JP7231430B2 - resin composition, ink and optical filter - Google Patents

Description

The present invention relates to a resin composition containing an oxocarbon compound, an ink containing the resin composition, and an optical filter having a resin layer formed from the resin composition or the ink.

Oxocarbon compounds such as squarylium compounds and croconium compounds utilize the spectral characteristics of being able to selectively absorb light in the red to near-infrared region while transmitting light in the visible region with high transmittance. Therefore, it is expected to be applied to near-infrared cut filters, near-infrared absorbing films, security inks, and the like. When applying the oxocarbon-based compound to such uses, it is desirable to handle the oxocarbon-based compound as a resin composition.

Patent Documents 1 to 3 disclose various resin compositions containing oxocarbon compounds. Patent Document 1 discloses a resin composition containing a specific oxocarbon compound, Patent Document 2 discloses a resin composition containing a specific squarylium compound, and Patent Document 3 discloses an oxocarbon compound. and a curing catalyst and a mercapto group-containing compound are disclosed. The resin composition disclosed in D3 uses an epoxy resin, which is a thermosetting resin, as a base resin, and contains a curing catalyst for curing the resin. Then, by including a mercapto group-containing compound in the resin composition together with the oxocarbon compound and the curing catalyst, when the resin is thermally cured to form a cured product, the oxocarbon compound deteriorates due to the epoxy resin or the curing catalyst. is suppressed, and the light selective transmission of the resulting cured product can be enhanced.

JP 2016-074649 A JP 2014-148567 A JP 2017-149896 A

The resin composition disclosed in Patent Document 3 contains a mercapto group-containing compound in order to suppress adverse effects when an epoxy resin, which is a thermosetting resin, is used as a base resin. In other words, when a thermoplastic resin is used as the base resin, there is no need to add a mercapto group-containing compound.

On the other hand, considering the industrial use of a resin composition containing an oxocarbon-based compound, it is preferable that it can be stored for a long period of time without particularly strict temperature control, for example, it is desirable that it can be stored at room temperature for several months or longer. This makes it possible to store a large amount of resin composition.

The present invention has been made in view of the above circumstances, and its object is to provide a resin composition containing a thermoplastic resin and an oxocarbon compound, which has excellent long-term storage stability, and the resin An object of the present invention is to provide an ink containing the composition and an optical filter formed from the resin composition or the ink.

［式（１）および式（２）中、Ｒ¹～Ｒ⁴はそれぞれ独立して、下記式（３）または下記式（４）で表される基を表す。］

［式（３）中、
環Ｐは、置換基を有していてもよい芳香族炭化水素環、芳香族複素環、またはこれらの環構造を含む縮合環を表し、
Ｒ¹¹～Ｒ¹³はそれぞれ独立して、水素原子、有機基または極性官能基を表し、Ｒ¹²とＲ¹³は互いに連結して環を形成してもよく、
＊は、式（１）中の４員環または式（２）中の５員環との結合部位を表す。］

［式（４）中、
Ｒ¹⁴～Ｒ¹⁸はそれぞれ独立して、水素原子、有機基または極性官能基を表し、Ｒ¹⁴とＲ¹⁵、Ｒ¹⁵とＲ¹⁶、Ｒ¹⁶とＲ¹⁷、Ｒ¹⁷とＲ¹⁸はそれぞれ、互いに連結して環を形成していてもよく、
＊は、式（１）中の４員環または式（２）中の５員環との結合部位を表す。］
［４］ さらにシランカップリング剤、その加水分解物、およびその加水分解縮合物よりなる群から選ばれる少なくとも１種を含有する［１］～［３］のいずれかに記載の樹脂組成物。
［５］ さらに紫外線吸収剤を含有する［１］～［４］のいずれかに記載の樹脂組成物。
［６］ ［１］～［５］のいずれかに記載の樹脂組成物と溶媒とを含有することを特徴とするインク。
［７］ 基板と、前記基板上に形成され、［１］～［５］のいずれかに記載の樹脂組成物または［６］に記載のインクから形成された樹脂層とを有することを特徴とする光学フィルター。
［８］ ［７］に記載の光学フィルターを備えることを特徴とする撮像素子。 The present invention includes the following inventions.
[1] A resin composition comprising a thermoplastic resin, an oxocarbon compound, and a polyhydric mercaptan compound.
[2] The resin composition according to [1], wherein the content of the polyhydric mercaptan compound is 0.5 parts by mass or more and 8 parts by mass or less in 100 parts by mass of the solid content of the resin composition.
[3] The resin according to [1] or [2], wherein the oxocarbon compound is a squarylium compound represented by the following formula (1) and/or a croconium compound represented by the following formula (2) Composition.

[In Formulas (1) and (2), R ¹ to R ⁴ each independently represent a group represented by Formula (3) or Formula (4) below. ]

[In formula (3),
Ring P represents an optionally substituted aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures,
R ¹¹ to R ¹³ each independently represent a hydrogen atom, an organic group or a polar functional group, R ¹² and R ¹³ may be linked together to form a ring,
* represents a binding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2). ]

[In formula (4),
R ¹⁴ to R ¹⁸ each independently represent a hydrogen atom, an organic group or a polar functional group, R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ each may be linked to form a ring,
* represents a binding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2). ]
[4] The resin composition according to any one of [1] to [3], further comprising at least one selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a hydrolyzed condensate thereof.
[5] The resin composition according to any one of [1] to [4], further containing an ultraviolet absorber.
[6] An ink comprising the resin composition according to any one of [1] to [5] and a solvent.
[7] A substrate, and a resin layer formed on the substrate and formed from the resin composition according to any one of [1] to [5] or the ink according to [6]. optical filter.
[8] An imaging device comprising the optical filter according to [7].

The resin composition and ink of the present invention contain a polyhydric mercaptan compound in addition to a thermoplastic resin and an oxocarbon-based compound, so that long-term storage stability is enhanced and stored at room temperature (for example, about 25° C.) for about half a year. The deterioration of the oxocarbon-based compound is suppressed even during storage. By using such a resin composition or ink, it is possible to easily form an optical filter having desired light selective transmission performance and high transparency even after long-term storage.

4 shows transmission spectra of optical filters produced in Examples.

The resin composition of the present invention contains (A) a thermoplastic resin, (B) an oxocarbon compound, and (C) a polyhydric mercaptan compound. Since the resin composition of the present invention contains the polyhydric mercaptan compound as the component (C) in addition to the thermoplastic resin as the component (A) and the oxocarbon compound as the component (B), the long-term storage stability is improved, and the room temperature is improved. Even if it is stored at (for example, about 25° C.) for about half a year, deterioration of the oxocarbon-based compound is suppressed. Therefore, by curing the resin composition to form a resin molding or by forming a resin layer on a substrate, it is possible to form an optical filter or the like having desired light selective transmission performance and high transparency. The resin composition of the present invention will be described in detail below.

In the resin composition of the present invention, (A) a thermoplastic resin is used as a base resin. The thermoplastic resin used as component (A) is not particularly limited as long as it is a resin that softens when heated. As the thermoplastic resin, it is preferable to use a resin having high transparency. polyethylene resin, polypropylene resin), cycloolefin resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (e.g., nylon), aramid resin, polyimide resin, polyamideimide resin, polyester resin (e.g., polybutylene terephthalate ( PBT), polyethylene terephthalate (PET), etc.), butyral resin, polycarbonate resin, polyether resin, polysulfone resin, ABS resin (acrylonitrile butadiene styrene resin), AS resin (acrylonitrile-styrene copolymer), fluorine resin (e.g. , fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), fluorinated polyaryletherketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorine polyethernitrile (FPEN), etc.). Among these, (meth)acrylic resins, cycloolefin resins, polyimide resins, polyamideimide resins, polyester resins, polyarylate resins, polyamide resins, polycarbonate resins, polysulfone resins, fluorine Preferred are aromatic polymers.

(Meth)acrylic resin is a polymer having repeating units derived from (meth)acrylic acid or a derivative thereof. A resin having such a property is preferably used. The (meth)acrylic resin preferably has a ring structure in the main chain, for example, a lactone ring structure, a glutaric anhydride structure, a glutarimide structure, a maleic anhydride structure, a carbonyl group-containing ring structure such as a maleimide ring structure; Carbonyl group-free ring structures such as ring structures, azetidine ring structures, tetrahydrofuran ring structures, pyrrolidine ring structures, tetrahydropyran ring structures, and piperidine ring structures can be mentioned. In addition, the carbonyl group-containing ring structure includes a structure containing a carbonyl group derivative group such as an imide group. (Meth) acrylic resins having a carbonyl group-containing ring structure, for example, JP-A-2004-168882, JP-A-2008-179677, WO 2005/54311, JP-A-2007-31537, etc. Those described can be used.

