Resin composition

Abstract

A resin composition comprises a thermoplastic resin (A) having an ester bond and a glass transition temperature of 80°C or higher, an epoxy compound (B), and a solvent (C) having a boiling point of 100°C or higher, wherein the mass ratio ((A) / (B)) of the thermoplastic resin (A) and the epoxy compound (B) is 5 or more.

Description

resin composition

[0001] This disclosure relates to a resin composition, and to an optical filter and an image sensor having a resin layer formed from the resin composition.

[0002] Imaging devices such as mobile phone cameras, digital cameras, in-car cameras, video cameras, and display elements (LEDs, etc.) typically use image sensors that convert the light from a subject into electrical signals for output. Such image sensors include a detection element (sensor) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) and a lens, and may also include optical filters such as near-infrared cut filters to remove optical noise (e.g., ghosting and flare) that interferes with image processing, in order to improve performance.

[0003] When forming an optical filter from a resin composition, a resin film is obtained by forming the resin composition containing a solvent into a film and then drying or curing it, thereby obtaining a thin optical filter. For example, Patent Document 1 discloses an optical filter formed from a resin composition containing a polyester resin or a polymethacrylate resin, a solvent, and a dye, and Patent Document 2 discloses an optical filter formed from a resin composition containing a polyester resin and a silane coupling agent or its hydrolysis (condensation) product.

[0004] Japanese Patent Publication No. 2014-59550 Japanese Patent Publication No. 2020-19207

[0005] Resin compositions containing resins having ester bonds, such as polyester resins, are prone to hydrolysis. For example, if a resin film is formed from the resin composition and placed under high temperature and high humidity conditions, it may absorb water or cause defects in appearance. This disclosure aims to provide a resin composition containing a resin having ester bonds that exhibits excellent resistance to high temperature and high humidity. This disclosure also provides an optical filter and an image sensor having a resin layer formed from the resin composition.

[0006] The resin composition, optical filter, and imaging device according to the present disclosure that have solved the above problems are as follows. [1] A resin composition containing a thermoplastic resin (A) having an ester bond and a glass transition temperature of 80°C or higher, an epoxy compound (B), and a solvent (C) having a boiling point of 100°C or higher, wherein the mass ratio ((A) / (B)) of the thermoplastic resin (A) to the epoxy compound (B) is 5 or more. [2] The resin composition according to [1], wherein the epoxy compound (B) is a polyfunctional epoxy compound having two or more oxirane rings in one molecule. [3] The resin composition according to [1] or [2], wherein the epoxy compound (B) has an epoxy equivalent of 200 g / eq or less. [4] The resin composition according to any one of [1] to [3], which does not contain a curing catalyst for curing the epoxy compound (B). [5] The resin composition according to any one of [1] to [4], wherein the thermoplastic resin (A) is at least one selected from polyester resins, polycarbonate resins, and polyolefin resins having an ester bond. [6] The resin composition according to any one of [1] to [5], further containing a dye (D). [7] The resin composition according to [6], wherein the dye (D) is at least one selected from squarylium dyes, croconium dyes, and cyanine dyes. [8] The resin composition according to [6] or [7], wherein the dye (D) is a compound having a styrene structure. [9] The resin composition according to [8], wherein the compound having a styrene structure is a compound represented by the following formula (14). [In formula (14), R ９１ represents a cyano group, an acyl group, a carboxylic acid ester group, or an amide group; R ９２ represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group, or a heteroaryl group; R ９１ and R ９２ when both are an acyl group, a carboxylic acid ester group, or an amide group, R ９１ and R ９２ may be linked to each other to form a ring; R ９３ represents a hydrogen atom or an alkyl group; R ９４ represents a hydrogen atom, an organic group, or a polar functional group, and a plurality of R ９４

[10] A resin composition according to any one of [1] to [9], further comprising at least one (E) selected from a silane coupling agent, its hydrolysate, and its hydrolyzed condensate.

[11] A resin composition according to any one of [1] to

[10] , further comprising a compound (F) containing an M-O-C bond (wherein M represents Ti, Zr, or Al).

[12] An optical filter having a substrate made of silicate glass, borosilicate glass, soda glass, phosphate-based glass, or fluorine-based glass, and a resin layer provided on the substrate and formed from the resin composition according to any one of [1] to

[11] .

[13] The optical filter according to

[12] , further comprising a dielectric film.

[14] An image sensor having the optical filter according to

[12] or

[13] .

[0007] Despite having ester bonds, the resin composition according to this disclosure suppresses water absorption and maintains a good appearance of the resin film even when placed under high temperature and high humidity conditions after forming a resin film. Therefore, it exhibits excellent resistance to high temperature and high humidity.

[0008] The resin composition according to this disclosure contains a thermoplastic resin (A) having ester bonds and a glass transition temperature of 80°C or higher, an epoxy compound (B), and a solvent (C) having a boiling point of 100°C or higher, wherein the mass ratio ((A) / (B)) of the thermoplastic resin (A) to the epoxy compound (B) is 5 or higher. The resin composition according to this disclosure contains a thermoplastic resin having ester bonds and a solvent, and can be used as a paint-type resin composition, and is suitably used, for example, to form a resin film. Resin compositions containing resins having ester bonds are generally prone to hydrolysis, and for example, when a resin film is formed from the resin composition and placed under high temperature and high humidity, water absorption occurs and reactions such as hydrolysis occur, which can result in appearance defects such as turbidity, bubble formation, and cracking. However, despite having ester bonds, the resin composition according to this disclosure suppresses water absorption and maintains a good appearance even when a resin film is formed and placed under high temperature and high humidity, and exhibits excellent resistance to high temperature and high humidity. The resin composition according to this disclosure will be described in detail below.

[0009] Resin (A) is not particularly limited as long as it has ester bonds and a glass transition temperature of 80°C or higher. The ester bonds may be included in the main chain or side chains of the polymer constituting resin (A). That is, resin (A) may have ester bonds in the main chain or in the side chains. Organic groups may be bonded to both sides of the ester bond, or heteroatoms may be bonded to one or both sides, forming a bond that includes an ester bond. In other words, resin (A) may have ester bonds alone or may have bonds that partially include ester bonds. Examples of bonds that partially include ester bonds include carbonate bonds and urethane bonds. Examples of resin (A) having ester bonds in the main chain include polyester resins, polycarbonate resins, and polyurethane resins. Examples of resin (A) having ester bonds in the side chains include poly(meth)acrylic acid ester resins and polyolefin resins that have ester bonds in the side chains. As for the polyolefin resin, cycloolefin resins are preferably used from the viewpoint of transparency.

[0010] Polyester resins are polymers that contain ester bonds in the repeating units of their main chain, and can be obtained, for example, by condensation polymerization of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. For example, OKP series from Osaka Gas Chemical Co., Ltd., TRN series from Teijin Ltd., Theonex®, Lynite® from DuPont, Novapex® from Mitsubishi Chemical Corporation, Novaduran® from Mitsubishi Engineering Plastics Corporation, Lumirror® and Torecon® from Toray Industries, Inc. can be used.

[0011] The polyester resin may also be a polyarylate resin. Polyarylate resin is a polymer obtained by condensation polymerization of a divalent phenol compound and a dibasic acid (for example, an aromatic dicarboxylic acid such as phthalic acid), and the repeating units of the main chain contain aromatic rings and ester bonds. Examples of polyarylate resins that can be used include Vectran® manufactured by Kuraray Co., Ltd. and U Polymer® manufactured by Unitika Corporation.

[0012] Polycarbonate resins are polymers that contain carbonate bonds (-O-(C=O)-O-) in the repeating units of their main chain. Examples of polycarbonate resins that can be used include Panlite® manufactured by Teijin, Yupizeta® manufactured by Mitsubishi Gas Chemical Company, Yupiron®, Novalex®, and Zanter® manufactured by Mitsubishi Engineering Plastics Corporation, and SD Polyca® manufactured by Sumika Styron Polycarbonate Co., Ltd.

[0013] Polyurethane resins are polymers that contain urethane bonds (-NH-C(=O)-O-) in the repeating units of their main chain. Examples of polyurethane resins that can be used include Hydran® and Barnock® from DIC Corporation, Takelac®, Takenate®, and Fortimo® from Mitsui Chemicals, Ltd., Juliano® from Arakawa Chemical Industries, Ltd., and Adeka New Ace® from ADEKA Corporation.

[0014] Poly(meth)acrylic acid ester resins are polymers having repeating units derived from at least (meth)acrylic acid esters. Poly(meth)acrylic acid ester resins may have a ring structure in their main chain, and examples include carbonyl group-containing ring structures such as lactone ring structures, glutaric acid anhydride structures, glutarimide structures, maleic acid anhydride structures, and maleimide ring structures; and carbonyl group-free ring structures such as oxetane ring structures, azetidine ring structures, tetrahydrofuran ring structures, pyrrolidine ring structures, tetrahydropyran ring structures, and piperidine ring structures. Note that carbonyl group-containing ring structures also include structures containing carbonyl group derivative groups such as imide groups. Examples of (meth)acrylic resins having a carbonyl group-containing ring structure can be found in Japanese Patent Publication No. 2004-168882, Japanese Patent Publication No. 2008-179677, International Publication No. 2005 / 54311, Japanese Patent Publication No. 2007-31537, etc.

[0015] Cycloolefin resins are polymers obtained by polymerizing cycloolefins as at least a portion of their monomer components, and are not particularly limited as long as they have an alicyclic structure in part of their main chain. Examples of cycloolefin resins that can be used include Arton® manufactured by JSR Corporation, Topas® manufactured by Polyplastics Corporation, Appel® manufactured by Mitsui Chemicals Corporation, Zeonex® and Zeonor® manufactured by Nippon Zeon Corporation.

[0016] Resin (A) is preferably at least one selected from polyester resins, polycarbonate resins, and polyolefin resins having ester bonds. Using such a resin makes it easier to improve the transparency of the resin film formed from the resin composition. Resin (A) is more preferably one having ester bonds in its main chain, which further enhances the above effect. Therefore, it is more preferable for resin (A) to be at least one selected from polyester resins and polycarbonate resins.

[0017] Resin (A) is thermoplastic and has a glass transition temperature of 80°C or higher. This makes it possible to increase the heat resistance of the resin film formed from the resin composition and to easily increase the hardness of the resin film. The glass transition temperature of the resin is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher. There is no particular upper limit to the glass transition temperature of resin (A), but for example, it is preferably 300°C or lower, more preferably 270°C or lower, and even more preferably 250°C or lower.

[0018] The content of resin (A) in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 65% ​​by mass or more, preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less, based on 100% by mass of the solid content of the resin composition. Note that the solid content of the resin composition refers to the amount of resin composition excluding solvent (C).

[0019] The epoxy compound (B) is not particularly limited as long as it is a compound having an oxirane ring in one molecule. The epoxy compound (B) can react with the ester bonds of the resin (A), thereby improving the appearance of the resin film formed from the resin composition. Specifically, when the epoxy compound (B) reacts with the ester bonds of the resin, water absorption of the resin film is suppressed when the resin film formed from the resin composition is placed under high temperature and high humidity, thereby improving the appearance of the resin film. The reaction between the epoxy compound (B) and the ester bonds of the resin (A) can be carried out, for example, by heating the resin composition, thereby curing the resin composition. The resin composition may contain only one type of epoxy compound (B), or it may contain two or more types.

[0020] The epoxy compound (B) may contain the oxirane ring in the form of a glycidyl group, or the oxirane ring and the aliphatic hydrocarbon ring may be in a form that shares a carbon atom, such as in a cycloalkene oxide.

[0021] The epoxy compound (B) may have only one oxirane ring in one molecule, or it may have two or more oxirane rings. Preferably, the epoxy compound (B) is a polyfunctional epoxy compound having two or more oxirane rings in one molecule, so that the epoxy compound (B) acts as a crosslinking agent for the resin (A) and accelerates the curing of the resin film formed from the resin composition. The epoxy compound (B) may have three or more oxirane rings in one molecule. There is no particular upper limit to the number of oxirane rings in the epoxy compound (B), and for example, it may be 10 or less, 8 or less, or 6 or less.

[0022] The epoxy compound (B) preferably has monovalent or divalent or more hydrocarbon groups, and it is preferable that these hydrocarbon groups include aliphatic hydrocarbon groups and / or aromatic hydrocarbon groups. This can increase the solubility of the epoxy compound (B) in the resin (A). The aliphatic hydrocarbon groups may be linear, branched, or cyclic. Linear or branched aliphatic hydrocarbon groups (excluding ethylene groups included in the oxirane ring) preferably have 2 or more carbon atoms, more preferably 3 or more, preferably 8 or fewer, and more preferably 6 or fewer.

[0023] The molecular weight of epoxy compound (B) is preferably 100 or more, more preferably 130 or more, even more preferably 160 or more, and even more preferably 180 or more. This increases the persistence of epoxy compound (B) in the resin composition. For example, a resin film can be formed by depositing the resin composition and heating it. In this case, increasing the molecular weight of epoxy compound (B) makes it less likely for epoxy compound (B) to volatilize from the resin composition when it is heated. This allows a larger amount of epoxy compound (B) to contribute to the reaction with the ester bonds of resin (A). On the other hand, the upper limit of the molecular weight of epoxy compound (B) is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. This increases the solubility of epoxy compound (B) in resin (A).

[0024] The epoxy equivalent of epoxy compound (B) is preferably 200 g / eq or less, more preferably 180 g / eq or less, and even more preferably 150 g / eq or less. Epoxy equivalent refers to the mass of the epoxy compound containing 1 gram equivalent of epoxy groups; the smaller the epoxy equivalent value, the greater the number of epoxy groups per unit mass of the epoxy compound. By using epoxy compound (B) with an epoxy equivalent of 200 g / eq or less, epoxy compound (B) reacts more efficiently with the ester bonds of resin (A), making it easier to improve the appearance of the resin film with a smaller amount of epoxy compound (B). The lower limit of the epoxy equivalent of epoxy compound (B) is not particularly limited and may be, for example, 70 g / eq or more, 80 g / eq or more, or 90 g / eq or more.

[0025] When epoxy compound (B) contains an oxirane ring in the form of a glycidyl group, it is preferable that epoxy compound (B) has a substructure represented by the following formula (1).

[0026]

[0027] The substructure represented by formula (1) is preferably the substructure represented by formula (1A) or formula (1B) below. In formula (1A) below, X represents an oxygen atom, a sulfur atom, or NH.

[0028]

[0029] Epoxy compound (B) is preferably a compound in which a group represented by formula (1A) and / or formula (1B) is bonded to a monovalent or divalent or more hydrocarbon group, and the hydrocarbon group is preferably composed of an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group. On the other hand, epoxy compound (B) may also be an alicyclic epoxy compound in which a glycidyl group is bonded to an aliphatic hydrocarbon ring, or in which an oxirane ring and an aliphatic hydrocarbon ring share a carbon atom.

[0030] The resin composition contains resin (A) and epoxy compound (B) such that the mass ratio of resin (A) to epoxy compound (B) ((A) / (B)) is 5 or more. That is, the content of epoxy compound (B) in the resin composition is 1 / 5 or less of the content of resin (A). It is desirable that the reaction of epoxy compound (B) contained in the resin composition is promoted more by the reaction with the ester bonds of resin (A) than by the reaction of epoxy compound (B) itself, and for this reason the mass ratio of resin (A) to epoxy compound (B) ((A) / (B)) is 5 or more. By including epoxy compound (B) in the resin composition in this way, the appearance of the resin film formed from the resin composition can be made good. The mass ratio of resin (A) to epoxy compound (B) may be 6 or more, 7 or more, or 8 or more. The upper limit of the mass ratio of resin (A) to epoxy compound (B) is not particularly limited, but from the viewpoint of ensuring that the resin composition contains a certain amount of epoxy compound (B), it is preferably 200 or less, more preferably 150 or less, even more preferably 100 or less, and even more preferably 75 or less.

