X3 In the case of R X2 With R X3 They can be arbitrarily bonded together to form a ring. In X A3 For CR X3 And X A4 For CR X4 In the case of R X3 With R X4 They can be arbitrarily bonded together to form a ring. * indicates a connection key. In equation (A-2), X A5 Indicates O, S or NR X5 , X A6 CR X6 Or N, X A7 CR X7 Or N, X A8 CR X8 Or N, R X5 ~R X8 Each can be used independently to represent a hydrogen atom or a substituent. In X A7 For CR X7 And X A8 For CR X8 In the case of R X7 With R X8 They can be arbitrarily bonded together to form a ring. * indicates a connection key. In equation (A-3), Y A1 ~Y A5 Represent N or CR independently, respectively. Y1 R Y1 Represents a hydrogen atom or a substituent. Y A1 ~Y A5 1 to 3 of them are N. In Y A1 ~Y A5 Two or more adjacent ones are CR Y1 In the case of two adjacent CRs Y1 R in Y1 They can be arbitrarily bonded together to form a ring. * indicates a connection key.

3. The composition according to claim 2, wherein, A in equation (1) 1 and A 2 At least one of them is a group represented by any one of the formulas (A-1) to (A-3).

4. The composition according to claim 2, wherein, A in equation (1) 1 and A 2 At least one of them is a group represented by any one of the formulas (A-1) to (A-2).

5. The composition according to claim 1 or 2, wherein, Curable compounds include polymerizable compounds.

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

7. A membrane obtained using the composition of claim 1 or 2.

8. A filter having the membrane of claim 7.

9. A solid-state imaging element having the membrane of claim 7.

10. An image display device having the membrane of claim 7.

11. An infrared sensor having the membrane of claim 7.

12. A camera module having the membrane of claim 7.

13. A compound represented by formula (1), In equation (1), A 1 and A 2 Each can be independently represented as aryl, heteroaryl, or alkyl. X 1 ~X 4 Each can independently represent an aryl, heteroaryl, alkoxy, aryloxy, or halogen atom. R 1 ~R 8 Each can be used independently to represent a hydrogen atom or a substituent. X 1 With X 2 X 3 With X 4 They can be arbitrarily connected to form a ring. in, A 1 A 2 X 1 X 2 X 3 and X 4 At least one of them represents a heteroaryl group.

Images