The cycloolefin-based resin is a polymer obtained by polymerizing a cycloolefin as at least part of a monomer component, and is not particularly limited as long as it has an alicyclic structure in part of its main chain. Examples of cycloolefin-based resins include Topas (registered trademark) manufactured by Polyplastics, APEL (registered trademark) manufactured by Mitsui Chemicals, Zeonex (registered trademark) and Zeonor (registered trademark) manufactured by Nippon Zeon, and JSR Corporation. Arton (registered trademark) manufactured by Sanyo Denki Co., Ltd., etc. can be used.

Polyimide resin is a polymer containing an imide bond in the repeating unit of the main chain, for example, tetracarboxylic acid dianhydride and diamine are polymerized to obtain polyamic acid, which is dehydrated and cyclized (imidization). It can be manufactured by As the polyimide resin, it is preferable to use aromatic polyimide in which aromatic rings are linked by imide bonds. Examples of polyimide resins include Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Merdin (registered trademark) manufactured by Saint-Gobain, and TPS (registered trademark) TI3000 series manufactured by Toray Plastics Seiko Co., Ltd. etc. can be used.

A polyamideimide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. For example, Torlon (registered trademark) manufactured by Solvay Advanced Polymers, Vylomax (registered trademark) manufactured by Toyobo Co., Ltd., and TPS (registered trademark) TI5000 series manufactured by Toray Plastics Seiko Co., Ltd. can be used.

A polyester resin is a polymer containing an ester bond in the repeating unit of the main chain, and can be obtained, for example, by condensation polymerization of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. For example, OKP series manufactured by Osaka Gas Chemicals, TRN series manufactured by Teijin, Teonex ( registered trademark), Rynite (registered trademark) manufactured by DuPont, Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation, Nova Duran (registered trademark) manufactured by Mitsubishi Engineering-Plastics, Lumirror (registered trademark) manufactured by Toray Industries, Toraycon ( registered trademark), etc. can be used.

A polyarylate resin is a polymer obtained by condensation polymerization of a dihydric phenol compound and a dibasic acid (e.g., an aromatic dicarboxylic acid such as phthalic acid). and a repeating unit containing Examples of polyarylate resins that can be used include Vectran (registered trademark) manufactured by Kuraray Co., Ltd., U Polymer (registered trademark) and Unifiedr (registered trademark) manufactured by Unitika.

A polyamide resin is a polymer containing an amide bond in the repeating unit of the main chain, and can be obtained, for example, by condensation polymerization of a diamine and a dicarboxylic acid. The polyamide resin may have an aliphatic skeleton in its main chain, and nylon, for example, can be used as such an amide resin. The polyamide resin may have an aromatic skeleton, and an aramid resin is known as such a polyamide resin. Aramid resin is preferably used because it has excellent heat resistance and strong mechanical strength. (registered trademark) and the like can be used.

A polycarbonate resin is a polymer containing a carbonate group (--O--(C=O)--O--) in a repeating unit of the main chain. Polycarbonate resins include Panlite (registered trademark) manufactured by Teijin Limited, Iupilon (registered trademark) manufactured by Mitsubishi Engineering-Plastics Corporation, Novarex (registered trademark), and Zanter (registered trademark) manufactured by Sumika Styron Polycarbonate Co., Ltd. (registered trademark) and the like can be used.

Polysulfone resins are polymers having repeating units containing aromatic rings, sulfonyl groups (--SO ₂ --) and oxygen atoms. Examples of polysulfone resins that can be used include Sumika Excel (registered trademark) PES3600P and PES4100P manufactured by Sumitomo Chemical Co., Ltd., and UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers.

The fluorinated aromatic polymer is a repeat comprising an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is a polymer having a unit, and among these, a polymer essentially containing a repeating unit containing an aromatic ring having one or more fluorine atoms and an ether bond is preferable. As the fluorinated aromatic polymer, for example, those described in JP-A-2008-181121 can be used.

The thermoplastic resin preferably has high transparency, which facilitates suitable application of the resin composition to optical applications. For example, the thermoplastic resin preferably has a total light transmittance of 75% or more, more preferably 80% or more, even more preferably 85% or more at a thickness of 0.1 mm. The upper limit of the total light transmittance of the thermoplastic resin is not particularly limited as long as the total light transmittance is 100% or less. Total light transmittance is measured based on JIS K7105.

The thermoplastic resin preferably has a high glass transition temperature (Tg), which can improve the heat resistance of the resin layer formed from the resin composition. The glass transition temperature of the thermoplastic resin is, for example, preferably 110° C. or higher, more preferably 120° C. or higher, and even more preferably 130° C. or higher. Although the upper limit of the glass transition temperature of the thermoplastic resin is not particularly limited, it is preferably 380° C. or less from the viewpoint of improving the moldability of the resin composition.

The content of component (A) in the resin composition is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, still more preferably 60 parts by mass or more, or 99 parts by mass, based on 100 parts by mass of the solid content of the resin composition. It is preferably 97 parts by mass or less, even more preferably 95 parts by mass or less. In addition, when the resin composition contains a solvent, the solid content of the resin composition means the amount of the resin composition excluding the solvent.

The oxocarbon compound used as component (B) is not particularly limited as long as it is a compound containing a carbon oxide as a basic skeleton. It is preferable to use a squarylium compound or a croconium compound widely known as a compound having a relatively high . If such an oxocarbon-based compound is included, the resin composition can be cured to form a resin molding, or a resin layer can be formed on the substrate to cut off light in the red to near-infrared region. It can be applied to filters and the like.

The oxocarbon compound contained in the resin composition may be a squarylium compound, a croconium compound, or both. The number of oxocarbon compounds contained in the resin composition may be one, or two or more.

Specific examples of the squarylium compound include compounds having a squarylium skeleton represented by the following formula (1), and specific examples of the croconium compound include compounds having a croconium skeleton represented by the following formula (2). be In formulas (1) and (2) below, R ¹ to R ⁴ each independently represent an organic group.

As the oxocarbon compound, in the above formulas (1) and (2), R ¹ to R ⁴ are each independently a group represented by the following formula (3) or the following formula (4). . A squarylium compound or croconium compound having a group represented by the following formula (3) has a broad absorption peak in the red to near-infrared region, and can cut light in a relatively wide wavelength range. On the other hand, since the squarylium compound or croconium compound having a group represented by the following formula (4) has a sharp absorption peak in the red to near-infrared region, light in the wavelength region corresponding to this absorption peak is selected. It is possible to cut it effectively.

In formula (3), ring P represents an optionally substituted aromatic hydrocarbon ring, aromatic heterocyclic ring, or condensed ring containing these ring structures, and R ¹¹ to R ¹³ are each independently represents a hydrogen atom, an organic group or a polar functional group, and R ¹² and R ¹³ may be linked together to form a ring. In formula (4), R ¹⁴ to R ¹⁸ each independently represent a hydrogen atom, an organic group or a polar functional group, R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and Each R ¹⁸ may be linked to each other to form a ring. * represents a binding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2).

A squarylium compound and a croconium compound may have a compound having a resonance relationship. Also included are compounds in a resonance relationship.

In the above formula (1), the groups bonded to one side and the other side of the squarylium skeleton may be the same or different. In formula (2) above, the groups bonded to one side and the other side of the croconium skeleton may be the same or different. When the groups bonded to one side and the other side of the squarylium skeleton or croconium skeleton are the same, the durability of the squarylium compound or croconium compound to heat and light can be improved. When the groups bonded to one side and the other side of the squarylium skeleton or croconium skeleton are different from each other, association or aggregation of molecules of the squarylium compound or croconium compound is suppressed, and improved solubility in solvents and resins can be expected.

Examples of organic groups represented by R ¹¹ to R ¹⁸ include alkyl groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, alkylsulfonyl groups, alkylsulfinyl groups, aryl groups, aralkyl groups, aryloxy groups, arylthio groups, and aryloxycarbonyl groups. group, arylsulfonyl group, arylsulfinyl group, heteroaryl group, amino group, amide group, sulfonamide group, carboxy group (carboxylic acid group), cyano group and the like. Polar functional groups of R ¹¹ to R ¹⁸ include halogeno group, hydroxyl group, nitro group, sulfo group (sulfonic acid group) and the like.