[0031] The resin composition does not need to contain a curing catalyst for curing the epoxy compound (B). The resin composition according to this disclosure can be cured even without containing a curing catalyst for curing the epoxy compound (B). Therefore, the resin composition according to this disclosure does not need to contain a curing catalyst that is generally used for curing epoxy resins. Examples of curing catalysts for curing the epoxy compound (B) include polyamines, polyamides, polymer captans, tertiary amine compounds, imidazoles, amidines, guanidines, acid anhydrides, boron trifluoride-amine complexes, polymer captans, polysulfides, novolac-type phenolic resins, dicyandiamides, and organic acid hydrazides.

[0032] The content of epoxy compound (B) in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less, based on 100% by mass of the solid content of the resin composition.

[0033] The solvent (C) is not particularly limited as long as it has a boiling point of 100°C or higher. By containing solvent (C), the resin composition can be used as a paint-like resin composition, which facilitates the coating of the resin composition and makes it easy to form a thin resin film. Solvent (C) may function to dissolve each component contained in the resin composition, or it may function as a dispersion medium.

[0034] In resin compositions, the boiling point of solvent (C) is 100°C or higher, which suppresses the evaporation of solvent (C) during coating, making it easier to obtain a resin film with uniform thickness and high transparency. For example, spin coating is generally performed under reduced pressure, but under reduced pressure, the solvent tends to evaporate all at once, resulting in uneven thickness of the resulting resin film or the inclusion of fine bubbles inside the resin film, making it prone to clouding. However, by using solvent (C) with a boiling point of 100°C or higher, such problems can be avoided, and it becomes easier to coat the resin film with high uniformity. The boiling point of solvent (C) may be 105°C or higher, or it may be 250°C or lower, 200°C or lower, or 150°C or lower.

[0035] Examples of solvents (C) include ketones such as methyl isobutyl ketone and cyclohexanone; glycol derivatives such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); amides such as N,N-dimethylacetamide; esters such as propyl acetate and butyl acetate; pyrrolidones such as N-methylpyrrolidone (specifically, 1-methyl-2-pyrrolidone, etc.); aromatic hydrocarbons such as toluene, xylene, and trimethylbenzene; aliphatic hydrocarbons such as octane and cycloheptane; and ethers such as tetrahydropyran, 4-methyloxane, dioxane, and dibutyl ether. These solvents may be used individually or in combination of two or more. For example, a squarylium-based dye or a croconium-based dye may be used as the dye (D) and aromatic hydrocarbons as the solvent (C), or a cyanine-based dye may be used as the dye (D) and ethers as the solvent (C). Aromatic hydrocarbons and ethers may also be used in combination.

[0036] The solvent (C) content is preferably, for example, 30% by mass or more, more preferably 45% by mass or more, even more preferably 60% by mass or more, preferably less than 100% by mass, and more preferably 95% by mass or less, based on 100% by mass of the resin composition. By adjusting the solvent (C) content within this range, the coating properties of the resin composition can be improved.

[0037] The resin composition may contain a dye (D). The dye may be a dye that absorbs visible light, a dye that absorbs near-infrared light on the longer wavelength side of visible light, or a dye that absorbs ultraviolet light on the shorter wavelength side of visible light. Preferably, the dye (D) has an absorption maximum in the wavelength range of 200 nm to 1100 nm. If the resin composition contains a dye (D), the resin film formed from the resin composition can be suitably applied to an optical filter having light-selective transmission properties.

[0038] If the dye (D) is a visible light absorbing dye, the dye only needs to have an absorption maximum in the visible light region (for example, in the range of wavelengths greater than 420 nm and less than 680 nm), and it is preferable that it has an absorption maximum in the range of wavelengths greater than 500 nm and less than 680 nm, where luminous sensitivity is high. Resin compositions containing a visible light absorbing dye can be suitably used in the manufacture of optical filters such as colored filters and blue light reduction filters.

[0039] When the dye (D) is a near-infrared absorbing dye, it is preferable that the dye has an absorption maximum in the wavelength range of 680 nm to 1100 nm. A resin composition containing a near-infrared absorbing dye can be suitably used in the manufacture of optical filters that suppress the transmission of light in the near-infrared region and preferentially transmit light in the visible light region. It can also be used in the manufacture of near-infrared cut filters that cut out light in the red to near-infrared region.

[0040] The near-infrared absorbing dye preferably has a peak with an absorption maximum in the wavelength range of 680 nm to 1100 nm in its absorption spectrum in the wavelength range of 200 nm to 1100 nm, and the absorption maximum of the absorption peak preferably takes its maximum value in the wavelength range of 200 nm to 1100 nm. The wavelength of the absorption maximum is more preferably 685 nm or higher, even more preferably 690 nm or higher, even more preferably 1000 nm or lower, even more preferably 900 nm or lower, and even more preferably 800 nm or lower.

[0041] When the dye (D) is an ultraviolet absorbing dye, it is preferable that the dye has an absorption maximum in the range of 200 nm to 420 nm. A resin composition containing an ultraviolet absorbing dye can be suitably used in the manufacture of optical filters that suppress the transmission of light in the violet to ultraviolet region and preferentially transmit light in the visible light region. It can also be used in the manufacture of ultraviolet cut filters that cut out light in the ultraviolet region. Furthermore, even when exposed to ultraviolet light during storage of the resin composition or during the manufacture and processing of optical filters (e.g., vapor deposition or mounting), the resin component and other components contained in the resin composition can be protected from such ultraviolet light, and the degradation of these components can be suppressed.

[0042] The ultraviolet absorbing dye preferably has an absorption spectrum in the range of 200 nm to 1100 nm, with a peak having an absorption maximum in the range of 200 nm to 420 nm, and the absorption maximum of the absorption peak preferably takes its maximum value in the range of 200 nm to 1100 nm. The wavelength of the absorption maximum is more preferably 250 nm or higher, even more preferably 300 nm or higher, and even more preferably 400 nm or lower.

[0043] The dye (D) is not particularly limited, and may be an organic dye, an inorganic dye, or an organic-inorganic composite dye (for example, an organic compound to which a metal atom or ion is coordinated).

[0044] Examples of near-infrared and visible light absorbing dyes include squarylium dyes, crokonium dyes, cyclic tetrapyrrole dyes (porphyrins, chlorines, phthalocyanines, naphthalocyanines, cholines, etc.) which may have copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as the central metal ion, cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes, quaterylene dyes, diimonium dyes, perylene dyes, quinacdrin dyes, oxazine dyes, dipyromethene dyes, nickel complex dyes, copper ion dyes, etc. These dyes may be used individually or in combination of two or more.

[0045] As ultraviolet absorbing dyes, known compounds known as ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinon compounds, cyanoacrylate compounds, benzoxazole compounds, merocyanine compounds, triazine compounds, and triazole compounds can be used. One ultraviolet absorbing dye may be used alone, or two or more may be used.

[0046] When the resin composition contains a dye (D), the content of dye (D) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on 100% by mass of the solid content of the resin composition. The content of dye (D) per 100 parts by mass of resin (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less.

[0047] The resin composition preferably contains a near-infrared absorbing dye and / or an ultraviolet absorbing dye as the dye (D). As a result, the resin film formed from the resin composition suppresses the transmission of light in the near-infrared and / or ultraviolet regions and preferentially transmits light in the visible light region, making it suitable for use in optical filters such as near-infrared cut filters and ultraviolet cut filters.

[0048] As the dye (D), squarylium-based dyes, crokonium-based dyes, and cyanine-based dyes can be suitably used. By containing such dyes in the resin composition, the resin composition can be suitably used in the manufacture of optical filters and the like that cut out light in the red to near-infrared region. In this case, the resin composition only needs to contain at least one selected from squarylium-based dyes, crokonium-based dyes, and cyanine-based dyes.

[0049] As squarylium-based dyes, compounds having a squarylium skeleton, i.e., squarylium compounds, can be used. As crokonium-based dyes, compounds having a crokonium skeleton, i.e., crokonium compounds, can be used. As cyanine-based dyes, compounds having a polymethine chain can be used.

[0050] The squarylium compound and the crokonium compound, which are suitably used as dyes (D), will be described in detail. The squarylium compound is shown as the compound represented by the following formula (2), and the crokonium compound is shown as the compound represented by the following formula (3). In the following formulas (2) and (3), R １１ ~R １４ Each of these independently represents an organic group.

[0051]

[0052] In formulas (2) and (3) above, the squarylium compound and the crokonium compound are R １１ ~R １４ Preferably, each of these groups is independently represented by the following formula (4) or formula (5). Squirrium compounds or crokonium compounds having the group represented by formula (4) form a broad absorption peak in the red to near-infrared region, allowing for the filtering of light across a relatively wide wavelength range. On the other hand, squarylium compounds or crokonium compounds having the group represented by formula (5) form a sharp absorption peak in the red to near-infrared region, making it possible to selectively filter out light in the wavelength range corresponding to this absorption peak.

[0053]

[0054] In formula (4), ring P represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing these ring structures, which may have substituents. ２１ ~R ２３ Each of these independently represents a hydrogen atom, an organic group, or a polar functional group, and R ２２ and R ２３ They may be connected to each other to form a ring. In formula (5), R ２４ ~R ２８ Each of these independently represents a hydrogen atom, an organic group, or a polar functional group, and R ２４ and R ２５ , R ２５ and R ２６ , R ２６ and R ２７ , R ２７ and R ２８These may each be linked to each other to form a ring. * indicates a bonding site with the four-membered ring in formula (2) or the five-membered ring in formula (3).

[0055] While there may be compounds that are in a resonance relationship with squarylium compounds and crokonium compounds, the squarylium compound represented by formula (2) and the crokonium compound represented by formula (3) above also include these resonance-related compounds.

[0056] In formula (2) above, the groups bonded to one side and the other side of the squarylium skeleton may be the same or different. In formula (3) above, the groups bonded to one side and the other side of the crokonium skeleton may be the same or different. When the groups bonded to one side and the other side of the squarylium skeleton or crokonium skeleton are the same, improved resistance to heat and light of the squarylium compound or crokonium compound can be expected. When the groups bonded to one side and the other side of the squarylium skeleton or crokonium skeleton are different, association and aggregation of molecules of the squarylium compound or crokonium compound are suppressed, and improved solubility in solvents and resins can be expected.

[0057] R ２１ ~R ２８ Examples of organic groups include alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, alkylsulfonyl groups, alkylsulfinyl groups, aryl groups, aralkyl groups, aryloxy groups, arylthio groups, aryloxycarbonyl groups, arylsulfonyl groups, arylsulfinyl groups, heteroaryl groups, amino groups, amide groups, sulfonamide groups, carboxyl groups (carboxylic acid groups), cyano groups, etc. ２１ ~R ２８ Examples of polar functional groups include halogen groups, hydroxyl groups, nitro groups, and sulfo groups (sulfonic acid groups).

[0058] R ２１ ~R ２８Examples of alkyl groups include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups; and cyclic (alicyclic) alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups. Alkyl groups may have substituents, and examples of such substituents include aryl, heteroaryl, halogeno, hydroxyl, carboxyl, alkoxy, cyano, nitro, amino, and sulfo groups. Examples of alkyl groups having a halogen group include monohalogenoalkyl groups, dihalogenoalkyl groups, alkyl groups having a trihalomethyl unit, and perhalogenoalkyl groups. Preferred halogen groups are fluoro groups, chloro groups, and bromo groups, with fluoro groups being particularly preferred. The number of carbon atoms (excluding substituents) of the alkyl group is preferably 1 to 20. Specifically, for linear or branched alkyl groups, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. For cyclic alkyl groups, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8.

[0059] R ２１ ~R ２８ For specific examples of alkyl groups included in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfinyl group, please refer to the explanation of alkyl groups above.

[0060] R ２１ ~R ２８Examples of aryl groups include phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, and indenyl groups. The aryl group may have substituents, and examples of substituents on the aryl group include alkyl, alkoxy, heteroaryl, halogeno, halogenoalkyl, hydroxyl, cyano, nitro, amino, thiocyanate, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and sulfamoyl groups. The number of carbon atoms in the aryl group (excluding substituents) is preferably 6 to 20, and more preferably 6 to 12.

[0061] R ２１ ~R ２８ Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, and naphthylmethyl groups. Aralkyl groups may have substituents, and examples of substituents on aralkyl groups include alkyl groups, alkoxy groups, halogeno groups, halogenoalkyl groups, cyano groups, nitro groups, thiocyanate groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfo groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and sulfamoyl groups. The number of carbon atoms in the aralkyl group (excluding substituents) is preferably 7 to 25, and more preferably 7 to 15.

[0062] R ２１ ~R ２８ For specific examples of aryl groups included in aryloxy, arylthio, aryloxycarbonyl, arylsulfonyl, and arylsulfinyl groups, please refer to the explanation of aryl groups above.

[0063] R ２１ ~R ２８Examples of heteroaryl groups include thienyl group, thiopyranyl group, isothioclomenyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyraridinyl group, pyrimidinyl group, pyridadinyl group, thiazolyl group, isothiazolyl group, furanyl group, and pyranyl group. Heteroaryl groups may have substituents, and examples of substituents on heteroaryl groups include alkyl groups, alkoxy groups, aryl groups, halogeno groups, halogenoalkyl groups, hydroxyl groups, cyano groups, amino groups, nitro groups, thiocyanate groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfo groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and sulfamoyl groups. The number of carbon atoms (excluding substituents) of the heteroaryl group is preferably 2 to 20, and more preferably 3 to 15.

[0064] R ２１ ~R ２８ The amino group is given by formula: -NR ａ１ R ａ２ It is represented as R ａ１ and R ａ２ Examples include hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, and heteroaryl groups, each independently. Specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups are given in the descriptions of these groups above. Alkenyl groups and alkynyl groups include groups in which some of the carbon-carbon single bonds of the alkyl groups exemplified above are replaced by double or triple bonds. ａ１ and R ａ２ They may be connected to each other to form a ring.

[0065] R ２１ ~R ２８ The amide group is given by formula: -NH-C(=O)-R ａ３ It is represented as R ａ３ Examples include alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups. For specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups, please refer to the descriptions of these groups above.

[0066] R２１ ~R ２８ The sulfonamide group is of the formula: -NH-SO ２ -R ａ４ It is represented as R ａ４ Examples include alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups. For specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups, please refer to the descriptions of these groups above.

[0067] R ２１ ~R ２８ Examples of halogen groups include fluoro groups, chloro groups, bromo groups, and iodine groups.

[0068] R ２２ ~R ２８ Examples of ring structures formed from these include hydrocarbon rings and heterocycles. These ring structures may or may not be aromatic, but it is preferable that they be non-aromatic hydrocarbon rings or non-aromatic heterocycles. Examples of non-aromatic hydrocarbon rings include cycloalkanes such as cyclopentane, cyclohexane, and cycloheptane; and cycloalkenes such as cyclopentene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene. Examples of non-aromatic heterocycles include rings in which one or more carbon atoms constituting the non-aromatic hydrocarbon ring described above are replaced by at least one atom selected from N (nitrogen atom), S (sulfur atom), and O (oxygen atom). Examples of non-aromatic heterocycles include pyrrolidine rings, tetrahydrofuran rings, tetrahydrothiophene rings, piperidine rings, tetrahydropyran rings, tetrahydrothiopyran rings, morpholine rings, hexamethyleneimine rings, hexamethylene oxide rings, hexamethylene sulfide rings, and heptamethyleneimine rings.