Alkyl groups for R ¹¹ to R ¹⁸ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and other linear or branched alkyl groups; cyclopropyl group, cyclobutyl cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and other cyclic (alicyclic) alkyl groups. The alkyl group may have a substituent, and examples of such substituents include an aryl group, a heteroaryl group, a halogeno group, a hydroxyl group, a carboxy group, an alkoxy group, a cyano group, a nitro group, an amino group, and a sulfo group. etc. Examples of alkyl groups having a halogeno group include monohalogenoalkyl groups, dihalogenoalkyl groups, alkyl groups having a trihalomethyl unit, and perhalogenoalkyl groups. As the halogeno group, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom is particularly preferable. The number of carbon atoms in the alkyl group (the number of carbon atoms excluding substituents) is preferably 1 to 20. Specifically, if the alkyl group is linear or branched, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5, and if it is a cyclic alkyl group, it preferably has 4 to 10 carbon atoms, more preferably 5 to 8 carbon atoms.

For specific examples of the alkyl groups included in the alkoxy groups, alkylthio groups, alkoxycarbonyl groups, alkylsulfonyl groups and alkylsulfinyl groups of R ¹¹ to R ¹⁸ , the above explanations regarding alkyl groups are referred to.

Aryl groups of R ¹¹ to R ¹⁸ include phenyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group and indenyl group. The aryl group may have a substituent, and the substituents that the aryl group has include an alkyl group, an alkoxy group, a heteroaryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, a nitro group, an amino group, thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like. The number of carbon atoms in the aryl group (the number of carbon atoms excluding substituents) is preferably 6-20, more preferably 6-12.

Aralkyl groups represented by R ¹¹ to R ¹⁸ include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, naphthylmethyl group and the like. The aralkyl group may have a substituent, and examples of the substituents that the aralkyl group has include an alkyl group, an alkoxy group, a halogeno group, a halogenoalkyl group, a cyano group, a nitro group, a thiocyanate group, an acyl group, and an alkoxycarbonyl group. , aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like. The number of carbon atoms in the aralkyl group (the number of carbon atoms excluding substituents) is preferably 7-25, more preferably 7-15.

For specific examples of the aryl group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylsulfonyl group, and arylsulfinyl group of R ¹¹ to R ¹⁸ , the above description of the aryl group can be referred to.

Examples of heteroaryl groups for R ¹¹ to R ¹⁸ include thienyl, thiopyranyl, isothiochromenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyraridinyl, pyrimidinyl, pyridazinyl, thiazolyl and isothiazolyl. group, furanyl group, pyranyl group, and the like. The heteroaryl group may have a substituent, and the substituents that the heteroaryl group has include an alkyl group, an alkoxy group, an aryl group, a halogeno group, a halogenoalkyl group, a hydroxyl group, a cyano group, an amino group, and a nitro group. , thiocyanate group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group and the like. The number of carbon atoms in the heteroaryl group (the number of carbon atoms excluding substituents) is preferably 2-20, more preferably 3-15.

The amino group of R ¹¹ to R ¹⁸ is represented by the formula: —NR ^a1 R ^a2 , where R ^a1 and R ^a2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an aralkyl group. , which are heteroaryl groups. For specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group, the above descriptions of these groups can be referred to, and the alkenyl group and alkynyl group are one of the carbon-carbon single bonds of the alkyl groups exemplified above. Examples include groups in which a moiety is replaced with a double bond or triple bond. R ^a1 and R ^a2 may be linked together to form a ring.

Amido groups of R ¹¹ to R ¹⁸ include those represented by the formula: -NH-C(=O)-R ^a3 , where R ^a3 is an alkyl group, an aryl group, an aralkyl group or a heteroaryl group. For specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups, refer to the above descriptions of these groups.

The sulfonamide groups represented by R ¹¹ to R ¹⁸ include those represented by the formula: --NH--SO ₂ --R ^a4 , where R ^a4 is an alkyl group, an aryl group, an aralkyl group or a heteroaryl group. For specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups, refer to the above descriptions of these groups.

Halogeno groups of R ¹¹ to R ¹⁸ include fluoro, chloro, bromo and iodo groups.

Each ring structure formed from R ¹² to R ¹⁸ includes a hydrocarbon ring and a heterocyclic ring, and these ring structures may or may not have aromaticity. A hydrocarbon ring or a non-aromatic heterocyclic ring is preferred. Non-aromatic hydrocarbon rings include, for example, cycloalkanes such as cyclopentane, cyclohexane and cycloheptane; is mentioned. As the non-aromatic heterocyclic ring, one or more of the carbon atoms constituting the ring of the non-aromatic hydrocarbon ring as described above are N (nitrogen atom), S (sulfur atom) and O (oxygen atom). A ring substituted with at least one or more atoms selected from is exemplified. Non-aromatic heterocycles include, for example, pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, piperidine ring, tetrahydropyran ring, tetrahydrothiopyran ring, morpholine ring, hexamethyleneimine ring, hexamethylene oxide ring, hexamethylene sulfide ring, A heptamethyleneimine ring and the like are included.

When R ¹¹ to R ¹³ in formula (3) are independent groups, R ¹¹ to R ¹³ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group. is preferred, and a hydrogen atom, an alkyl group, or an aryl group is more preferred. Preferred examples of alkyl and aryl groups for R ¹¹ to R ¹³ include methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, cyclopentyl group, cyclohexyl group and phenyl group.

In formula (3), the ring structure formed by linking R ¹² and R ¹³ is preferably a 4- to 9-membered unsaturated hydrocarbon ring, especially cyclopentene, cyclohexene, cycloheptene, cyclooctene, and the like. is more preferred. If the group of formula (3) is constituted in this way, the shoulder peak of the absorption waveform in the red to near-infrared region is reduced, and the absorption peak becomes sharp.

Examples of the aromatic hydrocarbon ring of ring P in formula (3) include benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, fluoranthene ring, cyclotetradecaheptaene ring and the like. The aromatic hydrocarbon ring may have only one ring structure, or two or more ring structures may be condensed. The aromatic heterocyclic ring of ring P contains one or more atoms selected from N (nitrogen atom), O (oxygen atom) and S (sulfur atom) in the ring structure and has aromaticity, for example , 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 and the like. The aromatic heterocyclic ring may have only one ring structure, or may have two or more ring structures condensed. The condensed ring containing these ring structures of the ring P has a structure in which an aromatic hydrocarbon ring and an aromatic heterocyclic ring are condensed, such as indole ring, isoindole ring, benzimidazole ring, quinoline ring , benzopyran ring, acridine ring, xanthene ring, carbazole ring and the like. By appropriately setting the π-conjugated system of the ring P, the absorption wavelength in the red to near-infrared region can be easily adjusted.

The ring P may have a substituent, and examples of the substituent include the above-described organic groups and polar functional groups. When the ring P has a substituent, the number thereof is preferably 1-3, more preferably 1-2, and still more preferably 1. Ring P may not have a substituent.

For details of the squarylium compound and croconium compound having a group represented by formula (3), see, for example, the description in JP-A-2016-74649.

When R ¹⁴ to R ¹⁸ in formula (4) are independent groups, each of R ¹⁴ to R ¹⁸ is independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, an amido group, or a hydroxyl group. Preferably. By appropriately selecting R ¹⁴ to R ¹⁸ , it is possible to control the maximum absorption wavelength of the squarylium compound or croconium compound to a desired value. Among them, from the viewpoint of stability of the squarylium compound and croconium compound and ease of production, it is preferable that each of R ¹⁴ to R ¹⁸ is independently a hydrogen atom, an alkyl group, or an amide group. The alkyl group in this case is preferably linear or branched, and preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms.

In the group represented by formula (4), R ¹⁵ and R ¹⁶ are preferably linked to form a ring, and R ¹⁶ and R ¹⁷ may be linked to form a ring. In this case, at least R ¹⁴ and R ¹⁸ are independent groups. If the group of formula (4) is constructed in this way, the absorption peak in the red to near-infrared region will be sharp. The number of ring members of the ring structure formed from R ¹⁵ and R ¹⁶ and the ring structure formed from R ¹⁶ and R ¹⁷ is preferably 5 or more, more preferably 6 or more, preferably 12 or less, and more preferably 10 or less. Preferably, 8 or less is more preferable.

In the group represented by formula (4), R ¹⁶ is an amino group, R ¹⁶ which is an amino group is linked to R ¹⁵ to form a ring, or is linked to R ¹⁷ to form a ring preferably. In this case, the maximum absorption wavelength shifts to the long wavelength side (for example, 685 nm or more), the transmittance of light in the red region is increased, and the color of the transmitted light can be brought closer to the actual color. From the same point of view, R ¹⁴ or R ¹⁸ is preferably an amide group.

In the squarylium compound and croconium compound having a group represented by formula (4), the benzene rings on both sides of the squarylium skeleton or croconium skeleton may be connected by a connecting group. Examples of such compounds include squarylium compounds disclosed in JP-A-2015-176046.

The content of the component (B) in the resin composition is preferably 0.01 parts by mass or more, preferably 0.03 parts by mass, based on 100 parts by mass of the solid content of the resin composition, from the viewpoint of expressing the desired performance. Part or more is more preferable, and 0.1 part by mass or more is even more preferable. Further, from the viewpoint of improving the moldability and film-forming properties of the resin composition, the content of the component (B) in the resin composition is preferably 25 parts by mass or less in 100 parts by mass of the solid content of the resin composition. 20 parts by mass or less is more preferable, and 15 parts by mass or less is even more preferable. The content of component (B) in the resin composition means the total content of the multiple types of oxocarbon compounds when multiple types of oxocarbon compounds are included as component (B).

The resin composition contains a polyhydric mercaptan compound as the (C) component. The inventors of the present invention examined the storage stability of a resin composition containing a thermoplastic resin and an oxocarbon compound. 25 ° C.) for about half a year, the spectral characteristics of the oxocarbon compound deteriorate (for example, the transmittance of light in the visible light region decreases and the absorbance of light in the near-infrared region decreases). It was confirmed that a slight haze occurred in the Therefore, when an optical filter or the like is formed using such a resin composition after long-term storage, desired light selective transmission performance may not be obtained, or the transparency may deteriorate.

Therefore, in the present invention, the resin composition contains a polyhydric mercaptan compound in order to ensure long-term storage stability of the resin composition containing the thermoplastic resin and the oxocarbon compound. By containing the polyhydric mercaptan compound, deterioration of the oxocarbon compound contained in the resin composition is suppressed, and the long-term storage stability of the resin composition is improved. Such an effect of suppressing deterioration of oxocarbon-based compounds cannot be obtained by adding a general antioxidant, and by using a polyhydric mercaptan compound, the oxocarbon-based compound can be particularly effectively suppressed. Deterioration can be suppressed. Polyhydric mercaptan compounds are not only preferable in that a plurality of mercapto groups that suppress the deterioration of oxocarbon compounds are present in one molecule, but also because the molecular weight increases, volatilization from the resin composition even after long-term storage. It is also preferable in that it is easy to remain without delamination.

The polyhydric mercaptan compound is not particularly limited as long as it is a compound having two or more mercapto groups in one molecule. Examples include 1,2-ethanedithiol, 1,2-propanedithiol, bis(2-mercaptoethyl). Ether, bis(2-mercaptoethyl) sulfide, 1,3-bis(2-mercaptoethylthio)propane, 2,3-bis(2-mercaptoethylthio)propane-1-thiol and other alkanepolythiols or alkanepolythiols Polythiol containing —CH ₂ — partially replaced with —O—, —S—; trimethylolpropane trimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercapto propionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakismercaptoacetate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakismercaptoacetate, dipentaerythritol hexakis(3-mercaptopropionate), etc. mercaptoalkylcarboxylic acid and polyol (for example, alkanepolyol, polyol in which a portion of —CH ₂ — contained in alkanepolyol is replaced with —O—, tris(hydroxyalkyl)isocyanurate), and the like. be done. The number of polyhydric mercaptan compounds contained in the resin composition may be one, or two or more. Among these, an ester of a mercaptoalkylcarboxylic acid and a polyol is preferable because it is easy to obtain a polyhydric mercaptan compound having more mercapto groups. In addition, since such a mercaptan compound has a relatively large molecular weight, it tends to remain in the resin composition without volatilizing even after long-term storage.

The polyhydric mercaptan compound preferably has 3 or more mercapto groups, more preferably 4 or more, from the viewpoint of further enhancing the effect of suppressing deterioration of the oxocarbon compound. On the other hand, the number of mercapto groups possessed by the polyvalent mercaptan compound is preferably 10 or less, more preferably 8 or less, from the viewpoint of easy availability and production easiness of the polyvalent mercaptan compound.

The polyhydric mercaptan compound is preferably an organic mercaptan compound. Specifically, the organic mercaptan compound is preferably a compound composed only of a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, and a halogen atom. A compound composed only of atoms and nitrogen atoms is more preferred. The polyhydric mercaptan compound also includes a group represented by the formula: --OC(=O)--R ²⁰ --SH (wherein R ²⁰ represents a linear or branched alkylene group having 1 to 6 carbon atoms). ) is preferable.

The content of component (C) in the resin composition is preferably 0.5 parts by mass or more based on 100 parts by mass of the solid content of the resin composition from the viewpoint of enhancing the long-term storage stability of the resin composition. 1 part by mass or more is more preferable, and 2 parts by mass or more is even more preferable. On the other hand, even if the component (C) is excessively contained in the resin composition, the effect of increasing the long-term storage stability is not much improved. The content of the component is preferably 8 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less.

The content of the component (C) in the resin composition is 1.0 of the content of the oxocarbon compound of the component (B) in order to suppress decomposition of the oxocarbon compound during long-term storage of the resin composition. It is preferably at least 1.2 times by mass, more preferably at least 1.2 times by mass, even more preferably at least 1.5 times by mass, and even more preferably at least 2.0 times by mass. On the other hand, even if the resin composition contains an excessive amount of the component (C), the effect of suppressing the decomposition of the oxocarbon compound during long-term storage is not much improved. The content is preferably 8.0 times by mass or less, more preferably 6.0 times by mass or less, and even more preferably 5.0 times by mass or less the content of component (B).

The resin composition preferably contains, as component (D), at least one selected from silane coupling agents, hydrolyzates of silane coupling agents, and hydrolyzed condensates of silane coupling agents. By including the component (D) in the resin composition, when the resin composition is used to form a resin layer on a substrate, the adhesion of the resin layer to the substrate can be enhanced. A resin layer laminated substrate formed from such a resin composition can be suitably applied to an optical filter. Hereinafter, the silane coupling agent, the hydrolyzate of the silane coupling agent, and the hydrolyzed condensate of the silane coupling agent may be collectively referred to as a "specific silane compound".

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 a compound having such a functional group and an alkoxysilyl group can be used. preferable. The silane coupling agent may contain only one or a plurality of the above functional groups, and may contain only one or a plurality of alkoxysilyl groups. good too.

When the silane coupling agent contains only one alkoxysilyl group, an alkoxysilane represented by the following formula (5) is preferably used as the silane coupling agent. Therefore, as component (D), it is preferable to use at least one selected from silane coupling agents represented by the following formula (5), hydrolyzates thereof, and hydrolyzed condensates thereof.
^SiR21kR22m ( ^OR23 ) _n ( _OH ) _{4-kmn (} 5 ⁾

In formula (5), R ²¹ represents an epoxy group-containing group, amino group-containing group, mercapto group-containing group or polymerizable double bond-containing group, R ²² and R ²³ each independently represent an alkyl group, and k represents an integer of 1 to 3, m represents an integer of 0 to 2, and n represents an integer of 1 to 3. When k is 2 or more, a plurality of R ²¹ may be the same or different; when m is 2, a plurality of R ²² may be the same or different; In the above case, the plurality of ORs ²³ may be the same or different. R ²¹ , R ²² , OR ²³ and OH are groups directly bonded to Si, respectively.

The epoxy group-containing group of R ²¹ is not particularly limited as long as it contains an epoxy group, and examples thereof include glycidoxy group-containing groups and cycloalkene oxide (alicyclic epoxy group)-containing groups. A glycidoxy group or a cycloalkene oxide may be bonded to a silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). Preferably, R ²¹ contains only one epoxy group. Epoxy-containing groups for R ²¹ include glycidoxy, 3-glycidoxypropyl, 8-(glycidoxy)-n-octyl, 3,4-epoxycyclohexyl, and 2-(3,4-epoxycyclohexyl). An ethyl group etc. are mentioned.

The amino group-containing group for R ²¹ is not particularly limited as long as it has an amino group, and may have a primary amino group, may have a secondary amino group, may have a tertiary It may have an amino group, or may have a plurality of 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). Examples of amino group-containing groups for R ²¹ include 3-aminopropyl group, 3-(2-aminoethyl)aminopropyl group, 3-(6-aminohexyl)aminopropyl group and 3-(N,N-dimethylamino). propyl group, N-phenylaminomethyl group, N-phenyl-3-aminopropyl group, N-benzyl-3-aminopropyl group, N-cyclohexylaminomethyl group and the like.

The mercapto group-containing group for R ²¹ 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 preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. Preferably, R ²¹ contains only one mercapto group. The mercapto group-containing group for R ²¹ includes 3-mercaptopropyl group, 2-mercaptoethyl group, 2-mercaptopropyl group, 6-mercaptohexyl group and the like.