[0069] In equation (4), R ２１ ~R ２３ If R is an independent group, ２１ ~R ２３Each of these is preferably independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group, and more preferably a hydrogen atom, an alkyl group, or an aryl group. ２１ ~R ２３ Preferred alkyl and aryl groups include methyl, ethyl, isopropyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, and phenyl groups.

[0070] In equation (4), R ２２ and R ２３ The ring structure formed by the linkage of these groups is preferably a 4- to 9-membered unsaturated hydrocarbon ring, and among these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are more preferred. When the group of formula (4) is configured in this way, the shoulder peak of the absorption waveform in the red to near-infrared region is reduced, and the absorption peak becomes sharper.

[0071] Examples of aromatic hydrocarbon rings for ring P in formula (4) include benzene rings, naphthalene rings, phenanthrene rings, anthracene rings, fluorantene rings, and cyclotetradecaheptaene rings. The aromatic hydrocarbon ring may have only one ring structure, or it may be a condensed ring of two or more ring structures. The aromatic heterocycle of ring P contains one or more atoms selected from N (nitrogen atom), O (oxygen atom), and S (sulfur atom) in its ring structure and is aromatic. Examples include furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, thiazole rings, imidazole rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, purine rings, and pteridine rings. The aromatic heterocycle may have only one ring structure, or it may be a condensed ring of two or more ring structures. The fused rings containing these ring structures of ring P have a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are fused together. Examples include indole rings, isoindole rings, benzimidazole rings, quinoline rings, benzopyran rings, acridine rings, xanthene rings, and carbazole rings. By appropriately setting the π-conjugated system of ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

[0072] Ring P may have a substituent, and examples of the substituent include the organic groups and polar functional groups described above. When ring P has a substituent, the number thereof is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1. Ring P may have no substituent.

[0073] For details of the squarylium compound and croconium compound having the group represented by formula (4), reference is made to, for example, the description in JP-A-2016-74649.

[0074] In formula (5), when R ２４ to R ２８ are independent groups, R ２４ to R ２８ are each independently preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, an amide group, or a hydroxyl group. By appropriately selecting R ２４ to R ２８ , it is possible to control the absorption maximum wavelength of the squarylium compound and croconium compound to a desired value. Among them, from the viewpoints of the stability and ease of production of the squarylium compound and croconium compound, R ２４ to R ２８ are each independently preferably a hydrogen atom, an alkyl group, or an amide group. In this case, the alkyl group is preferably linear or branched, and the number of carbon atoms thereof is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.

[0075] The group represented by formula (5) is preferably such that R ２５ and R ２６ are linked to form a ring, and further R ２６ and R ２７ may be linked to form a ring. In this case, at least R ２４ and R ２８ are independent groups. If the group of formula (5) is thus constituted, the absorption peak in the red to near-infrared region becomes sharp. Note that the ring structure formed from R ２５ and R ２６ and the ring structure formed from R ２６ and R ２７The number of ring members of the ring structure formed therefrom is preferably 5 or more, more preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0076] In the group represented by the formula (5), R ２６ is an amino group, or R ２６ which is an amino group is linked to R ２５ to form a ring, or further linked to R ２７ to form a ring. It is preferable that R ２６ which is an amino group is linked to R ２５ or R ２７ The number of ring members of the ring formed by the linkage is preferably 5 or more, more preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. In this case, the absorption maximum wavelength is shifted to the long wavelength side (for example, 685 nm or more), the transmittance of light in the red region is increased, and the color tone of the transmitted light can be made closer to the actual one. Also, from the same viewpoint, it is preferable that R ２４ or R ２８ is an amide group.

[0077] The squarylium compound and croconium compound having the group represented by the formula (5) may have benzene rings on both sides of the squarylium skeleton or croconium skeleton linked by a linking group. Examples of such compounds include the squarylium compounds disclosed in JP-A-2015-176046.

[0078] As the cyanine-based dye used for the dye (D), a compound represented by the following formula (6) (hereinafter referred to as "cyanine compound") is preferably mentioned. In the formula (6), M represents a methine chain having 3 or more carbon atoms, and each methine group contained in the methine chain may independently have a substituent, and the substituents may be linked to each other. Z ＋ and Z represent groups bonded to the methine chain M, and A － represents a monovalent anion. The cyanine compound of the formula (6) also includes compounds in a resonance relationship.

[0079]

[0080] In formula (6), the methine chain M having 3 or more carbon atoms means a connected methine chain in which 3 or more methine groups (-CH=) form conjugated double bonds. The upper limit of the number of carbon atoms in the methine chain M is not particularly limited, but it is preferably 15 or less, more preferably 13 or less, even more preferably 11 or less, and particularly preferably 9 or less.

[0081] Each methine group (i.e., hydrogen atom on the methine group) in the methine chain M may independently have substituents, and these substituents may be linked to each other. Examples of substituents that the methine group may have (hereinafter sometimes referred to as "substituents Q") include halogen groups (halogen atoms) and organic groups. Note that the number of carbon atoms in the methine chain M refers to the number of carbon atoms excluding substituents if the methine groups in the methine chain have substituents.

[0082] The methine chain M is preferably composed of an odd number of methine groups. For example, if the number of carbon atoms in the methine chain M is between 3 and 9, it is preferable that the methine chain M consists of 3, 5, 7, or 9 methine groups. In this case, the cyanine compound represented by formula (6) will be represented by the following formulas (6A) to (6D). In formulas (6A) to (6D), R ３１ ~R ３９ Each of these independently represents a hydrogen atom, a halogen atom, or an organic group.

[0083]

[0084] The organic group of substituent Q that the methine group may have is the above-mentioned R. ２１ ~R ２８ Examples of organic groups include the above R. ２１ ~R ２８The description of the organic group is referenced. Among these, the substituent Q is preferably a halogeno group, alkyl group, alkoxy group, aryl group, aralkyl group, or amino group, and more preferably a halogeno group, alkyl group, aryl group, or amino group. In this case, the number of carbon atoms of the alkyl group or alkoxy group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 3; the number of carbon atoms of the aryl group is preferably 6 to 12, more preferably 6 to 10; and the number of carbon atoms of the aralkyl group is preferably 7 to 13, and more preferably 7 to 11. The amino group is of the formula: -NR ａ１ R ａ２ It is represented as R ａ１ and R ａ２ Each of these is preferably independently a hydrogen atom, an alkyl group, or an aryl group, the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.

[0085] When substituents Q on a methine group are linked to each other, it is preferable that substituents attached to two adjacent methine groups are linked to each other to form a ring. In formulas (6A) to (6D), R ３１ and R ３３ , R ３２ and R ３４ , R ３３ and R ３５ , R ３４ and R ３６ , R ３５ and R ３７ , R ３６ and R ３８ or R ３７ and R ３９ It is preferable that they are connected to each other to form a ring.

[0086] The ring formed by the linkage of substituents Q of the methine group is preferably a 5- to 8-membered ring, more preferably a 5- to 7-membered ring, and even more preferably a 5 or 6-membered ring. The ring formed by the linkage of substituents Q of the methine group is formed in partial co-existence with the methine chain, but may or may not have unsaturated bonds in the portion other than the portion shared with the methine chain. Preferably, the ring formed by the linkage of substituents Q of the methine group does not have unsaturated bonds in the portion other than the portion shared with the methine chain.

[0087] The ring formed by the linkage of substituents Q on the methine group may have substituents, and such substituents include organic groups and polar functional groups. Details of organic groups and polar functional groups are described in the above R ２１ ~R ２８ See the description of organic groups and polar functional groups. Among these, halogen groups, alkyl groups, alkoxy groups, aryl groups, and amino groups are preferred substituents on the ring formed by the linkage of substituent Qs. In this case, the number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2, while the number of carbon atoms in the aryl group is preferably 6 to 12.

[0088] The substituent Q that the methine group may have is preferably bonded to the meso position (center) or an adjacent methine group, and it is preferable that the other methine groups do not have substituents. In formula (6A), R ３１ ~R ３３ R may be a hydrogen atom, an organic group, or a polar functional group. In formula (6B), R ３２ ~R ３４ R may be a hydrogen atom, an organic group, or a polar functional group. ３１ and R ３５ It is preferable that R is a hydrogen atom. In formula (6C), ３３ ~R ３５ R may be a hydrogen atom, an organic group, or a polar functional group. ３１ , R ３２ , R ３６ , R ３７ It is preferable that R is a hydrogen atom. In formula (6D), ３４ ~R ３６ R may be a hydrogen atom, an organic group, or a polar functional group. ３１ ~R ３３ , R ３７ ~R ３９ Preferably, the substituent is a hydrogen atom. More preferably, substituents that do not link to form a ring are bonded to the methine group at the meso position, and substituents that link to form a ring are bonded to the methine group adjacent to the meso position, and are linked to each other. The methine chain M may also preferably have no substituents.

[0089] In equation (6), Z＋ And Z represents a group bonded to the methine chain M. The cyanine compound represented by formula (6) is formed from the methine chain M to Z ＋ It is preferable that the π electron system extends to Z, ＋ And Z is preferably a group that forms such a π-electron system. ＋ And Z is preferably represented by the groups shown in formulas (7) to (11) below.

[0090]

[0091] In formula (7), R ４１ represents an organic group, R ４２ ~R ４７ Each of these independently represents a hydrogen atom, a halogen atom, or an organic group, and * represents the bonding site with the methine chain M in formula (6).

[0092]

[0093] In formula (8), R ５０ represents an organic group, ring S represents a hydrocarbon ring having a fused ring structure which may have substituents, or a heterocycle having a fused ring structure which may have substituents, and is spirobonded to an adjacent pyrrole ring, ring T represents an aromatic hydrocarbon ring which may have substituents, an aromatic heterocycle which may have substituents, or a fused ring containing these ring structures which may have substituents, and * represents the bonding site to the methine chain M of formula (6).

[0094]

[0095] In formula (9), R ５１ ~R ５４ Each of these independently represents a hydrogen atom, a halogen atom, or an organic group, or R ５１ and R ５２ , R ５３ and R ５４ They may be connected to each other to form a ring, Y １ is -O-, -S-, or -NR ５５ - represents R ５５ represents an organic group, and * represents the binding site to the methine chain M in formula (6).

[0096]

[0097] In formula (10), R ６１ ~R ６４ Each of these independently represents a hydrogen atom, a halogen atom, or an organic group, Y ２ is -O-, -S-, or -NR ６５ - represents R ６５ represents an organic group, and * represents the binding site to the methine chain M in formula (6).

[0098]

[0099] In formula (11), R ７１ represents an organic group, R ７２ ~R ７５ Each of these independently represents a hydrogen atom, a halogen atom, or an organic group, or R ７２ and R ７３ , R ７３ and R ７４ , R ７４ and R ７５ They may be connected to each other to form a ring, Y ３ is -O-, -S-, -CH=CH- or -C(R ７６ ) (Caution ７７ ) represents R ７６ and R ７７ Each represents an organic group, and * represents the binding site to the methine chain M in formula (6).

[0100] In equations (7) to (11), R ４２ ~R ４７ , R ５１ ~R ５４ , R ６１ ~R ６４ , R ７２ ~R ７５ Examples of halogen atoms (halogeno groups) include fluorine atoms (fluoro groups), chlorine atoms (chloro groups), bromine atoms (bromo groups), and iodine atoms (iodine groups). ４１ ~R ４７ , R ５０ , R ５１ ~R ５４ , R ６１ ~R ６５ , R ７１ ~R ７５ Details of the organic group are as follows: ２１ ~R ２８The explanation of the organic group is referenced.

[0101] In equation (7), R ４１ The alkyl group is preferably an alkyl group, an aryl group, or an aralkyl group, with alkyl groups being more preferred. Examples of the alkyl group include linear or branched alkyl groups, with linear alkyl groups being more preferred. ４１ The alkyl group preferably has 3 or more carbon atoms, more preferably 4 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0102] In equation (7), R ４２ ~R ４７ The group is preferably a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, or amino group, more preferably a hydrogen atom, halogen atom, alkyl group, or alkoxy group, and even more preferably a hydrogen atom, alkyl group, or alkoxy group. The alkyl group or alkoxy group has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group or aryloxy group has 6 to 12 carbon atoms, more preferably 6 to 10, and the aralkyl group has 7 to 13 carbon atoms, and even more preferably 7 to 11.

[0103] In equation (8), R ５０ The alkyl group is preferably an alkyl group, an aryl group, or an aralkyl group, with alkyl groups being more preferred. Examples of the alkyl group include linear or branched alkyl groups, with linear alkyl groups being more preferred. ５０ The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms, and is particularly preferably a methyl group or an ethyl group.

[0104] In formula (8), ring S represents a hydrocarbon ring or heterocycle having a fused ring structure. The hydrocarbon ring and heterocycle of ring S may or may not be aromatic. The number of members of ring S is not particularly limited, but the number of members of the hydrocarbon ring or heterocycle spirobonded to the adjacent pyrrole ring is preferably 5 to 8, more preferably 5 to 7, and even more preferably 5 or 6. Examples of hydrocarbon rings or heterocycles having a fused ring structure of ring S include indene rings, naphthalene rings, anthracene rings, fluorene rings, benzofluorene rings, indole rings, isoindole rings, benzimidazole rings, quinoline rings, benzopyran rings, acridine rings, xanthene rings, carbazole rings, purine rings, pteridine rings, and the like.

[0105] Base Z represented by formula (8) ＋ In cyanine compounds containing the group Z, the ring S is spirobonded to the adjacent pyrrole ring, resulting in a twisted bond between the ring S and the pyrrole ring. This creates molecular distortion, affecting the band gap and allowing for the extension of the absorption wavelength. Furthermore, molecular association and aggregation are suppressed, improving solubility in organic solvents and resins.

[0106] The hydrocarbon ring or heterocycle of ring S may have substituents, such as organic groups and polar functional groups. Details of these organic groups and polar functional groups are described in the above R. ２１ ~R ２８ See the description of the organic group and polar functional group. Preferred substituents that ring S may have are alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, aryl groups, aryloxycarbonyl groups, and halogen groups; more preferably alkyl groups, alkoxy groups, alkylthio groups, halogen groups, and aryl groups; and more preferably alkyl groups, alkoxy groups, and halogen groups.

[0107] Ring S preferably has π bonds, and more specifically, the hydrocarbon ring or heterocycle spirobonded to the pyrrole ring preferably has π bonds. This makes it easier for the entire ring S to be twisted relative to the pyrrole ring, thereby increasing molecular strain. In this case, it is preferable that the atom one position away from the carbon atom spirobonded to the pyrrole ring and the atom two positions away from it are connected by a π bond. Examples of such π bonds include double bonds, such as a double bond between carbon atoms, a double bond between carbon atoms and nitrogen atoms, or a double bond between nitrogen atoms. The π bonds of the hydrocarbon ring or heterocycle spirobonded to the adjacent pyrrole ring of ring S may also partially share with the fused ring.

[0108] In ring S, it is preferable that the fused ring is formed such that it shares a bond between the atom one position away from the carbon atom spirobonded to the pyrrole ring and the atom two positions away. This allows ring S to be formed in a twisted state relative to the pyrrole ring, resulting in a large molecular strain.

[0109] Ring S is particularly preferably a hydrocarbon ring or heterocycle having a fused ring structure represented by the following formulas (12-1) to (12-4). In the following formulas (12-1) to (12-4), ring U １ ~Circle U ６ Each of these independently represents a hydrocarbon ring which may have substituents, and Y １１ is, -CH ２ -, -NH-, -O-, or -S- represent Y １２ ~Y １５ Each is independent of the other, -CH ２ -, -CH=, -NH-, -N=, -O-, or -S- represent the sites of spirobonding with adjacent pyrrole rings. Ring U １ ~Circle U ６ For information on substituents that may be present, please refer to the description of substituents that may be present on ring S above.

[0110]

[0111] U １ ~Circle U ６Examples of hydrocarbon rings include aromatic hydrocarbon rings and aliphatic hydrocarbon rings. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, phenanthrene rings, anthracene rings, fluorantene rings, etc. Aromatic hydrocarbon rings may have only one ring structure or may be formed by the condensation of two or more ring structures. Examples of aliphatic hydrocarbon rings include monocyclic cycloalkanes with 3 to 10 carbon atoms such as cyclopentane, cyclohexane, and cycloheptane; and monocyclic cycloalkenes with 3 to 10 carbon atoms such as cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene. Ring U １ ~Circle U ６ It is preferably a monocyclic ring, more preferably a monocyclic cycloalkene or benzene ring having 3 to 10 carbon atoms (preferably 5 to 8 carbon atoms), and more preferably a benzene ring (specifically, a benzene ring fused with a 5-membered or 6-membered ring spirobonded at the * position).

[0112] In formula (8), ring T represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing these ring structures, and these ring structures may have substituents. By having ring T, the cyanine compound has a wide π-electron system extending from the methine chain M through the pyrrole ring to ring T, which allows for the extension of the absorption wavelength to longer wavelengths.

[0113] The aromatic hydrocarbon ring of ring T is composed of carbon atoms and hydrogen atoms and is not particularly limited as long as it has an aromatic ring structure, for example, a benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, fluorantene ring, etc. The aromatic hydrocarbon ring may have only one ring structure or may be a fused ring of two or more ring structures. The aromatic heterocycle of ring T is not particularly limited as long as it contains one or more atoms selected from N (nitrogen atom), O (oxygen atom), and S (sulfur atom) in its ring structure and has aromaticity, for example, a furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, purine ring, pteridine ring, etc. The aromatic heterocycle may have only one ring structure or may be a fused ring of two or more ring structures. These fused rings, which include these ring structures, have a structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are fused together. Examples include indole rings, isoindole rings, benzimidazole rings, quinoline rings, benzopyran rings, acridine rings, xanthene rings, and carbazole rings.

[0114] Ring T may have substituents, such as organic groups and polar functional groups. Details of these organic groups and polar functional groups are described in the above R. ２１ ~R ２８ See the description of organic groups and polar functional groups. Preferred substituents that ring T may have are alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, aryl groups, aryloxycarbonyl groups, amino groups, cyano groups, halogeno groups, nitro groups, and more preferably alkyl groups, alkoxy groups, alkylthio groups, halogeno groups, and aryl groups. If ring T has substituents, the number is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2. If ring T has multiple substituents, the substituents may be the same or different. Ring T may not have substituents.

[0115] The number of π electrons contained in ring T, that is, the number of π electrons contained in the aromatic hydrocarbon ring, aromatic heterocycle, or fused ring containing these ring structures, is not particularly limited and may be, for example, four or more, or six or more. There is no particular upper limit to the number of π electrons contained in ring T, but it is preferably 18 or less, more preferably 14 or less, and even more preferably 10 or less. Note that the number of π electrons contained in ring T refers to the number of π electrons including those of the carbon-carbon bond shared by ring T and the pyrrole ring. From the viewpoint of ease of compound production, ring T is preferably an aromatic hydrocarbon ring, and particularly preferably a benzene ring or a naphthalene ring.

[0116] In equation (9), R ５１ ~R ５４ If R is an independent group, ５１ ~R ５４ Each of these groups is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, or an amino group, more preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and even more preferably a hydrogen atom, an alkyl group, or an alkoxy group. The alkyl group or alkoxy group has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group or aryloxy group has 6 to 12 carbon atoms, more preferably 6 to 10, and the aralkyl group has 7 to 13 carbon atoms, and even more preferably 7 to 11.

[0117] In equation (9), R ５１ and R ５２ , R ５３ and R ５４ Each ring formed by the linkage of these elements (hereinafter referred to as "ring R") can be a hydrocarbon ring or a heterocycle, and these ring structures may or may not be aromatic. Examples of ring R include aromatic hydrocarbon rings, aromatic heterocycles, non-aromatic hydrocarbon rings, and non-aromatic heterocycles. The number of members in ring R is preferably 5 to 8, more preferably 5 to 7, and even more preferably 5 or 6.

[0118] For aromatic hydrocarbons and aromatic heterocycles of ring R, refer to the description of ring T above. Examples of non-aromatic hydrocarbon rings of ring R include aliphatic hydrocarbon rings, such as monocyclic cycloalkanes with 3 to 10 carbon atoms, such as cyclopentane, cyclohexane, and cycloheptane; and monocyclic cycloalkenes with 3 to 10 carbon atoms, such as cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene. Examples of non-aromatic heterocycles of ring R include rings in which one or more carbon atoms constituting the aliphatic hydrocarbon ring are replaced by at least one atom selected from N (nitrogen atom), S (sulfur atom), and O (oxygen atom). Examples of non-aromatic heterocycles include pyrrolidine rings, tetrahydrofuran rings, tetrahydrothiophene rings, piperidine rings, tetrahydropyran rings, tetrahydrothiopyran rings, morpholine rings, hexamethyleneimine rings, hexamethylene oxide rings, hexamethylene sulfide rings, and heptamethyleneimine rings. Ring R may have a fused ring structure formed by fusion with other rings. Examples of such ring structures include indene rings, fluorene rings, benzofluorene rings, indole rings, isoindole rings, benzimidazole rings, quinoline rings, benzopyran rings, acridine rings, xanthene rings, carbazole rings, purine rings, and pteridine rings.

[0119] Ring R may have substituents, such as organic groups and polar functional groups. Details of these organic groups and polar functional groups are described above for R. ２１ ~R ２８ Refer to the description of the organic group and polar functional group. A halogen group is preferred as the polar functional group. If ring R has multiple substituents, the substituents may be the same or different. Ring R may not have substituents.

[0120] In equation (9), Y １ ga-NR ５５ When representing -, R ５５ Details of the organic group are as follows: ２１ ~R ２８ The explanation of the organic group is referenced. ５５The group is preferably a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, with a hydrogen atom or an alkyl group being more preferred. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10, and the aralkyl group preferably has 7 to 13 carbon atoms, and even more preferably 7 to 11.

[0121] In equation (10), R ６１ ~R ６４ If R is an independent group, ６１ ~R ６４ Each of these groups is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, or an amino group, more preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and even more preferably a hydrogen atom, an alkyl group, or an alkoxy group. The alkyl group or alkoxy group has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group or aryloxy group has 6 to 12 carbon atoms, more preferably 6 to 10, and the aralkyl group has 7 to 13 carbon atoms, and even more preferably 7 to 11.

[0122] In equation (10), Y ２ ga-NR ６５ When representing -, R ６５ Details of the organic group are as follows: ２１ ~R ２８ The explanation of the organic group is referenced. ６５ The group is preferably a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, with a hydrogen atom or an alkyl group being more preferred. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10, and the aralkyl group preferably has 7 to 13 carbon atoms, and even more preferably 7 to 11.

[0123] In equation (11), R ７１The alkyl group is preferably an alkyl group, an aryl group, or an aralkyl group, with alkyl groups being more preferred. Examples of the alkyl group include linear or branched alkyl groups, with linear alkyl groups being more preferred. ７１ The alkyl group preferably has 3 or more carbon atoms, more preferably 4 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0124] In equation (11), R ７２ ~R ７５ If R is an independent group, ７２ ~R ７５ Each of these groups is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, or an amino group, more preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and even more preferably a hydrogen atom, an alkyl group, or an alkoxy group. The alkyl group or alkoxy group has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group or aryloxy group has 6 to 12 carbon atoms, more preferably 6 to 10, and the aralkyl group has 7 to 13 carbon atoms, and even more preferably 7 to 11.

[0125] In equation (11), R ７２ and R ７３ , R ７３ and R ７４ , R ７４ and R ７５ When the elements are linked to each other to form a ring, each ring is described in the above description of ring R.

[0126] In equation (11), Y ３ When -CH=CH- represents the base Z ＋ The base Z will have a quinoline skeleton. ３ ga-C(R ７６ ) (Caution ７７ ) - When representing R ７６ and R ７７ Details of the organic group are as follows: ２１ ~R ２８ The explanation of the organic group is referenced. ７６ and R ７７Each of these is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or an amino group, and more preferably a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. The alkyl group or alkoxy group has 1 to 8 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The aryl group has 6 to 12 carbon atoms, more preferably 6 to 10, and the aralkyl group has 7 to 13 carbon atoms, and more preferably 7 to 11.

[0127] In equation (6), A － Examples of anions include halogen ions and BF ４ － , PF ６ － , ClO ４ － These are some examples. － The conjugate acid is preferably an anion with a pKa of -8.0 or less; that is, the cyanine compound preferably has a conjugate acid anion with a pKa of -8.0 or less. This can improve the heat resistance of the cyanine compound.

[0128] Examples of acids with a pKa of -8.0 or less include those listed in Table 1 of Agnes Kutt et al., “Equilibrium Acidities of Super Acids”, J. Org. Chem., 76, 391-395 (2011). － The pKa of the conjugate acid of the anion is preferably -10.0 or less, more preferably -11.0 or less, and even more preferably -18.0 or less. － The anion is preferably a low nucleophilic anion, and is preferably an anion formed when a low pKa acid, generally called a super acid, dissociates a proton.

[0129] A － Examples of anions include those represented by the following formulas (13-1) to (13-3). In formulas (13-1) to (13-3), R ８１ ~R ８７Each of these independently represents a fluorine atom, a fluoroalkyl group, a fluoroaryl group, or a cyano group, R ８８ and R ８９ Each of these is independently a fluorine atom, a fluoroalkyl group, a fluoroaryl group, a cyano group, or -SO ２ -R ９０ Represents R ９０ This represents a fluorine atom, a fluoroalkyl group, a fluoroaryl group, or a cyano group.

[0130]

[0131] A － In addition to the anions of formulas (13-1) to (13-3), the anions may also be perchlorate ions, fluorosulfonate ions, fluoroalkyl sulfonate ions, cyanoalkyl sulfonate ions, 2,4,6-trinitrobenzenesulfonate ions, 1,1,3,3-tetracyanoallyl ions, fluorophosphate ions, fluoroantimonate ions, and the like.

[0132] In formulas (13-1) to (13-3), R ８１ ~R ９０ The fluoroalkyl group can be linear, branched, or cyclic fluoroalkyl groups, with linear or branched being preferred, and more preferably linear. The fluoroalkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 4 carbon atoms, and is preferably a perfluoroalkyl group. ８１ ~R ９０ The number of carbon atoms in the fluoroaryl group is preferably 6 to 12, more preferably 6 to 10, and preferably a perfluoroaryl group. Furthermore, the fluoroalkyl sulfonate ion, fluorophosphate ion, and fluoroantimonate ion listed above as anions other than the anions of formulas (13-1) to (13-3) are preferably perfluoroalkyl sulfonate ion, hexafluorophosphate ion, and hexafluoroantimonate ion, respectively. The number of carbon atoms in the alkyl group of the fluoroalkyl sulfonate ion is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0133] A － The anion is preferably an anion represented by formula (13-1), i.e., a borate ion, and therefore, the cyanine compound is preferably a borate ion. This can further enhance the heat resistance of the cyanine compound. In this case, R ８１ ~R ８４ It is more preferably a fluoroalkyl group, a fluoroaryl group, or a cyano group, even more preferably a fluoroalkyl group or a fluoroaryl group, and particularly preferably a fluoroaryl group. Examples of borate ions having a fluoroaryl group and a conjugate acid pKa of -8.0 or less include tetrakis(pentafluorophenyl)borate anion (conjugate acid pKa of approximately -30).

[0134] It is also preferable to use a compound having a styrene structure represented by the following formula (14) (hereinafter referred to as "styrene-based compound") as the dye (D). The styrene-based compound represented by the following formula (14) functions as an ultraviolet absorbing dye, forming an absorption wavelength range in the wavelength range of 350 nm to 395 nm, and at the longer wavelength side of the absorption wavelength range, it can form a sharp boundary between the absorption wavelength range and the transmission wavelength range. Therefore, if the resin composition contains such a styrene-based compound, the resin film formed from the resin composition can be suitably applied to optical filters and the like that cut out light in the violet to ultraviolet region.

[0135]

[0136] In the above formula (14), R ９１ R represents a cyano group, acyl group, carboxylic acid ester group, or amide group. ９２ R represents a hydrogen atom, cyano group, acyl group, carboxylic acid ester group, amide group, hydrocarbon group, or heteroaryl group. ９１ and R ９２ If both are acyl groups, carboxylic acid ester groups, or amide groups, ９１ and R ９２ They may be connected to each other to form a ring, R ９３ R represents a hydrogen atom or an alkyl group. ９４R represents a hydrogen atom, an organic group, or a polar functional group, and there are multiple R ９４ The groups may be the same or different from each other, Y represents a sulfur atom or an oxygen atom, L represents a hydrogen atom or a linking group with two or more valents, a represents an integer of 2 or more, and the multiple groups bonded to L may be the same or different from each other. In formula (14), R ９１ (or R ９２ ) is R ９３ In contrast, it may be in the cis position or the trans position.

[0137] R ９１ and R ９２ Examples of acyl groups (alkanoyl groups) include methanoloyl, ethanoloyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and eicosayl groups. Some hydrogen atoms in the acyl group may be substituted with aryl, alkoxy, halogeno, or hydroxyl groups. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms in the acyl group (number of carbon atoms excluding substituents) is preferably 2 to 21, more preferably 2 to 11, and even more preferably 2 to 6.

[0138] R ９１ and R ９２ The carboxylic acid ester group is given by formula: -C(=O)-O-R ｂ１ It is represented as R ｂ１ Examples include alkyl groups, aryl groups, and aralkyl groups. Specific examples of alkyl groups, aryl groups, and aralkyl groups are shown above. ２１ ~R ２８ The explanations of these bases are referenced.

[0139] R ９１ and R ９２ The amide group is given by formula: -C(=O)-NR ｂ２ R ｂ３ It is represented as R ｂ２ is a hydrogen atom or an alkyl group, R ｂ３Examples include those in which the group is an alkyl group, acyl group, aryl group, or aralkyl group. ｂ２ and R ｂ３ Specific examples of alkyl, aryl, and aralkyl groups are shown above in R ２１ ~R ２８ The explanations of these bases are referenced, R ｂ３ A specific example of the acyl group is the above R ９１ and R ９２ The explanation of the acyl group is referenced.