The polymerizable double bond-containing group for R ²¹ is not particularly limited as long as it has a polymerizable double bond group. is mentioned. The polymerizable double bond group may be directly bonded to the silicon atom, or 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). . Examples of the polymerizable double bond-containing group for R ²¹ include vinyl group, 2-propenyl group, styryl group, and 3-(meth)acryloxypropyl group.

From the viewpoint of enhancing the adhesion of the resin layer to the substrate, it is preferable that the distance between the epoxy group, amino group, mercapto group or polymerizable double bond group contained in R ²¹ and the silicon atom is not too far. is preferably directly bonded to the silicon atom or bonded to the silicon atom via an alkylene group having 1 to 6 carbon atoms.

The alkyl groups of R ²² and R ²³ preferably have 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 3 carbon atoms. R ²² preferably includes a methyl group, an ethyl group, an n-propyl group and an isopropyl group. OR ²³ preferably includes a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group.

In formula (5), k is preferably 1 or 2, more preferably 1, which makes it easier to improve the adhesion of the resin layer to the substrate. Further, m is preferably 0 or 1, more preferably 0, and n is preferably 2 or 3.

When the silane coupling agent contains a plurality of alkoxysilyl groups, a polymer-type polyfunctional silane coupling agent can be used as the silane coupling agent. Polymer-type polyfunctional silane coupling agents have a structure in which a group and an alkoxysilyl group-containing group are bonded to an organic polymer chain. It can also contain multiple functional groups such as groups, polymerizable double bond groups, and the like. Polysiloxane is not included in the organic chain of the polymer type polyfunctional silane coupling agent. By configuring the polymer-type polyfunctional silane coupling agent in this way, many reaction points with the resin and the substrate are formed, and the adhesion of the resin layer to the substrate can be enhanced.

The hydrolyzate of the silane coupling agent used as component (D) can be obtained by converting the alkoxysilyl groups contained in the silane coupling agent into silanol groups by hydrolysis. Further, the hydrolytic 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--). can be done. When a silane coupling agent is usually hydrolyzed, a hydrolyzate of the silane coupling agent is obtained, and a dehydration condensation reaction of the silanol groups contained in the hydrolyzate also occurs, resulting in hydrolytic condensation of the silane coupling agent. Things are easy to get. The hydrolytic condensate of the silane coupling agent may be a dehydration condensate of the hydrolyzate of the silane coupling agent of the same kind, or may be a dehydration condensate of the hydrolyzate of the silane coupling agent of a different kind. .

As component (D), it is preferable to use at least one selected from the group consisting of an epoxy group-containing silane coupling agent, its hydrolyzate, and its hydrolyzed condensate. Therefore, R ²¹ in formula (5) above is preferably an epoxy group-containing group. This makes it easier to improve the adhesion between the resin layer and the substrate.

The resin composition may contain only one type of component (D), or may contain two or more types. The resin composition preferably contains at least a hydrolyzate and/or a hydrolyzed condensate of a silane coupling agent as the component (D), thereby improving the adhesion of the resin layer to the substrate, especially under harsh conditions. Adhesion after boiling in water, which is a condition, can be enhanced. More preferably, component (D) contains at least a hydrolyzate or hydrolyzed condensate of an epoxy group-containing silane coupling agent.

Component (D) more preferably contains a hydrolytic condensate of a silane coupling agent. The dehydration condensate in this case preferably contains at least a dimer or trimer of alkoxysilane (for example, the alkoxysilane represented by the above formula (5)). For example, when the weight-average molecular weight of the specific silane compound used as component (D) is measured, it is preferably equal to or less than the molecular weight of a pentamer (assuming that all alkoxy groups are hydroxyl groups). It is more preferable that the molecular weight is equal to or less than that of the tetramer. Specific values of the weight average molecular weight are, for example, preferably 300 or more, preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.

The content of component (D) in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more based on 100 parts by mass of the solid content of the resin composition. It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less. If the content of component (D) is 0.1 part by mass or more in 100 parts by mass of the solid content of the resin composition, when a resin layer is formed on a substrate using the resin composition, It becomes easy to improve the adhesion of the resin layer to the substrate. On the other hand, even if the component (D) is excessively contained in the resin composition, the effect of increasing the adhesion of the resin layer to the substrate is not much improved. , the content of component (D) is preferably 20 parts by mass or less. The content of component (D) based on the thermoplastic resin of component (A) is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, with respect to 100 parts by mass of the thermoplastic resin of component (A). is more preferably 3 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.

The resin composition may have an ultraviolet absorber as the (E) component. By including an ultraviolet absorber in the resin composition, deterioration of the resin composition caused by light in the ultraviolet to violet region can be suppressed. Further, by curing a resin composition to form a resin molding, or by forming a resin layer on a substrate, an optical filter that cuts even light in the ultraviolet to violet region can be formed. Furthermore, even if the resin composition is stored or the optical filter is manufactured or processed (e.g. vapor deposition, mounting, etc.), even if it is exposed to ultraviolet light, other substances contained in the resin component or the resin composition will be removed from the ultraviolet light. It can protect the components, especially the component (B), and suppress the deterioration of these components.

As the ultraviolet absorbing dye, known ultraviolet absorbers such as benzotriazole-based compounds, benzophenone-based compounds, salicylic acid-based compounds, benzoxazinone-based compounds, cyanoacrylate-based compounds, benzoxazole-based compounds, merocyanine-based compounds, and triazine-based compounds are used. can be used. Only one type of ultraviolet absorber may be used, or two or more types may be used. Commercially available substances may be used as the ultraviolet absorber, for example, ADEKA's ADEKA STAB (registered trademark) series, BASF's TINUVIN (registered trademark) series, and Sankyo Kasei Co., Ltd.'s Dislizer (registered trademark) series. , Sumisorb (registered trademark) series manufactured by Sumitomo Chemical Co., Ltd., Biosorb (registered trademark) series manufactured by Kyodo Pharmaceutical Co., Ltd., Seesorb (registered trademark) series manufactured by Cipro Kasei Co., Ltd., and the like can be used.

It is also preferable to use a styrene-based compound represented by the following formula (6) as the ultraviolet absorber. The styrene compound represented by the following formula (6) forms an absorption wavelength range in the wavelength range of 350 nm to 395 nm, and on the long wavelength side of the absorption wavelength range, the boundary between the absorption wavelength range and the transmission wavelength range. It can be formed sharp.

In the above formula (6), ^R31 represents a cyano group, an acyl group, a carboxylic acid ester group or an amide group, and ^R32 represents a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or represents a heteroaryl group, and when both R ³¹ and R ³² are an acyl group, a carboxylic acid ester group, or an amide, R ³¹ and R ³² may be linked together to form a ring, and R ³³ is a hydrogen atom; or an alkyl group, R ³⁴ represents a hydrogen atom, an organic group or a polar functional group, a plurality of R ³⁴ may be the same or different, X represents a sulfur atom or an oxygen atom, L represents a hydrogen atom or represents a divalent or higher linking group, a represents an integer of 1 or more, and when a is 2 or more, a plurality of groups bonded to L may be the same or different. In formula (6), R ³¹ (or R ³² ) may be in cis- or trans-position relative to R ³³ .

Acyl groups (alkanoyl groups) for R ³¹ and R ³² include methanoyl, ethanoyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl and dodecanoyl groups. , tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, eicosanoyl group and the like. A part of the hydrogen atoms of the acyl group may be substituted with an aryl group, an alkoxy group, a halogeno group, a hydroxyl group, or the like. The alkyl group in the acyl group may be linear or branched. The number of carbon atoms in the acyl group (the number of carbon atoms excluding substituents) is preferably 2-21, more preferably 2-11, still more preferably 2-6.

Carboxylic acid ester groups of R ³¹ and R ³² include those represented by the formula: -C(=O)-OR ^b1 , where R ^b1 is an alkyl group, an aryl group or an aralkyl group. For specific examples of the alkyl group, aryl group and aralkyl group, refer to the description of these groups for R ¹¹ to R ¹⁸ above.

The amide group of R ³¹ and R ³² is represented by the formula: -C(=O)-NR ^b2 R ^b3 , where R ^b2 is a hydrogen atom or an alkyl group, and R ^b3 is an alkyl group, an acyl group or an aryl group. or an aralkyl group. Specific examples of the alkyl group, aryl group and aralkyl group for R ^b2 and R ^b3 refer to the description of these groups for R ¹¹ to R ¹⁸ above, and specific examples of the acyl group for R ^b3 are the above R ³¹ and the description of the acyl group for R ³² .