[0140] R ９１ and R ９２ When both are acyl groups and are linked to each other to form a ring, R ９１ and R ９２ The group formed from this is given by formula: -C(=O)-R ｂ４ The group represented by -C(=O)- is shown. ９１ and R ９２ When both are carboxylic acid ester groups and are linked to each other to form a ring, R ９１ and R ９２ The group formed from this is given by formula: -C(=O)-O-R ｂ５ The group represented by -O-C(=O)- is shown. ９１ and R ９２ When both are amide groups and are linked to each other to form a ring, R ９１ and R ９２ The group formed from this is given by formula: -C(=O)-NR ｂ６ -R ｂ７ -NR ｂ８ The group represented by -C(=O)- is shown. In these formulas, R ｂ４ , R ｂ５ and R ｂ７ Each of these independently represents a linear or branched alkylene group, R ｂ６ and R ｂ８ Each of these independently represents a hydrogen atom or a hydrocarbon group, and the carbon atoms of the carbonyl groups at both ends of the structures shown in these formulas are bonded to the carbon atoms of the ethylene double bond in formula (14). ｂ４ , R ｂ５ and R ｂ７The alkylene group may have some of its hydrogen atoms substituted with aryl groups, alkoxy groups, cyano groups, halogeno groups, hydroxyl groups, nitro groups, etc. ｂ４ , R ｂ５ and R ｂ７ The number of carbon atoms in the alkylene group (excluding substituents) is preferably 2 to 10, and more preferably 3 to 8. ｂ６ and R ｂ８ Preferred hydrocarbon groups include alkyl groups, aryl groups, or aralkyl groups, and specific examples of these groups are as follows: ２１ ~R ２８ See the explanations of alkyl, aryl, and aralkyl groups.

[0141] R ９２ Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups (aryl groups). Aliphatic hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example of an aliphatic saturated hydrocarbon group is the above R ２１ ~R ２８ The explanation of alkyl groups is referenced, and specific examples of aliphatic unsaturated hydrocarbon groups are as described above. ２１ ~R ２８ Examples include alkyl groups in which some of the carbon-carbon single bonds are replaced by double or triple bonds. Specific examples of aromatic hydrocarbon groups (aryl groups) are shown above. ２１ ~R ２８ The explanation of the aryl group is referenced.

[0142] R ９２ A specific example of the heteroaryl group is the above R ２１ ~R ２８ See the explanation of the heteroaryl group. It is preferable that the heteroaryl group has a carbon atom bonded to the carbon atom of the ethylene double bond in formula (14), and more preferably that the carbon atom adjacent to the heteroatom is bonded to the carbon atom of the ethylene double bond in formula (14), which facilitates the synthesis of styrene compounds.

[0143] R in equation (14) ９３ R represents a hydrogen atom or an alkyl group, and specific examples of alkyl groups are shown above. ２１ ~R２８ See the explanation regarding alkyl groups. ９３ The alkyl group preferably has 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms. ９３ Hydrogen atoms are particularly preferred.

[0144] R in equation (14) ９４ Details of the organic groups and polar functional groups are as follows: ２１ ~R ２８ The explanation of organic groups and polar functional groups is referenced. ９４ Preferably, it is one or more selected from a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aralkyl group, aryloxy group and arylthio group, and preferably a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 4, and more preferably 1 to 3. In particular, the four Rs bonded to the benzene ring of formula (14) ９４ Preferably, two or more of these are hydrogen atoms, more preferably three or more are hydrogen atoms, and particularly preferably all four are hydrogen atoms.

[0145] In formula (14), Y represents a sulfur atom or an oxygen atom. Y is R ９１ ~R ９３ The ethylene structure containing Y may be bonded at the ortho position, the meta position, or the para position. From the viewpoint of ease of production of styrene-based compounds, it is preferable that Y is bonded at the para position to the ethylene structure. Furthermore, it is preferable that Y is a sulfur atom.

[0146] In formula (14), L represents a linking group with two or more valent values, and such linking groups include alkylene groups, arylene groups, heteroarylene groups, -O-, -CO-, -S-, -SO-, and -SO ２ Examples include divalent linking groups such as - and -NH-; trivalent linking groups such as methine groups (-CH<) and -N< which may be substituted with alkyl groups; tetravalent linking groups such as >C<; and linking groups combining these. The alkylene group may be linear, branched, or cyclic. Furthermore, the alkylene group and the arylene group may have a hydroxyl group and / or a thiol group.

[0147] The linking group L is preferably an alkylene group in which some of the hydrogen atoms may be replaced by hydroxyl groups and / or thiol groups, an arylene group in which some of the hydrogen atoms may be replaced by hydroxyl groups and / or thiol groups, -O-, -S-, and linking groups that combine these groups (however, ether bonds and thioether bonds are not continuous). The number of carbon atoms (number of consecutive carbon atoms) of a linear or branched alkylene group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. If it is a cyclic alkylene group, the number of carbon atoms is preferably 4 or more, more preferably 5 or more, preferably 10 or less, and even more preferably 8 or less. The number of carbon atoms of an arylene group is preferably 5 or more, more preferably 6 or more, preferably 10 or less, and even more preferably 8 or less.

[0148] As a styrene-based compound, the styrene-based compound shown in the following formula (14A) is particularly preferred. Such a styrene-based compound has, for example, a peak with an absorption maximum in the wavelength range of 300 nm to 420 nm, and can effectively absorb light in the ultraviolet (UVA) to violet region, and is also highly stable and easy to manufacture. In the following formula (14A), R ９１ａ and R ９１ｂ The explanation is as follows (R) ９１ The explanation of R is referenced. ９２ａ and R ９２ｂ The explanation is as follows (R) ９２ The explanation of R is referenced. ９３ａ and R ９３ｂ The explanation is as follows (R) ９３ The explanation of Y is referenced. ａ and Y ｂ For further explanation, please refer to the explanation for Y above.

[0149]

[0150] For details on the styrene compounds represented by formula (14) and formula (14A), please refer to International Publication No. 2019 / 009093.

[0151] The resin composition may contain at least one (E) selected from a silane coupling agent, a hydrolysate of a silane coupling agent, and a hydrolyzed condensate of a silane coupling agent. This improves the adhesion of the resin layer to the substrate when the resin composition is coated onto a substrate to form a resin layer. A laminated substrate with a resin layer formed from such a resin composition can be suitably applied to optical filters. Hereinafter, the silane coupling agent, the hydrolysate of a silane coupling agent, and the hydrolyzed condensate of a silane coupling agent may be collectively referred to as "specific silane compounds."

[0152] The silane coupling agent preferably has an epoxy group-containing group, an amino group-containing group, a mercapto group-containing group, or a polymerizable double bond-containing group, and it is preferable to use a compound having such a functional group and an alkoxysilyl group. The silane coupling agent may contain only one of the above functional groups or multiple functional groups, and may contain only one or multiple alkoxysilyl groups.

[0153] When the silane coupling agent contains only one alkoxysilyl group, an alkoxysilane represented by the following formula (15) is preferably used as the silane coupling agent. Therefore, as the specific silane compound (E), it is preferable to use at least one selected from the silane coupling agent represented by the following formula (15), its hydrolysate, and its hydrolysis condensate. SiR １０１ ｋ R １０２ ｍ (OR １０３ ) ｎ (OH) ４－ｋ－ｍ－ｎ (15)

[0154] In formula (15), R １０１ R represents an epoxy group-containing group, an amino group-containing group, a mercapto group-containing group, or a polymerizable double bond-containing group. １０２ and R １０３ Each of these independently represents an alkyl group, where k is an integer from 1 to 3, m is an integer from 0 to 2, and n is an integer from 1 to 3. When k is 2 or greater, multiple R １０１They may be the same or different from each other, and when m is 2, there are multiple R １０２ The elements may be the same or different from each other, and when n is 2 or greater, there are multiple ORs. １０３ They may be the same or different from each other. １０１ and R １０２ and OR １０３ OH and OH are groups that bond directly to Si.

[0155] R １０１ The epoxy group-containing group is not particularly limited as long as it contains an epoxy group, and examples include glycidoxy group-containing groups and cycloalkene oxide (alicyclic epoxy group)-containing groups. The glycidoxy group and cycloalkene oxide may be bonded to the silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). １０１ It is preferable that it contains only one epoxy group. １０１ Examples of epoxy group-containing groups include glycidoxy group, 3-glycidoxypropyl group, 8-(glycidoxy)-n-octyl group, 3,4-epoxycyclohexyl group, and 2-(3,4-epoxycyclohexyl)ethyl group. １０１ If the group is an epoxy group-containing group, the specific silane compound (E) also functions as epoxy compound (B) and can be considered as epoxy compound (B).

[0156] R １０１ The amino group-containing group is not particularly limited as long as it has an amino group, it may have a primary amino group, a secondary amino group, a tertiary amino group, or it may have multiple amino groups (for example, a primary amino group and a secondary amino group). The amino group is preferably bonded to the silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). １０１Examples of amino group-containing groups include 3-aminopropyl group, 3-(2-aminoethyl)aminopropyl group, 3-(6-aminohexyl)aminopropyl group, 3-(N,N-dimethylamino)propyl group, N-phenylaminomethyl group, N-phenyl-3-aminopropyl group, N-benzyl-3-aminopropyl group, and N-cyclohexylaminomethyl group.

[0157] R １０１ The mercapto group-containing group is not particularly limited as long as it has a mercapto group, but a mercaptoalkyl group is preferred. The alkyl group in the mercaptoalkyl group may be linear or branched, and its carbon number is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 6. １０１ It is preferable that it contains only one mercapto group. １０１ Examples of mercapto group-containing groups include 3-mercaptopropyl group, 2-mercaptoethyl group, 2-mercaptopropyl group, and 6-mercaptohexyl group.

[0158] R １０１ The polymerizable double bond-containing group is not particularly limited as long as it has a polymerizable double bond group, and examples of polymerizable double bond groups include vinyl groups, styryl groups, (meth)acrylic groups, etc. The polymerizable double bond group may be directly bonded to the silicon atom, or it may be bonded to the silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). １０１ Examples of polymerizable double bond-containing groups include vinyl groups, 2-propenyl groups, styryl groups, and 3-(meth)acryloxypropyl groups.

[0159] Furthermore, from the viewpoint of improving the adhesion of the resin layer to the substrate, R １０１ It is preferable that the epoxy group, amino group, mercapto group, or polymerizable double bond group contained in the material is not too far from the silicon atom, and that these groups are either directly bonded to the silicon atom or bonded to the silicon atom via an alkylene group having 1 to 6 carbon atoms.

[0160] R １０２ and R １０３The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms. １０２ Preferred examples include methyl groups, ethyl groups, n-propyl groups, and isopropyl groups. １０３ Preferred examples include methoxy groups, ethoxy groups, n-propoxy groups, and isopropoxy groups.

[0161] In formula (15), k is preferably 1 or 2, more preferably 1, which makes it easier to improve the adhesion of the resin layer to the substrate. Also, m is preferably 0 or 1, more preferably 0, and n is preferably 2 or 3.

[0162] When a silane coupling agent contains multiple alkoxysilyl groups, a polymer-type polyfunctional silane coupling agent can be used. A polymer-type polyfunctional silane coupling agent has a structure in which a group and an alkoxysilyl group-containing group are bonded to an organic polymer chain, and can contain multiple alkoxysilyl groups in one molecule, as well as multiple functional groups such as epoxy groups, amino groups, mercapto groups, and polymerizable double bond groups. Note that the organic chain of the polymer-type polyfunctional silane coupling agent does not contain polysiloxane. With this configuration, a polymer-type polyfunctional silane coupling agent can form many reaction sites with the resin and substrate, thereby improving the adhesion of the resin layer to the substrate.

[0163] Among the specified silane compounds (E), the hydrolysate of the silane coupling agent can be obtained by converting the alkoxysilyl groups contained in the silane coupling agent to silanol groups by hydrolysis. Furthermore, the hydrolyzed condensate of the silane coupling agent can be obtained by dehydrating and condensing the silanol groups contained in the hydrolyzate of the silane coupling agent to form a siloxane bond (-Si-O-Si-). Normally, when a silane coupling agent is hydrolyzed, the hydrolyzate of the silane coupling agent is obtained, and a dehydration condensation reaction of the silanol groups contained in the hydrolyzate also occurs, so the hydrolyzed condensate of the silane coupling agent can also be easily obtained. The hydrolyzed condensate of the silane coupling agent may be a dehydration condensate of the hydrolyzate of the same type of silane coupling agent, or it may be a dehydration condensate of the hydrolyzate of a different type of silane coupling agent.

[0164] As the specific silane compound (E), it is preferable to use at least one selected from the group consisting of epoxy group-containing silane coupling agents, their hydrolysates, and their hydrolyzed condensates. Therefore, R in the above formula (15) １０１ It is preferable that the group contains epoxy groups. This makes it easier to improve the adhesion between the resin layer and the substrate.

[0165] The resin composition may contain only one specific silane compound (E), or it may contain two or more. Preferably, the resin composition contains at least a hydrolyzate and / or hydrolyzed condensate of a silane coupling agent as the specific silane compound (E), which can improve the adhesion of the resin layer to the substrate. More preferably, the specific silane compound (E) contains at least a hydrolyzate or hydrolyzed condensate of an epoxy group-containing silane coupling agent.

[0166] The specific silane compound (E) more preferably contains a hydrolysis condensate of the silane coupling agent. In this case, the dehydration condensate preferably contains at least a dimer or trimer of an alkoxysilane (for example, an alkoxysilane represented by formula (15) above). For example, when the weight-average molecular weight of the specific silane compound (E) is measured, it is preferably less than or equal to the molecular weight of a pentamer (assuming all alkoxy groups are hydroxyl groups), and more preferably less than or equal to the molecular weight of a tetramer. As for the specific value of the weight-average molecular weight, for example, it is preferably 300 or more, preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.

[0167] The content of the specific silane compound (E) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the solid content of the resin composition. The content of the specific silane compound (E) per 100 parts by mass of resin (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[0168] The resin composition may contain a compound (F) containing an M-O-C bond (where M represents Ti, Zr, or Al). This improves the adhesion of the resin layer to the substrate when the resin composition is coated onto the substrate to form a resin layer. A laminated resin substrate formed from such a resin composition can be suitably applied to optical filters. In particular, when a resin layer is formed on a substrate made of phosphoric acid-based or fluoric acid-based glass, which is usually difficult to achieve good adhesion to, the adhesion between the resin layer and the substrate can be improved. Furthermore, even when ordinary glass such as borosilicate glass or soda glass is used as the substrate, the adhesion between the resin layer and the substrate can be improved.

[0169] The compound (F) containing the M-O-C bond is not particularly limited as long as it is a compound having a structure in which a metal atom M, selected from Ti, Zr, and Al, is connected to a carbon atom via an oxygen atom in one molecule. The compound (F) containing the M-O-C bond is more reactive than silane coupling agents and their condensates, and is thought to act on P=O bonds and P-O-P bonds present on the surface of phosphate-based or fluorine-based glass, forming, for example, P-O-M bonds. Therefore, by including the compound (F) containing the M-O-C bond in the resin composition, the adhesion between the resin layer formed from the resin composition and the phosphate-based or fluorine-based glass can be improved. The resin composition may contain only one type of compound (F) containing the M-O-C bond, or it may contain two or more types. For example, the resin composition may contain two or more types selected from compounds containing Ti-O-C bonds, compounds containing Zr-O-C bonds, and compounds containing Al-O-C bonds.

[0170] Compound (F) containing an M-O-C bond may have a Ti atom, Zr atom, or Al atom that is covalently bonded to the oxygen atom, or it may be connected by a coordinate bond. Therefore, the bond between M and O may be covalent or it may be a coordinate bond. Examples of compounds (F) containing an M-O-C bond where the bond between M and O is covalent include compounds in which an alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc., is bonded to a Ti atom, Zr atom, or Al atom. Examples of compounds (F) containing an M-O-C bond where the bond between M and O is a coordinate bond include compounds in which an enolate or oxalate, etc., is bonded (coordinated) to a Ti atom, Zr atom, or Al atom. Compound (F) containing an M-O-C bond may have multiple M-O bonds, some of which are covalent and others which are coordinate bonds.

[0171] In a compound (F) containing an M-O-C bond, when an alkoxy group is bonded to a Ti atom, Zr atom, or Al atom, the number of carbon atoms in the alkyl group contained in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, even more preferably 1 to 8, and even more preferably 3 to 8. The alkyl group is preferably linear or branched. Examples of alkyl groups contained in the alkoxy group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icosyl group.

[0172] In a compound (F) containing an M-O-C bond, when an aryloxy group is bonded to a Ti atom, Zr atom, or Al atom, the number of carbon atoms in the aryl group is preferably 6 to 20, and more preferably 6 to 12. Examples of aryl groups included in the aryloxy group are phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, indenyl group, and the like.

[0173] In a compound (F) containing an M-O-C bond, when an aralkyloxy group is bonded to a Ti atom, Zr atom, or Al atom, the number of carbon atoms in the aralkyl group is preferably 7 to 25, and more preferably 7 to 15. Examples of aralkyl groups included in the aralkyloxy group include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, naphthylmethyl group, and the like.

[0174] In a compound (F) containing an M-O-C bond, when an acyloxy group is bonded to a Ti atom, Zr atom, or Al atom, the acyloxy group is defined by the formula: -O-C(=O)-R ｃ１ It is represented as R ｃ１ Examples include those in which the group is an alkyl group, an aryl group, or an aralkyl group. ｃ１For alkyl groups, aryl groups, and aralkyl groups, refer to the explanations of alkyl groups included in alkoxy groups, aryl groups included in aryloxy groups, and aralkyl groups included in aralkyloxy groups mentioned above. ｃ１ The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, even more preferably 1 to 8, and even more preferably 1 to 4.

[0175] In a compound (F) containing an M-O-C bond, when an enolate is bonded (coordinated) to a Ti atom, Zr atom, or Al atom, the enolate is represented by the following formula (16), and R １１１ and R １１２ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and R １１３ is a hydrogen atom, alkyl group, aryl group, aralkyl group, or -C(=O)-R １１４ And R １１４ Examples include those in which the group consists of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.

[0176]

[0177] In the above formula (16), R １１１ ~R １１４ For the alkoxy group, refer to the explanation of alkoxy groups above. １１１ ~R １１４ For alkyl groups, aryl groups, and aralkyl groups, refer to the explanations of alkyl groups included in alkoxy groups, aryl groups included in aryloxy groups, and aralkyl groups included in aralkyloxy groups mentioned above. １１１ ~R １１４ The number of carbon atoms in the alkyl and alkoxy groups is preferably 1 to 20, more preferably 1 to 12, even more preferably 1 to 8, and even more preferably 1 to 4. １１１ The group is preferably an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and more preferably an alkyl group or an aryl group. １１２ A hydrogen atom or an alkyl group is preferred, and a hydrogen atom is more preferred. １１３ is an alkyl group, aryl group, aralkyl group or -C(=O)-R １１４Preferably, an alkyl group or -C(=O)-R １１４ This is more preferable. １１３ Ha -C(=O)-R １１４ It is particularly preferable that this be the case, in which case the enolate of formula (16) above is represented by the following formula (16A). １１４ The group is preferably an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, with an alkyl group or an aryl group being more preferred.

[0178]

[0179] A compound (F) containing an M-O-C bond may have only one metal atom M of Ti, Zr, or Al in a single molecule, or it may have two or more. In the latter case, it is preferable that two or more metal atoms M are bonded via an oxygen atom to form an M-O-M bond. It is also preferable that each metal atom M forms an M-O-C bond. Such a compound can be obtained, for example, by hydrolysis and dehydration condensation of a metal alkoxide, and the compound can be considered a condensate of a metal alkoxide. A compound (F) containing an M-O-C bond may have two or three types of metal atoms M.

[0180] Compound (F) containing an M-O-C bond may contain one or more M-O-C bonds in one molecule, more preferably two or more M-O-C bonds, and even more preferably three or more M-O-C bonds. When a molecule contains two or more M-O-C bonds, the groups forming the M-O-C bonds may be the same or different from each other. Compound (F) containing an M-O-C bond may have organic groups that do not form an M-O-C bond bonded to the Ti atom, Zr atom, or Al atom, such as alkyl groups, aryl groups, aralkyl groups, etc. It is particularly preferable that all of the groups bonded to the Ti atom, Zr atom, or Al atom in Compound (F) containing an M-O-C bond form an M-O-C bond.

[0181] Compounds having an M-O-C bond are preferably metal alkoxides or metal enolates. Therefore, compounds having an M-O-C bond are preferably those in which an alkoxy group and / or an enolate is bonded to a Ti atom, a Zr atom, or an Al atom. Examples of such compounds include tetraisopropoxytitanium, tetra-n-butythoxytitanium, tetratert-butythoxytitanium, titanium tetra-2-ethylhexyl oxide, tetrastearyltitanium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetratert-butoxyzirconium, octoxytridecoxyzirconium, triisopropoxyaluminum, tritert-butythoxyaluminum, titanium tetraacetylacetonate, titanium diisopropoxide bis(acetylacetonate), titanium phosphate ester complexes, and titanium octylene glycolate.

[0182] Compound (F) containing an M-O-C bond preferably has a ratio of 10% or more, more preferably 30% or more, and even more preferably 50% or more, of the total number of bonds between the Ti, Zr, or Al atoms. The ratio of alkoxy groups and enolates bonded to the Ti, Zr, or Al atoms is 10% or more, more preferably 30% or more, and still more preferably 50% or more. The ratio is even more preferably higher, and may be 60% or more, 70% or more, 80% or more, or 90% or more.

[0183] In metal alkoxides or metal enolates, it is preferable that all groups bonded to the Ti atom, Zr atom, or Al atom are alkoxy groups or enolates. For example, if there is a compound having a Ti-O-C bond, titanium tetraalkoxide, titanium tetraenolate, titanium alkoxydo trisenolate, titanium dialkoxide bisenolate, and titanium trialkoxide enolate are preferred; if there is a compound having a Zr-O-C bond, zirconium tetraalkoxide, zirconium tetraenolate, zirconium alkoxydo trisenolate, zirconium dialkoxide bisenolate, and zirconium trialkoxide enolate are preferred; and if there is a compound having an Al-O-C bond, aluminum trialkoxide, aluminum trisenolate, aluminum alkoxydo bisenolate, and aluminum dialkoxide enolate are preferred.

[0184] In metal alkoxide condensates, it is preferable that, excluding the M-O-M (where M represents Ti, Zr, or Al) bond, all groups bonded to the Ti, Zr, or Al atoms are alkoxy groups or enolates.

[0185] Compound (F) containing an M-O-C bond may react with resin (A) to form a bond. Since resin (A) has ester bonds, when compound (F) containing an M-O-C bond reacts with the ester bonds of resin (A), these ester bonds are cleaved by the reaction with compound (F), and compound (F) containing an M-O-C bond may bond with the cleaved portion of resin (A) via an -O-M bond (where M represents Ti, Zr, or Al). Such a reaction can be carried out, for example, by heating the resin composition.

[0186] The content of compound (F) containing an M-O-C bond in the resin composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less, based on 100% by mass of the solid content of the resin composition. The content of compound (F) containing an M-O-C bond per 100 parts by mass of resin (A) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0187] In the resin composition, the content of metal atoms M in the compound (F) containing an M-O-C bond is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.5% by mass or less, based on 100% by mass of the solid content.

[0188] It is preferable that the resin composition does not contain a large amount of water. This suppresses the hydrolysis of ester bonds contained in resin (A). The water content in the resin composition is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, based on 100% by mass of the resin composition. Furthermore, it is preferable that the water content in 100% by mass of the solid content of the resin composition be 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. It is particularly preferable that the resin composition does not contain water. The water content in the resin composition can be analyzed by the Karl Fischer method (volumetric titration).

[0189] The resin composition may contain an alcohol compound, which can improve the storage stability of the resin composition. The alcohol compound is not particularly limited as long as it has at least one alcoholic hydroxyl group, but it is preferably a polyhydric alcohol compound having two or more alcoholic hydroxyl groups. The upper limit of the number of alcoholic hydroxyl groups in the alcohol compound is not particularly limited and may be 10 or less, 8 or less, 6 or less, or 4 or less.

[0190] The alcohol compound is preferably a compound in which an alcoholic hydroxyl group is bonded to an aliphatic hydrocarbon chain. The alcohol compound preferably has 4 or more carbon atoms, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0191] When the resin composition contains an alcohol compound, the content of the alcohol compound in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, based on 100% by mass of the solid content of the resin composition. The content of the alcohol compound per 100 parts by mass of resin (A) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.

[0192] The resin composition may contain a surface modifier, which helps to suppress the occurrence of cosmetic defects such as striations and indentations in the resin layer when the resin composition is coated onto a substrate to form a resin layer. The type of surface modifier is not particularly limited, and siloxane-based surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, acrylic leveling agents, etc., can be used. Examples of surface modifiers include the BYK® series manufactured by BIC Chemie and the KF series manufactured by Shin-Etsu Chemical Co., Ltd.

[0193] The resin composition may contain a dispersant, which stabilizes the dispersibility of the resin composition and suppresses re-aggregation. The type of dispersant is not particularly limited, and can be used such as the EFKA series from FKA Additives, Inc., the BYK® series from BIC Chemie Inc., the Solspers® series from Lubrizol Nippon Co., Ltd., the Disparon® series from Kusumoto Chemical Co., Ltd., the Azisper® series from Ajinomoto Fine Techno Co., Ltd., the KP series from Shin-Etsu Chemical Co., Ltd., the Polyflow series from Kyoeisha Chemical Co., Ltd., the Megafac® series from DIC Corporation, and the DisperAid series from Sunopco Corporation.

[0194] The resin composition may optionally contain various additives such as plasticizers, surfactants, viscosity modifiers, defoamers, preservatives, resistivity modifiers, stability enhancers such as polyvalent mercaptans, and adhesion enhancers.

[0195] The resin composition according to this disclosure can be suitably used as a coated resin composition, and a thin resin film can be easily formed from the resin composition according to this disclosure. The coated resin composition can be coated by methods such as spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, slit coating, screen printing, flexographic printing, and inkjet printing. When the resin composition is coated onto a substrate to form a resin film, a resin layer can be formed on the substrate. In this case, by coating a liquid or paste-like resin composition onto a substrate (e.g., a resin plate, film, glass plate, etc.) and drying or curing it, a cured product in the form of a film with a thickness of 200 μm or less, or a sheet with a thickness of more than 200 μm, can be obtained, which becomes a resin layer formed on the substrate. The resin layer formed in this way can be handled integrally with the substrate.

[0196] A resin laminate substrate, in which a resin layer is formed on a substrate, can be applied to filters used in a variety of applications, such as optodevices, display devices, mechanical parts, and electrical and electronic components. The resin composition of this disclosure can be preferably used as a resin composition for filter formation. The resin composition and resin laminate substrate according to this disclosure can be used, for example, in optical filter applications such as near-infrared cut filters and light selective transmission filters.

[0197] The optical filter may have a resin layer provided on only one side of the substrate, or on both sides. The optical filter may be formed from a single or multiple resin layers, or it may be formed integrally with the substrate.

[0198] An optical filter integrated with a substrate can be formed, for example, by applying a resin composition to the substrate surface (or, if there is another layer such as a binder layer between the substrate and the resin layer, to the surface of that other layer) by a spin coating method or a solvent casting method, and then drying or curing it. Alternatively, an optical filter may be formed by thermocompressing a planar molded body made from the resin composition onto the substrate.

[0199] The thickness of the resin layer is not particularly limited, but for example, it is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, and also preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less. When the resin layer is formed by coating a resin composition in paint form onto a substrate, the strength of the filter can be ensured by the substrate, so the thickness of the resin layer can be made even thinner. When the resin layer is formed on a substrate, for example, the thickness of the resin layer is preferably 50 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0200] As the substrate, it is preferable to use a transparent substrate such as a resin plate, resin film, or glass plate. Among these, it is preferable to use a glass substrate. By providing a resin layer on a glass substrate, an optical filter with excellent heat resistance can be obtained. The optical filter obtained in this way can be mounted on an electronic component, for example, by solder reflow, thereby enabling miniaturization of the electronic component. In addition, since glass substrates are less prone to cracking or warping even when exposed to high temperatures, it is easier to ensure adhesion with the resin layer.

[0201] The glass used for the glass substrate can be any known glass such as silicate glass, borosilicate glass, soda glass, borate glass, phosphate glass, or fluorine-based glass. In these glasses, silicon atoms, boron atoms, or phosphorus atoms form a network structure with oxygen atoms to form the main framework of the glass. In addition to these atoms, atoms or ions such as sodium, potassium, calcium, magnesium, barium, aluminum, iron, silver, copper, cobalt, nickel, lead, zinc, and fluorine may also be present in the glass. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application.

[0202] The thickness of the substrate is preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of ensuring strength, and preferably 0.4 mm or less, more preferably 0.3 mm or less, from the viewpoint of thinning.

[0203] The optical filter may have a protective layer as a second resin layer, which is made of the same or a different resin as the above-mentioned resin layer. By providing a protective layer, the durability (resistance to decomposition) of each component contained in the resin layer can be increased. Preferably, the protective layer is provided on the side of the resin layer opposite to the substrate.

[0204] The optical filter may have a layer (anti-reflective coating) that has anti-reflective and anti-glare properties to reduce reflections from fluorescent lights, etc., a layer that has scratch-resistant properties, or a transparent substrate with other functions. The optical filter may also have an ultraviolet reflective coating or a near-infrared reflective coating on the resin layer. It is preferable that the ultraviolet reflective coating or the near-infrared reflective coating is provided on the light-receiving side of the resin layer. If the optical filter is provided with an ultraviolet reflective coating or a near-infrared reflective coating, ultraviolet and near-infrared rays can be cut more effectively from the light transmitted through the optical filter. The ultraviolet reflective coating and the near-infrared reflective coating may be a single coating that has both ultraviolet reflection and near-infrared reflection functions.

[0205] Ultraviolet reflective films, near-infrared reflective films, and anti-reflective films (visible light anti-reflective films) can be composed of dielectric films. Dielectric films are usually composed of dielectric multilayer films in which high refractive index material layers and low refractive index material layers are alternately stacked, but they may also be composed of only one of the high refractive index material layers or the low refractive index material layers. As the material constituting the high refractive index material layer, a material with a refractive index of 1.7 or higher can be used, and it is preferable that a material with a refractive index in the range of 1.7 to 2.5 is selected, more preferably 1.8 or higher, and even more preferably 2.0 or higher. Examples of materials constituting the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; nitrides such as silicon nitride; mixtures of the oxides and nitrides, or those doped with metals such as aluminum and copper or carbon (for example, tin-doped indium oxide (ITO), antimond-doped tin oxide (ATO)). As the material constituting the low refractive index material layer, a material with a refractive index of less than 1.7 can be used, and it is preferable that a material with a refractive index in the range of 1.2 to 1.6 be selected, and more preferably that a material with a refractive index in the range of 1.3 to 1.5 be selected. Examples of materials constituting the low refractive index material layer include silicon dioxide (silica, SiOx (x=1 to 2)), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride. Among these, it is preferable that the high refractive index material layer be composed of titanium dioxide, and that the low refractive index material layer be composed of silicon dioxide.