When both R ³¹ and R ³² are acyl groups and are linked together to form a ring, the group formed from R ³¹ and R ³² has the formula: -C(=O)-R ^b4 -C( A group represented by =O)- is shown. When both R ³¹ and R ³² are carboxylic acid ester groups and are linked together to form a ring, the group formed from R ³¹ and R ³² has the formula: -C(=O)-OR A group represented by ^b5 -OC(=O)- is shown. When both R ³¹ and R ³² are amido groups and are linked together to form a ring, the group formed from R ³¹ and R ³² has the formula: -C(=O)-NR ^b6 -R ^b7 A group represented by -NR ^b8 -C(=O)- is shown. In these formulas, R ^b4 , R ^b5 and R ^b7 each independently represent a linear or branched alkylene group, and R ^b6 and R ^b8 each independently represent a hydrogen atom or a hydrocarbon group. , 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 of formula (6). Some of the hydrogen atoms in the alkylene groups of R ^b4 , R ^b5 and R ^b7 may be substituted with aryl groups, alkoxy groups, cyano groups, halogeno groups, hydroxyl groups, nitro groups and the like. The number of carbon atoms (the number of carbon atoms excluding substituents) of the alkylene groups of R ^b4 , R ^b5 and R ^b7 is preferably 2-10, more preferably 3-8. Preferred examples ^of hydrocarbon groups for R ^b6 and R ^b8 include alkyl groups, aryl groups and ^aralkyl groups. Reference is made to the description.

R ³³ in formula (6) represents a hydrogen atom or an alkyl group, and for specific examples of the alkyl group, refer to the above description of alkyl groups for R ¹¹ to R ¹⁸ . The alkyl group for R ³³ preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. A hydrogen atom is particularly preferred as R ³³ .

For details of the organic group and polar functional group of R ³⁴ in formula (6), refer to the description of the organic group and polar functional group of R ¹¹ to R ¹⁸ above. R ³⁴ is preferably one or more selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aralkyl group, an aryloxy group and an arylthio group, preferably a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-4, more preferably 1-3. Among the four R ³⁴ bonded to the benzene ring of formula (6), two or more are preferably hydrogen atoms, more preferably three or more are hydrogen atoms, and all four are hydrogen atoms. It is particularly preferred to have

In formula (6), X may be bonded at the ortho position, meta position, or para position with respect to the ethylene structure containing R ³¹ to R ³³ good too. From the viewpoint of ease of production of the styrenic compound, X is preferably bonded to the ethylene structure at the para-position.

In formula (6), when L is a divalent or higher linking group, the linking group includes an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, divalent linking groups such as —SO ₂ — and —NH—; trivalent linking groups such as a methine group (—C<) and —N< which may have an alkyl group; 4 such as >C< valent linking groups; and linking groups that are combinations thereof. The alkylene group may be linear, branched, or cyclic. Moreover, the alkylene group and the arylene group may have a hydroxyl group and/or a thiol group.

From the viewpoint of enhancing the heat resistance of the styrene compound, it is preferable that a is an integer of 2 or more and L represents a divalent or higher linking group. In addition, the linking group L is an alkylene group in which a portion of the hydrogen atoms may be replaced with a hydroxyl group and/or a thiol group, and an arylene group in which a portion of the hydrogen atoms may be replaced with a hydroxyl group and/or a thiol group. , —O—, —S—, and linking groups in which these groups are combined are preferred (wherein the ether bond and the thioether bond are discontinuous). The number of carbon atoms (the number of consecutive carbon atoms) in the 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 more preferably 8 or less. The number of carbon atoms in the arylene group is preferably 5 or more, more preferably 6 or more, and preferably 10 or less, more preferably 8 or less.

As the styrene compound, a styrene compound represented by the following formula (7) is particularly preferred. Such a styrenic 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 has excellent stability. becomes easier. In the following formula (7), the description of R ^31a and R ^31b is referred to the description of R ³¹ above, the description of R ^32a and R ^32b is referred to the description of R ³² above, and the description of R ^33a and R ^33b is referred to See the description of R ³³ above, and the description of X above for X ^a and X ^b .

For details of the styrenic compounds represented by Formula (6) and Formula (7), refer to the description in International Publication No. 2019/009093.

The content of the component (E) in the resin composition is preferably 0.01 parts by mass or more, preferably 0.03 parts by mass, based on 100 parts by mass of the solid content of the resin composition, from the viewpoint of expressing the desired performance. Part or more is more preferable, and 0.1 part by mass or more is even more preferable. In addition, from the viewpoint of improving the moldability and film-forming properties of the resin composition, the content of the component (E) in the resin composition is preferably 20 parts by mass or less in 100 parts by mass of the solid content of the resin composition. 15 parts by mass or less is more preferable, and 10 parts by mass or less is even more preferable. When the resin composition contains a styrenic compound as the component (E), the content of the styrenic compound is also preferably within the above range. The total content of component (B) and component (E) is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and 15 parts by mass in 100 parts by mass of the solid content of the resin composition. More preferred are:

The resin composition may further contain a near-infrared absorbing colorant and/or a visible light absorbing colorant other than the oxocarbon compound. The near-infrared absorbing dye and the visible light absorbing dye may be organic dyes, inorganic dyes, or organic-inorganic composite dyes (for example, organic compounds in which metal atoms or ions are coordinated). Not limited. Near-infrared absorbing dyes and visible light absorbing dyes other than oxocarbon-based compounds have, for example, copper (e.g., Cu(II)) or zinc (e.g., Zn(II)) as central metal ions. Cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, naphthalocyanines, cholines, etc.), cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indoline dyes, arylmethane dyes , quaterylene dyes, diimonium dyes, perylene dyes, quinacdrine dyes, oxazine dyes, dipyrromethene dyes, nickel complex dyes, copper ion dyes, and the like. When the resin composition contains a visible light absorbing dye, it can be used as a resin composition for forming a colored filter or a blue light reducing filter.

When the resin composition also contains other dyes, the content of the other dyes is preferably 60 parts by mass or less with respect to a total of 100 parts by mass of the oxocarbon compound of component (B) and the other dyes. It is more preferably 20 parts by mass or less, and particularly preferably contains substantially no other dyes. In addition, the total content of component (B) and other pigments is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and 15 parts by mass or less in 100 parts by mass of the solid content of the resin composition. More preferred. When the resin composition contains the ultraviolet absorber of component (E), the total content including the ultraviolet absorber of component (E) is preferably within the above range.

The resin composition may contain a solvent. For example, when the resin composition is a resin composition that has been made into a paint, the inclusion of a solvent facilitates the coating of the resin composition. A resin composition containing a solvent can be used as an ink composition.

The solvent may function to dissolve each component contained in the resin composition, or may function as a dispersion medium. Examples of solvents include ketones such as methyl ethyl ketone, 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 ethyl acetate, propyl acetate, butyl acetate; N-methyl-pyrrolidone (specifically, 1 -methyl-2-pyrrolidone, etc.); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane and heptane; ethers such as tetrahydrofuran, dioxane, diethyl ether and dibutyl ether; is mentioned. These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably, for example, 50 parts by mass or more, more preferably 70 parts by mass or more, and preferably less than 100 parts by mass, or 95 parts by mass in 100 parts by mass of the resin composition (or ink composition). Part or less is more preferable. By adjusting the content of the solvent within such a range, it becomes easy to obtain a resin composition having a high concentration of each component.

The resin composition may contain a surface modifier, which suppresses appearance defects such as striations and dents in the resin layer when the resin composition is cured to form a resin layer. can do. The type of the surface modifier is not particularly limited, and siloxane-based surfactants, acetylene glycol-based surfactants, fluorine-based surfactants, acrylic leveling agents, and the like can be used. As the surface conditioner, for example, the BYK (registered trademark) series manufactured by BYK Chemie, the KF series manufactured by Shin-Etsu Chemical Co., Ltd., or the like can be used.

The resin composition may contain a dispersant, which stabilizes the dispersibility of the resin composition and suppresses reaggregation. The type of dispersant is not particularly limited, and EFKA series manufactured by Efka Additives, BYK (registered trademark) series manufactured by BYK Chemie, Solsperse (registered trademark) series manufactured by Nippon Lubrizol, and Disparon manufactured by Kusumoto Kasei Co., Ltd. (registered trademark) series, Ajinomoto Fine Techno Co., Ltd. Ajisper (registered trademark) series, Shin-Etsu Chemical Co., Ltd. KP series, Kyoeisha Chemical Co., Ltd. Polyflow series, DIC Corporation Megafac (registered trademark) series, San Nopco's Disper Aid series or the like can be used.

The resin composition may contain various additives such as plasticizers, surfactants, viscosity modifiers, antifoaming agents, antiseptics, resistivity modifiers, adhesion improvers, etc., as necessary. .