[0206] The thicknesses of the high refractive index material layer and the low refractive index material layer are preferably adjusted to a range of 0.1λ to 0.5λ, and more preferably to a range of 0.2λ to 0.3λ, of the wavelength λ (nm) of the light to be blocked. By forming a dielectric film in this manner, light in a desired wavelength range can be selectively reflected, and the dielectric film can be used to form a near-infrared reflective film, an ultraviolet reflective film, an anti-reflective film (visible light anti-reflective film), etc. The ultraviolet reflective film and the near-infrared reflective film may be a single film that has both ultraviolet and near-infrared reflective functions.

[0207] The number of dielectric film layers is not particularly limited as long as it is one or more layers, but from the viewpoint of exhibiting desired optical performance as a near-infrared reflective film, ultraviolet reflective film, anti-reflective film, etc., it is preferable to have, for example, 2 to 80 layers. The number of dielectric film layers may be 5 or more layers, 10 or more layers, or 20 or more layers, and may also be 70 or less layers, or 60 or less layers. The thickness of the dielectric film is not particularly limited, and may be in the range of 0.01 μm to 10 μm, but from the viewpoint of sufficiently cutting the incidence of light in the desired wavelength range, it is preferable to have 0.02 μm or more, more preferably 0.03 μm or more, and from the viewpoint of thinning, it is preferable to have 5 μm or less, and more preferably 3 μm or less.

[0208] The optical filter may have an aluminum vapor-deposited film, a noble metal thin film, or a resin film in which metal oxide fine particles mainly composed of indium oxide and containing a small amount of tin oxide are dispersed.

[0209] The thickness of the optical filter is preferably, for example, 1 mm or less. This allows for sufficient meeting of the demand for miniaturization of the image sensor, for example. More preferably, the thickness of the optical filter is 500 μm or less, even more preferably 300 μm or less, even more preferably 150 μm or less, and also preferably 30 μm or more, and more preferably 50 μm or more.

[0210] The optical filters relating to this disclosure are particularly suitable for image sensor applications. The disclosure also includes image sensors having optical filters. An image sensor, also called a solid-state image sensor or image sensor chip, is an electronic component that converts light from a subject into an electrical signal and outputs it as an electrical signal. An image sensor typically has a detection element (sensor) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor), and may also have a lens. Image sensors are used, for example, in mobile phone cameras, digital cameras, in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.), etc. An image sensor includes one or more of the optical filters relating to this disclosure, and may further have other components as needed.

[0211] This application claims the benefit of priority based on Japanese Patent Application No. 2024-161368 filed on September 18, 2024. The entire contents of the specification of Japanese Patent Application No. 2024-161368 filed on September 18, 2024 are incorporated herein by reference.

[0212] Hereinafter, the content of the present disclosure will be described more specifically with reference to examples. However, the content of the present disclosure is not limited by the following examples, and it is also possible to appropriately modify and implement within the range that conforms to the gist of the foregoing and following, and all of them are included in the technical scope of the present disclosure.

[0213] (1) Synthesis of Compounds (1-1) Synthesis Example 1: Synthesis of Dye A According to the method described in Examples 1-18 of JP-A-2016-74649, Dye A shown in Table 1, which is a near-infrared absorbing dye, was synthesized. When the transmission spectrum of the near-infrared absorbing dye A in toluene was measured, the absorption maximum wavelength was 737 nm.

[0214] (1-2) Synthesis Example 2: Synthesis of Dye B According to Synthesis Example 2 described in the examples of JP-A-2020-132699, Dye B shown in Table 1, which is a near-infrared absorbing dye, was synthesized.

[0215] (1-3) Synthesis Example 3: Synthesis of Dye C According to the method described in Example 1-23 of JP-A-2016-74649, Dye C shown in Table 1, which is a near-infrared absorbing dye, was synthesized.

[0216] (1-4) Synthesis Example 4: Synthesis of Dye D According to the method described in Example 1-19 of JP-A-2016-74649, Dye D shown in Table 1, which is a near-infrared absorbing dye, was synthesized.

[0217] [[ID= (1-5) Synthesis Example 5: Synthesis of Dye E 3.00 g (5.89 mmol) of 2-hexadecyloctadecanoic acid and 28.1 g (0.236 mmol) of thionyl chloride were added to a 100 mL four-necked flask, and the mixture was stirred at 40 °C for 1 hour using a magnetic stirrer under a nitrogen flow (20 mL / min). Then, the excess thionyl chloride was distilled off under reduced pressure to obtain 3.11 g of 2-hexadecyloctadecanoyl chloride. The yield with respect to 2-hexadecyloctadecanoic acid was 100 mol%.

[0218] Next, 0.20 g (0.95 mmol) of 7-amino-1-(2-methylpropyl)-1,2,3,4-tetrahydroquinoline (intermediate 1), synthesized according to the method described in Example 1-3 of Japanese Patent Application Publication No. 2016-74649, and 2.5 g of super-dehydrated tetrahydrofuran were placed in a 50 mL three-necked flask. Under a nitrogen flow (5 mL / min), 0.14 g (1.43 mmol) of triethylamine and 0.55 g (1.05 mmol) of 2-hexadecyloctadecanoyl chloride were added while stirring with a magnetic stirrer, and the mixture was reacted at room temperature for 12 hours. After the reaction was complete, the resulting reaction solution was added to deionized water and extracted with chloroform. The extracted organic phase was dehydrated with anhydrous magnesium sulfate. After filtering off the solid matter (inorganic components) from this organic phase, the solvent was concentrated using an evaporator. Then, intermediate 2 was obtained by using silica gel column chromatography (eluent: chloroform) as appropriate, followed by concentration and vacuum drying. The yield relative to intermediate 1 was 87.5 mol%.

[0219] Next, 0.58 g (0.834 mmol) of intermediate 2, 0.05 g (0.417 mmol) of squalate, 2.9 g of 1-butanol, and 2.9 g of toluene were placed in a 50 mL two-necked flask. The mixture was stirred with a magnetic stirrer under a nitrogen flow (10 mL / min), and the reaction was carried out under reflux conditions for 3 hours, while removing eluted water using a Dean-Stark apparatus. After the reaction was complete, the mixture was cooled to room temperature, and the precipitate was filtered off. The filtered precipitate was washed with methanol, and the precipitate alone was filtered again to obtain the resulting cake (solid). The resulting cake was purified as appropriate by silica or alumina column chromatography (eluent: chloroform). The purified product was dried in a vacuum dryer at 60°C for 12 hours to obtain 0.32 g of dye E, a near-infrared absorption dye shown in Table 1. The yield relative to squalate was 52.8 mol%.

[0220]

[0221] (1-6) Synthesis Example 6: Synthesis of Cyanine Compound 1 Following the method described in paragraph

[0010] of International Publication No. 2012 / 026316, N-((1E)-2-chloro-3-((E)-(phenylimino)methyl)cyclohexa-2-ene-1-ylidene)methyl)aniline hydrochloride (dianiline salt 1) shown in Table 2 was synthesized.

[0222] In a 500 mL four-necked flask placed in a water bath, 21.9 g (0.195 mol) of potassium tert-butoxide, 98.1 g of super-dehydrated tetrahydrofuran, 10.8 g (0.065 mol) of fluorene, and 11.5 g (0.13 mol) of ethyl acetate were sequentially added under nitrogen flow (10 mL / min), while taking care to avoid exothermic reaction. The mixture was then stirred under reflux conditions for 3 hours while heating in a water bath. After cooling the resulting reaction solution, it was quenched with dilute hydrochloric acid, extracted with ethyl acetate, and washed three times with brine. The resulting organic phase was dehydrated with magnesium sulfate and concentrated using an evaporator. The resulting solid was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain 12.5 g of 9-acetyl-9H-fluorene (acetyl compound 1). The yield relative to fluorene was 92.4 mol%.

[0223] In a 500 mL separable flask, 6.2 g (0.026 mol) of acetyl compound 1, 3.8 g (0.026 mol) of phenylhydrazine hydrochloride, and 112.1 g of tert-amyl alcohol as solvent were charged. The mixture was reacted at 90°C for 4 hours with stirring under a nitrogen flow (10 mL / min). After the reaction was complete, the reaction mixture was cooled to room temperature, quenched with 100 g of water, and extracted with 100 g of ethyl acetate. The resulting organic phase was dehydrated with magnesium sulfate, concentrated using an evaporator, and the resulting solid was purified by silica gel column chromatography (eluent: chloroform) to obtain 4.4 g of indorenine compound 1. The yield was 51.3 mol%.

[0224] Next, 2.2 g (0.007 mol) of the indorenine compound 1 obtained above, 11.2 g (0.079 mol) of iodomethane, and 53.3 g of N,N-dimethylformamide were charged into a 100 mL four-necked flask, and the mixture was stirred at 80°C for 16 hours under a nitrogen flow (5 mL / min). After cooling to room temperature, the reaction mixture was precipitated in 300 g of toluene, and the precipitated solid was filtered off to obtain 1.8 g of indorenium salt 1. The yield was 56.5 mol%.

[0225] In a 100 mL four-necked flask, 1.0 g (0.0021 mol) of the indorhenium salt 1 obtained above, 0.42 g (0.0011 mol) of the dianiline salt 1, 0.28 g (0.003 mol) of sodium acetate, 9.9 g of acetic acid, and 10.1 g of acetic anhydride were added, and the mixture was stirred at 100°C for 8 hours. The reaction mixture was cooled to room temperature, 150 g of water was added to the reaction mixture, and the precipitated solid was filtered off. This solid was purified by silica gel column chromatography (eluent: chloroform), and recrystallized to obtain 0.21 g of cyanine compound 1 shown in Table 2. The yield was 40.7 mol%.

[0226]

[0227] (1-7) Synthesis Example 7: Synthesizing dye F. 0.50 g (0.50 mmol) of cyanine compound 1 was dissolved in 40 mL of acetone, and 6.7 g (0.10 mmol) of a 10.5% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (manufactured by Nippon Shokubai Co., Ltd.) was added. The mixture was stirred at 50°C for 3 hours. The solvent was then removed by distillation, and the resulting solid was washed with deionized water to obtain 0.57 g of dye F, a near-infrared absorption dye shown in Table 1. The yield was 89.9 mol%. The pKa of the tetrakis(pentafluorophenyl)borate anion of dye F was -8.0 or less.

[0228] (1-8) Synthesis Example 8: Synthesis of Dye G Dye G, a near-infrared absorbing dye shown in Table 1, was obtained by the same procedure as in Synthesis Example 6 and 7, except that 4-t-butylphenylhydrazine hydrochloride was used instead of phenylhydrazine hydrochloride, iodobutane was used instead of iodomethane, and malonaldehyde dianilide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dianiline salt 1. The yield was 65.8 mol%.

[0229] (1-9) Synthesis Example 9: Synthesis of dye H. Except that 4-t-butylphenylhydrazine hydrochloride was used instead of phenylhydrazine hydrochloride in Synthesis Example 6, iodobutane was used instead of iodomethane, and dianiline salt 2 shown in Table 2 was used instead of dianiline salt 1, the same procedure as in Synthesis Examples 6 and 7 was used to obtain cyanine compound 2 shown in Table 2. The yield was 46.0 mol%. Using cyanine compound 2, dye H, a near-infrared absorbing dye shown in Table 1, was obtained by the same procedure as described in paragraph

[0220] of International Publication No. 2014 / 057032. The yield was 93.0 mol%.

[0230] (1-10) Synthesis Example 10: Synthesis of Dye I Dye I, a near-infrared absorbing dye shown in Table 1, was obtained by the same procedure as in Synthesis Example 6 and 7, except that 4-t-butylphenylhydrazine hydrochloride was used instead of phenylhydrazine hydrochloride, iodobutane was used instead of iodomethane, and glutaconaldehyde dianyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dianiline salt 1. The yield was 60.2 mol%.

[0231] (1-11) Synthesis Example 11: Synthesis of dye J Dye J, which is a near-infrared absorbing dye, was obtained by the same procedure as in Synthesis Example 7, except that 1,1'-diethyl-4,4'-carbocyanine iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of cyanine compound 1. The yield was 72.2 mol%.

[0232] (1-12) Synthesis Example 12: Synthesis of dye K The dye K shown in Table 1 was obtained by the same procedure as in Synthesis Example 7, except that 1-butyl-2-(2-[3-(2-[1-butyl-1H-benzo[cd]indole-2-ylidene]ethylidene)-2-phenyl-1-cyclopenta-1-enyl]-vinyl)-benzo[cd]indolium tetrafluoroborate (manufactured by Few Chemicals, S0813) was used instead of cyanine compound 1. The yield was 90.1 mol%.

[0233] (1-13) Synthesis Example 13: Synthesis of Dye L Following Synthesis Example 12 described in the Examples of Japanese Patent Publication No. 2018-14707, dye L, which is an ultraviolet absorbing dye, was synthesized as shown in Table 1.

[0234]

[0235]

[0236] (2) Preparation of resin composition (2-1) Preparation example 1: Preparation of resin composition 1 In a 2 L reaction vessel equipped with a stirring blade, 10.0 g (0.044 mol) of 2,2'-bis(4-hydroxyphenyl)propane, 3.6 g (0.090 mol) of sodium hydroxide, and 300 g of deionized water were charged and dissolved. Then, 0.89 g (0.009 mol) of triethylamine was added and dissolved. A solution of 3.6 g (0.021 mol) of terephthalic acid dichloride and 3.6 g (0.021 mol) of isophthalic acid dichloride dissolved in 500 g of methylene chloride was placed in a dropping funnel and attached to the reaction vessel. The solution in the reaction vessel was stirred while maintaining the temperature at 20°C, and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Next, a solution of 0.71 g (0.005 mol) of benzoyl chloride dissolved in 10 g of methylene chloride was added, and the mixture was stirred for 60 minutes. The resulting reaction solution was neutralized with aqueous acetic acid to adjust the pH of the aqueous phase to 7, and then the oil phase and aqueous phase were separated using a separatory funnel. The obtained oil phase was added dropwise to methanol under stirring to reprecipitate the polymer, and the precipitate was recovered by filtration. The mixture was dried in an oven at 80°C to obtain 1.5 g of white solid polyarylate resin. The weight-average molecular weight (Mw) of the obtained polyarylate resin was 33,780, and the number-average molecular weight (Mn) was 8,130. The weight-average molecular weight and number-average molecular weight of the polyarylate resin are polystyrene equivalent values ​​determined by gel permeation chromatography. The glass transition temperature of the polyarylate resin was 193°C.

[0237] Ten parts by mass of the polyarylate resin (PAR resin) obtained above and 0.2 parts by mass of EP compound 1 (4,4'-methylenebis(N,N-diglycidylaniline), manufactured by Sumitomo Chemical Co., Ltd., SumiEpoxy® ELM-434) shown in Table 3 as an epoxy compound were added to 90 parts by mass of toluene and stirred overnight (for 12 hours or more) at 25°C to obtain resin composition 1.

[0238] (2-2) Preparation Example 2: Preparation of Resin Composition 2 Resin composition 2 was obtained in the same manner as in Preparation Example 1, except that 1.0 part by mass of EP compound 1 was added.

[0239] (2-3) Preparation Example 3: Preparation of Resin Composition 3 Resin composition 3 was obtained in the same manner as in Preparation Example 1, except that 1.0 part by mass of EP compound 2 (1,4-butanediol diglycidyl ether, manufactured by Tokyo Chemical Industry Co., Ltd.) shown in Table 3 was added instead of EP compound 1 as the epoxy compound.

[0240] (2-4) Preparation Example 4: Preparation of Resin Composition 4 Resin composition 4 was obtained in the same manner as in Preparation Example 1, except that 1.0 part by mass of EP compound 3 (4-(2,3-epoxypropane-1-yloxy)-N,N-bis(2,3-epoxypropane-1-yl)-2-methylaniline, manufactured by Sumitomo Chemical Co., Ltd., SumiEpoxy® ELM-100) shown in Table 3 was added instead of EP compound 1 as the epoxy compound.

[0241] (2-5) Preparation Example 5: Preparation of Resin Composition 5 Resin composition 5 was obtained in the same manner as in Preparation Example 1, except that 1.0 part by mass of EP compound 4 (3',4'-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl, manufactured by Daicel Corporation, Celoxide 2021P) shown in Table 3 was added instead of EP compound 1 as the epoxy compound.

[0242] (2-6) Preparation Example 6: Preparation of resin composition 6 Resin composition 6 was obtained in the same manner as in Preparation Example 1, except that 1.0 part by mass of EP compound 5 (1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Corporation, EHPE3150) shown in Table 3 was added instead of EP compound 1 as the epoxy compound.

[0243] (2-7) Preparation Example 7: Preparation of Resin Composition 7 To 100 parts by mass of resin composition 2, 0.67 parts by mass of Ti compound 1 (tetrakis(2-ethylhexyl) orthotitanate, manufactured by Tokyo Chemical Industry Co., Ltd.), as shown in Table 3, was added and stirred at room temperature for 12 hours to obtain resin composition 7.

[0244] (2-8) Preparation Example 8: Preparation of Resin Composition 8 In Preparation Example 7, as the compound containing M-O-C bond, 0.42 parts by mass of Ti Compound 2 (tetrakis(2,4-pentanedionato)titanium, manufactured by Tokyo Chemical Industry Co., Ltd.) shown in Table 3 was added instead of Ti Compound 1. A resin composition 8 was obtained in the same manner as in Preparation Example 7, except for this.

[0245] (2-9) Preparation Example 9: Preparation of Resin Composition 9 In Preparation Example 7, as the compound containing M-O-C bond, 0.67 parts by mass of Zr Compound 1 (zirconium acetylacetonate, manufactured by Kanto Chemical Co., Inc.) shown in Table 3 was added instead of Ti Compound 1. A resin composition 9 was obtained in the same manner as in Preparation Example 7, except for this.

[0246] (2-10) Preparation Example 10: Preparation of Resin Composition 10 In Preparation Example 7, as the compound containing M-O-C bond, 0.53 parts by mass of Zr Compound 2 (zirconium tetrabutoxide, manufactured by Tokyo Chemical Industry Co., Ltd.) shown in Table 3 was added instead of Ti Compound 1. A resin composition 10 was obtained in the same manner as in Preparation Example 7, except for this.

[0247] (2-11) Preparation Example 11: Preparation of Resin Composition 11 In Preparation Example 2, 10 parts by mass of Polycarbonate Resin 1 (PC Resin 1, manufactured by Mitsubishi Gas Chemical Company, Inc., Upizer (registered trademark) FPC-0820, glass transition temperature 230°C) was used instead of the polyarylate resin. A resin composition 11 was obtained in the same manner as in Preparation Example 2, except for this.

[0248] (2-12) Preparation Example 12: Preparation of Resin Composition 12 In Preparation Example 2, 10 parts by mass of Polycarbonate Resin 2 (PC Resin 2, manufactured by Mitsubishi Gas Chemical Company, Inc., Upizer (registered trademark) FPC-8225, glass transition temperature 156°C) was used instead of the polyarylate resin. A resin composition 12 was obtained in the same manner as in Preparation Example 2, except for this.

[0249] (2-13) Preparation Example 13: Preparation of Resin Composition 13 In Preparation Example 2, 10 parts by mass of Polycarbonate Resin 3 (PC Resin 3, manufactured by Mitsubishi Gas Chemical Company, Inc., Upizer (registered trademark) RA-2136P, glass transition temperature 126°C) was used instead of the polyarylate resin. A resin composition 13 was obtained in the same manner as in Preparation Example 2, except for this.

[0250] (2-14) Preparation Example 14: Preparation of resin composition 14. 9.9 parts by mass of polyarylate resin was added to a mixed solvent of 34 parts by mass of toluene and 52.3 parts by mass of o-xylene. Then, 0.8 parts by mass of dye A, 0.3 parts by mass of dye B, and 1.1 parts by mass of dye L were added, and the mixture was stirred at 40°C for 1 hour. Next, 0.03 parts by mass of BYK-310 (polyether-modified polydimethylsiloxane) manufactured by Bic Chemie was added as a surface modifier. 1.0 part by mass of EP compound 1 and 1.0 part by mass of silane coupling agent hydrolysate were added to the base resin composition obtained in this way, and the mixture was uniformly mixed at 25°C and stirred overnight (for 12 hours or more) at 25°C. The mixture was filtered through a 0.1 μm pore size filter (GL Sciences, non-aqueous 13N) to remove impurities and obtain resin composition 14. The silane coupling agent hydrolysate was prepared by combining 24.7 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Dow-Toray, OFS-6040), 32.1 parts by mass of 2-propanol, and 3.4 parts by mass of distilled water, mixing them uniformly at 25°C, then adding 1.54 parts by mass of formic acid and mixing for 90 minutes to allow the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane to proceed.

[0251] (2-15) Preparation Example 15: Preparation of Resin Composition 15 A resin solution was obtained by adding 10.8 parts by mass of polyarylate resin, 0.9 parts by mass of dye A, 0.3 parts by mass of dye B, and 1.3 parts by mass of dye L to a mixed solvent of 33.7 parts by mass of toluene and 5.68 parts by mass of o-xylene and mixing. A resin solution was obtained by adding 0.51 parts by mass of Ti compound 1 and 0.077 parts by mass of 2-ethyl-1,3-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an additive to a mixed solvent of 3.73 parts by mass of toluene and 5.68 parts by mass of o-xylene and mixing. After stirring for 1 hour, 1.0 part by mass of EP compound 1 and 90 parts by mass of the resin solution prepared above were added, and the mixture was stirred at room temperature for a further 12 hours to obtain resin composition 15.

[0252] (2-16) Preparation Example 16: Preparation of resin composition 16 Resin composition 16 was obtained in the same manner as in Preparation Example 15, except that 0.51 parts by mass of Zr compound 1 was used instead of Ti compound 1.

[0253] (2-17) Preparation Example 17: Preparation of resin composition 17 Resin composition 17 was obtained in the same manner as in Preparation Example 15, except that 0.51 parts by mass of Zr compound 2 was used instead of Ti compound 1.

[0254] (2-18) Preparation Example 18: Preparation of resin composition 18 To 88.6 parts by mass of toluene, 10.0 parts by mass of polyarylate resin, 1.0 part by mass of EP compound 1, and 0.40 parts by mass of dye C were added and mixed at 40°C for 2 hours to obtain resin composition 18.

[0255] (2-19) Preparation Example 19: Preparation of resin composition 19 Resin composition 19 was obtained in the same manner as in Preparation Example 18, except that 0.40 parts by mass of dye D was used instead of dye C.

[0256] (2-20) Preparation Example 20: Preparation of resin composition 20 Resin composition 20 was obtained in the same manner as in Preparation Example 18, except that 0.20 parts by mass of dye E was used instead of dye C.

[0257] (2-21) Preparation Example 21: Preparation of resin composition 21 Resin composition 21 was obtained in the same manner as in Preparation Example 18, except that 0.20 parts by mass of dye F was used instead of dye C.

[0258] (2-22) Preparation Example 22: Preparation of Resin Composition 22 88.8 parts by mass of 4-methyloxane were mixed with 10.0 parts by mass of polyarylate resin, 1.0 part by mass of EP compound 1, and 0.20 parts by mass of dye G, and the mixture was heated at 40°C for 2 hours to obtain resin composition 23.

[0259] (2-23) Preparation Example 23: Preparation of resin composition 23 Resin composition 24 was obtained in the same manner as in Preparation Example 18, except that 0.20 parts by mass of dye H was used instead of dye C.

[0260] (2-24) Preparation Example 24: Preparation of Resin Composition 24 Resin composition 24 was obtained in the same manner as in Preparation Example 18, except that 0.20 parts by mass of dye I was used instead of dye C.

[0261] (2-25) Preparation Example 25: Preparation of resin composition 25 Resin composition 25 was obtained in the same manner as in Preparation Example 18, except that 0.20 parts by mass of dye J was used instead of dye C.

[0262] (2-26) Preparation Example 26: Preparation of resin composition 26 Resin composition 26 was obtained in the same manner as in Preparation Example 22, except that 0.20 parts by mass of dye L was used instead of dye C.

[0263] (2-27) Preparation Example 27: Preparation of resin composition 27 As a resin having an ester bond in the side chain, 10 parts by mass of a cycloolefin resin (COP resin, manufactured by JSR, Arton® F5023, glass transition temperature 165°C) and 1 part by mass of EP compound 1 were added to 90 parts by mass of toluene and stirred overnight at 25°C to obtain resin composition 27.

[0264] (2-28) Preparation Example 28: Preparation of Resin Composition 28 Resin composition 28 was obtained in the same manner as in Preparation Example 27, except that 1.0 part by mass of EP compound 5 was added instead of EP compound 1 as the epoxy compound.

[0265] (2-29) Preparation Example 29: Preparation of resin composition 29 Resin composition 29 was obtained in the same manner as in Preparation Example 1, except that 5 parts by mass of EP compound 1 were added.

[0266] (2-30) Preparation Example 30: Preparation of resin composition 30 Resin composition 30 was obtained in the same manner as in Preparation Example 1, except that 10 parts by mass of EP compound 1 was added.

[0267] (2-31) Preparation Example 31: Preparation of resin composition 31 90 parts by mass of toluene were added to 10 parts by mass of polyarylate resin and stirred overnight at 25°C to obtain resin composition 31.

[0268] (2-32) Preparation Example 32: Preparation of resin composition 32 90 parts by mass of toluene and 10 parts by mass of polycarbonate resin 1 were added and stirred overnight at 25°C to obtain resin composition 32.

[0269] (2-33) Preparation Example 33: Preparation of resin composition 33 90 parts by mass of toluene was mixed with 10 parts by mass of polycarbonate resin 2 and stirred overnight at 25°C to obtain resin composition 33.

[0270] (2-34) Preparation Example 34: Preparation of resin composition 34 90 parts by mass of toluene 10 parts by mass of polycarbonate resin 3 were added and stirred overnight at 25°C to obtain resin composition 34.

[0271] (2-35) Preparation Example 35: Preparation of resin composition 35 Resin composition 35 was obtained in the same manner as in Preparation Example 14, except that EP compound 1 was not added.

[0272] (2-36) Preparation Example 36: Preparation of resin composition 36 Resin composition 36 was obtained in the same manner as in Preparation Example 17, except that EP compound 1 was not added.

[0273]

[0274] (3) Preparation and evaluation of resin films (3-1) Preparation of resin films Two cc of each of the resin compositions 1 to 36 prepared in Preparation Examples 1 to 36 was dropped onto an aluminum cup No. 2 with a handle (manufactured by AS ONE Corporation), and heated in an inert oven (manufactured by Yamato Scientific Co., Ltd., DN610I) under a nitrogen atmosphere at 150°C for 60 minutes to prepare resin films.

[0275] (3-2) Pressure Cooker Test (PCT Test) Each resin film prepared as described above was subjected to a pressure cooker test using a pressure cooker tester (PC-242HSE, manufactured by Hirayama Seisakusho) to evaluate the high temperature and high humidity resistance of the resin film. The test was conducted by heating and pressurizing the film for 24 hours under the conditions of a temperature of 121°C, a humidity of 100% RH, and a pressure of 0.1 MPa. The weight change of the resin film before and after the test was measured, and the appearance of the resin film after the test was observed and evaluated according to the following criteria. Appearance was evaluated as good if no turbidity, bubbles, or cracks were observed in the resin film, and as poor if any of the following were observed in the resin film. A: Weight increase of less than 10%, good appearance B: Weight increase of 10% or more, or decrease in weight, or poor appearance C: Weight increase of 10% or more, or decrease in weight, poor appearance

[0276]

[0277]

[0278]

[0279] (3-3) Test Results The results of the pressure cooker test are shown in Tables 4 to 6. Resin compositions 1 to 28 all contained a resin with ester bonds, an epoxy compound, and a solvent, and the mass ratio of resin to epoxy compound (resin / epoxy compound) in the resin composition was 5 or more. Therefore, the resin films formed from resin compositions 1 to 28 received an evaluation result of "A" in the pressure cooker test, showing high resistance to high temperature and humidity. The increase in weight of the resin film before and after the test is thought to be due to the absorption of water by the resin film. On the other hand, resin compositions 29 and 30 had mass ratios of resin to epoxy compound (resin / epoxy compound) of 2 and 1, respectively. Therefore, cracks were observed in the resin film after the pressure cooker test, and the evaluation result was "B". Resin compositions 31 to 36 did not contain epoxy compounds, so the resin films formed from resin compositions 31 to 36 had poor resistance to high temperature and humidity, and the evaluation result was "B" or "C".

[0280] The resin composition according to this disclosure can be formed into a resin film and used as an optical filter or the like, which is useful for applications such as optical devices, display devices, mechanical parts, and electrical and electronic components.

Claims

1. A resin composition comprising a thermoplastic resin (A) having ester bonds and a glass transition temperature of 80°C or higher, an epoxy compound (B), and a solvent (C) having a boiling point of 100°C or higher, wherein the mass ratio ((A) / (B)) of the thermoplastic resin (A) to the epoxy compound (B) is 5 or higher.

2. The resin composition according to claim 1, wherein the epoxy compound (B) is a polyfunctional epoxy compound having two or more oxirane rings in one molecule.

3. The resin composition according to claim 1, wherein the epoxy compound (B) has an epoxy equivalent of 200 g / eq or less.

4. The resin composition according to claim 1, which does not contain a curing catalyst for curing the epoxy compound (B).

5. The resin composition according to claim 1, wherein the thermoplastic resin (A) is at least one selected from polyester resins, polycarbonate resins, and polyolefin resins having ester bonds.

6. The resin composition according to claim 1, further containing a dye (D).

7. The resin composition according to claim 6, wherein the dye (D) is at least one selected from squarylium-based dyes, crokonium-based dyes, and cyanine-based dyes.

8. The resin composition according to claim 6, wherein the dye (D) is a compound having a styrene structure.

9. The resin composition according to claim 8, wherein the compound having a styrene structure is a compound represented by the following formula (14). [In formula (14), ９１ R represents a cyano group, an acyl group, a carboxylic acid ester group or an amide group, ９２ R represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or a heteroaryl group, ９１ When both R ９２ and R ９１ are an acyl group, a carboxylic acid ester group or an amide group, R ９２ and R ９３ may be linked to each other to form a ring, ９４ R represents a hydrogen atom or an alkyl group, ９４ R represents a hydrogen atom, an organic group or a polar functional group, and a plurality of R ９４ may be the same as or different from each other, Y represents a sulfur atom or an oxygen atom, a represents an integer of 2 or more, L represents a divalent or higher linking group, and a plurality of groups bonded to L may be the same as or different from each other.] 10. The resin composition according to claim 1, further comprising at least one (E) selected from a silane coupling agent, its hydrolysate, and its hydrolyzed condensate.

11. The resin composition according to claim 1, further comprising a compound (F) containing an M-O-C bond (wherein M represents Ti, Zr, or Al).

12. An optical filter comprising a substrate made of silicate glass, borosilicate glass, soda glass, phosphate-based glass, or phthalic acid-based glass, and a resin layer provided on the substrate and formed from a resin composition according to any one of claims 1 to 11.

13. The optical filter according to claim 12, further comprising a dielectric film.

14. An image sensor having the optical filter described in claim 12.

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