The resin composition can be made into a cured product by curing. The resin composition can be made into a cured product by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like. In this case, the resin composition may be molded after heating to about 150° C. to 350° C. for melting. The shape of the molded article is not particularly limited, but may be plate-like, sheet-like, granular, powdery, lumpy, particle aggregate, spherical, ellipsoidal, lens-like, cubic, columnar, rod-like, cone-like, Cylindrical, acicular, fibrous, hollow fiber, porous and the like can be mentioned. Further, when kneading the resin, an additive such as a plasticizer, which is used in general resin molding, may be added.

The resin composition can be coated by spin coating, solvent casting, roll coating, spray coating, bar coating, dip coating, slit coating, screen printing, flexographic printing, ink jet, or the like. It may be a modified one. When the resin composition is an ink composition, it can be applied to any substrate by such a method. In this case, a liquid or paste resin composition is coated on a substrate (for example, a resin plate, a film, a glass plate, etc.) to form a film having a thickness of 200 μm or less or a sheet having a thickness of more than 200 μm. A cured product can be obtained. The cured product of the resin composition obtained in this manner can be handled in an integrated manner with the substrate.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be preferably used as a resin composition for forming filters used in various applications such as optical device applications, display device applications, mechanical parts, electric/electronic parts and the like. The resin composition can be used, for example, for optical filters such as near-infrared cut filters and light selective transmission filters.

As the optical filter, a resin layer formed by curing the resin composition of the present invention is preferably formed on a substrate, whereby an optical filter in which the substrate and the resin layer are laminated and integrated can be obtained. The resin layer may be provided only on one surface of the substrate, or may be provided on both surfaces.

Although the thickness of the resin layer is not particularly limited, it is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint of ensuring desired light selective transmission performance. The upper limit of the thickness of the resin layer may be, for example, 1 mm or less, 500 μm or less, 200 μm or less, or 50 μm or less. When a resin composition that has been made into a paint is applied onto a substrate by a spin coating method, the thickness of the resin layer can be formed even thinner, and from the viewpoint of forming a thinner optical filter, the resin layer has a thickness of 20 μm or less. , more preferably 10 μm or less, even more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 2 μm or less.

As the substrate, it is preferable to use a transparent substrate such as a resin plate, a resin film, or a glass plate. Among them, it is preferable to use a glass substrate as the substrate. By providing the resin layer on the glass substrate, an optical filter having excellent heat resistance can be obtained. The optical filter thus obtained can be mounted on an electronic component by, for example, solder reflow, and the size of the electronic component can be reduced. In addition, since the glass substrate is less likely to crack or warp even when exposed to high temperatures, it becomes easier to secure adhesion to the resin layer. In particular, when the resin composition contains component (D), the effect of component (D) facilitates enhancing the adhesion between the resin layer and the glass substrate.

Known glasses such as silicate glass, borosilicate glass, borate glass, and phosphate glass can be used for the glass substrate. In these glasses, silicon atoms, boron atoms or phosphorus atoms form a network structure with oxygen atoms to form the main skeleton of the glass. In addition to these atoms, the glass contains sodium, potassium, calcium, Atoms or ions such as magnesium, barium, aluminum, iron, silver, copper, cobalt, nickel, lead, zinc, fluorine may be present. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application.

For example, 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 is preferably 0.4 mm or less, and more preferably 0.3 mm or less from the viewpoint of thinning. .

A protective layer made of the same or different resin as that of the resin layer may be laminated as a second resin layer on the resin layer formed from the resin composition of the present invention. By providing the protective layer, the durability (decomposition resistance) of each component contained in the resin layer can be enhanced. The protective layer may be provided only on one side of the resin layer, or may be provided on both sides.

The optical filter has an antireflection and antiglare layer (antireflection film) that reduces glare from fluorescent lights, etc., a layer that prevents scratches, and a transparent base material that has other functions. may The optical filter may have an ultraviolet reflecting film or a near-infrared reflecting film on the resin layer. It is preferable that the ultraviolet reflective film and the near-infrared reflective film are provided on the light incident side of the resin layer. If the optical filter is provided with an ultraviolet reflective film or a near-infrared reflective film, it is possible to cut more ultraviolet rays and near-infrared rays from the light transmitted through the optical filter. The ultraviolet reflective film and the near-infrared reflective film may be one having the ultraviolet reflective function and the near-infrared reflective function.

The ultraviolet reflective film, the near-infrared reflective film, and the antireflection film (visible light antireflection film) can be composed of a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. Therefore, when imparting such a function to an optical filter, the optical filter preferably has a dielectric multilayer film. A material having a refractive index of 1.7 or more can be used as a material constituting the high refractive index material layer, and a material having a refractive index ranging from 1.7 to 2.5 is usually selected. 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; silicon nitride; Nitrides such as; said oxides, mixtures of said nitrides, and those doped with metals such as aluminum and copper and carbon (e.g., tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. be done. A material having a refractive index of 1.6 or less can be used as a material constituting the low refractive index material layer, and a material having a refractive index ranging from 1.2 to 1.6 is usually selected. Examples of materials forming the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The optical filter may also have an aluminum deposition film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and a small amount of tin oxide are dispersed, or the like.

The thickness of the optical filter is preferably 1 mm or less, for example. As a result, for example, it is possible to sufficiently meet the demand for miniaturization of the imaging device. The thickness of the optical filter is more preferably 500 μm or less, still more preferably 300 μm or less, still more preferably 150 μm or less, more preferably 30 μm or more, and even more preferably 50 μm or more.

The optical filter of the present invention is particularly suitable for imaging device applications. The present invention also includes an imager having an optical filter. An imaging device, also called a solid-state imaging device or an image sensor chip, is an electronic component that converts light from an object into an electrical signal and outputs the electrical signal. The imaging element usually has a detection element (sensor) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor), and may have a lens. Imaging devices are used in, for example, mobile phone cameras, digital cameras, vehicle-mounted cameras, monitoring cameras, display devices (LEDs, etc.), and the like. The imaging device includes one or more optical filters of the present invention, and may have other members as necessary.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and can be carried out with appropriate changes within the scope that can conform to the gist of the above and later descriptions. All of them are included in the technical scope of the present invention.

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

(1-2) Synthesis Example 2: Synthesis of near-infrared absorbing dye B In a 300 mL four-necked flask, 110 g of chloroform, 1.8 g of acetic acid, 5.4 g of 7-nitro-1,2,3,4-tetrahydroquinoline ( 0.0303 mol) and 12.84 g (0.0606 mol) of sodium triacetoxyborohydride are added, and 4.37 g (0.0606 mol) of isobutyraldehyde is added to the solution while stirring with a stirring blade under nitrogen flow (10 mL/min). It was added dropwise over a period of minutes. After completion of dropping, the obtained reaction liquid was added to 300 g of water and neutralized with hydrochloric acid. 300 g of ethyl acetate was added thereto, the organic phase was extracted with a separating funnel, and magnesium sulfate (anhydrous) was added to the extracted organic phase for dehydration. After filtering off solids (inorganic matter) from this organic phase, after concentrating the solvent using an evaporator, using silica gel column chromatography (developing solvent: chloroform) as appropriate, and concentrating and vacuum drying, 1 -isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline.

Next, 2.8 g (0.012 mol) of 1-isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline and 9.0 g of concentrated hydrochloric acid (hydrochloric acid concentration: 36% by weight) were added, and nitrogen flow (5 mL) was added. /min), while stirring with a magnetic stirrer, a solution containing 9.1 g of tin chloride dihydrate and 9.1 g of concentrated hydrochloric acid (concentration of hydrochloric acid: 36% by weight) was added a little while paying attention to the heat of reaction. added one by one. After the addition, the mixture was stirred at room temperature for about 3 hours. After that, the obtained reaction liquid was added to a beaker containing 100 g of pure water and 100 g of ethyl acetate while stirring. Potassium hydroxide solution was added little by little, and after stirring for a while when the pH of the aqueous solution reached around 10, the organic phase was extracted with a separating funnel, and magnesium sulfate (anhydrous) was added to the extracted organic phase. dehydrated. After filtering off solids (inorganic matter) from this organic phase, after concentrating the solvent using an evaporator, optionally using silica gel column chromatography (developing solvent: chloroform), and concentrating and vacuum drying, 1 -isobutyl-7-amino-1,2,3,4-tetrahydroquinoline.

Next, 2.86 g (0.0143 mol) of 1-isobutyl-7-amino-1,2,3,4-tetrahydroquinoline and 50 g of superdehydrated chloroform are placed in a 100 mL three-necked flask, and nitrogen is passed through (5 mL/ min), while stirring with a magnetic stirrer, 4.34 g (0.0429 mol) of triethylamine and 7.86 g (0.0286 mol) of palmitoyl chloride (n-hexadecanoyl chloride) were added, and the mixture was stirred at room temperature for 12 hours. reacted. After completion of the reaction, the resulting reaction solution was added to ion-exchanged water and extracted with ethyl acetate. Magnesium sulfate (anhydrous) was added to the extracted organic phase for dehydration. After filtering off solids (inorganic matter) from this organic phase, after concentrating the solvent using an evaporator, using silica gel column chromatography (developing solvent: chloroform) as appropriate, and concentrating and vacuum drying, 1 -isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline.

Next, 6.3 g (0.0143 mol) of 1-isobutyl-7-(N-palmitoylamino)-1,2,3,4-tetrahydroquinoline and 0.82 g (0.0143 mol) of squaric acid were placed in a 300 mL two-necked flask. 0072 mmol), 30 g of 1-butanol, and 30 g of toluene are added, stirred with a magnetic stirrer under nitrogen flow (10 mL/min), and are brought to reflux conditions while removing eluted water using a Dean-Stark apparatus. and reacted for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitate was separated by filtration. The precipitate separated by filtration was washed with methanol, and only the precipitate was filtered again, and the resulting cake (solid matter) was purified by column chromatography (developing solvent: chloroform) using alumina. The obtained purified product was dried at 60° C. for 12 hours using a vacuum dryer to obtain a near-infrared absorbing dye B (squarylium compound) shown in Table 1. When the transmission spectrum of the near-infrared absorbing dye B in toluene was measured, the maximum absorption wavelength was 700 nm.

(1-3) Synthesis Example 3: Synthesis of UV Absorber A In a 200 mL four-necked flask, 4.98 g (0.039 mol) of 4-fluorobenzaldehyde, 3.57 g (0 .020 mol), 10.86 g (0.079 mol) of potassium carbonate, and 74 g of acetonitrile were charged and reacted at 60° C. for 12 hours under nitrogen flow (10 mL/min) with stirring using a stirring blade. After completion of the reaction, the insoluble matter was filtered off by filtration under reduced pressure, and the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 mL four-necked flask, and 11.09 g (0.079 mol) of isobutyl cyanoacetate, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added and reacted under reflux conditions for 4 hours. let me After completion of the reaction, the solvent was distilled off using an evaporator, and the resulting concentrate was purified by column chromatography (developing solvent: chloroform) to obtain UV absorber A shown in Table 1. When the transmission spectrum of UV absorber A in toluene was measured, the maximum absorption wavelength was 364 nm.

(2) Preparation of resin composition In a 2-liter reaction vessel equipped with a stirring blade, 10.01 g (0.044 mol) of 2,2'-bis(4-hydroxyphenyl)propane, 3.59 g of sodium hydroxide ( 0.090 mol) and 300 g of ion-exchanged water were charged and dissolved, and then 0.89 g (0.009 mol) of triethylamine was added and dissolved. A solution prepared by dissolving 3.57 g (0.021 mol) of terephthalic acid dichloride and 3.57 g (0.021 mol) of isophthalic acid dichloride 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 being kept at 20° C., and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Further, a solution of 0.71 g (0.005 mol) of benzoyl chloride dissolved in 10 g of methylene chloride was added thereto and stirred for 60 minutes. An acetic acid aqueous solution was added to the obtained reaction solution to neutralize it, and after adjusting the pH of the aqueous phase to 7, the oil phase and the aqueous phase were separated using a separating funnel. The obtained oil phase was added dropwise to methanol with stirring to reprecipitate the polymer, and the precipitate was collected by filtration and dried in an oven at 80° C. to obtain a white solid polyarylate resin (PAR resin). The obtained polyarylate resin had a polystyrene-equivalent weight average molecular weight (Mw) of 33,780 and a number average molecular weight (Mn) of 8,130 as measured by gel permeation chromatography.

Add 9.9 parts by mass of the polyarylate resin obtained above to a mixed solvent of 34.5 parts by mass of toluene and 52.5 parts by mass of o-xylene, and further add 0.8 parts by mass of the near-infrared absorbing dye A. , 0.3 parts by mass of near-infrared absorbing dye B, 1.1 parts by mass of ultraviolet absorber A, and 0.03 parts by mass of BYK-310 (polyether-modified polydimethylsiloxane) manufactured by BYK Chemie as a surface conditioner. , mixed uniformly. The base resin composition thus obtained was uniformly mixed with a hydrolyzed solution of an epoxy group-containing silane coupling agent at a mass ratio of 99:1 (base resin composition: silane coupling agent hydrolyzed solution) at 25°C. The resin composition A was obtained by mixing and filtering this with a filter having a pore size of 0.1 μm (manufactured by GL Sciences, non-aqueous 13N) to remove foreign substances. The hydrolyzed solution of the epoxy group-containing silane coupling agent contains 4.0 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., OFS-6040) and 5.7 parts by mass of 2-propanol. and 0.1 part by mass of distilled water were blended and uniformly mixed at 25° C., then 0.2 part by mass of formic acid was added and mixed for 90 minutes to initiate the hydrolysis reaction of 3-glycidoxypropyltrimethoxysilane. Prepared by proceeding.

(3) Evaluation of Storage Stability (3-1) Storage Stability of Resin Composition The resin composition A obtained above was examined for storage stability when stored for 6 months. Resin composition A, when pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) is added as an additive and when no additive is added, changes in viscosity after storage for 6 months, solid content concentration A change in the optical spectrum was investigated. When the additive was added to the resin composition A, 0.3 parts by mass of PEMP was added to 100 parts by mass of the resin composition A. Resin composition A (with/without additives) was placed in a container in which the solvent did not volatilize, and stored at 25° C. for 6 months under light shielding. As a reference, resin composition A with no additives was stored at 10° C. under the same conditions. For the optical spectrum, a resin solution obtained by diluting resin composition A 2000 times with toluene was examined for light transmittance at wavelengths of 550 nm and 720 nm.

The results are shown in Table 2. When PEMP was not added, after storage at 25° C. for 6 months, the transmittance at a wavelength of 550 nm in the visible light region decreased and the transmittance at a wavelength of 720 nm in the near infrared region increased. This indicates that the near-infrared absorbing dye squarylium compound contained in the resin composition A has deteriorated. On the other hand, when PEMP was added, the optical spectrum did not change even after storage at 25° C. for 6 months, and the storage stability was excellent. When stored at 10°C for 6 months without adding PEMP, the degree of deterioration was lower than when stored at 25°C for 6 months without adding PEMP, but even in that case PEMP was added. The storage stability was better when stored at 25°C.

(3-2) Optical properties of optical filter produced from resin composition after storage Resin composition A and PEMP before storage were added and stored at 25°C for 6 months. An optical filter was produced using resin composition A after being stored at 25° C. for 6 months without addition of PEMP, and resin composition A after being stored at 10° C. for 6 months without adding PEMP.

An optical filter was produced as follows. After dropping 1 cc of the resin composition onto a glass substrate (Schott, D263Teco), a spin coater (Mikasa, 1H-D7) was used to rotate 1900 times over 0.3 seconds, and the rotation speed was maintained for 1 second. It was held and formed into a film on a glass substrate. The glass substrate on which the resin composition was formed was replaced with nitrogen at 50° C. for 30 minutes using an inert oven (DN610I, manufactured by Yamato Kagaku Co., Ltd.), then heated to 190° C. in about 15 minutes, and heated to 190° C. in a nitrogen atmosphere. C. for 60 minutes to form a resin layer (absorbing layer) on the glass substrate. The thickness of the resin layer formed on the glass substrate was 1.6 μm. The thickness of the resin layer was obtained from the difference between the thickness of the glass substrate on which the resin layer was formed and the thickness of the glass substrate alone, which were each measured with a micrometer.

Resin composition A before storage, Resin composition A after adding PEMP and storing at 25 ° C. for 6 months, Resin composition A after storing at 10 ° C. for 6 months without adding PEMP Optical formed from All of the filters had excellent transparency with no defects observed even when irradiated with a strong light source (Polarion light). On the other hand, the optical filter formed from the resin composition A after being stored at 25° C. for 6 months without adding PEMP showed turbidity and haze due to foreign matter.

An optical filter (referred to as “optical filter 1”) prepared using resin composition A after adding PEMP and storing at 25° C. for 6 months, and an AR film (vapor deposition) on the resin layer side of optical filter 1 A transmission spectrum was measured for an optical filter 2 in which five layers of TiO ₂ films and SiO ₂ films were alternately laminated according to the method. The results are shown in FIG. 1. Optical filter 2 had high visible light transmittance and a broad absorption band in the near-infrared region. It was found that the optical filter 2 had high durability with no change in optical spectrum, appearance, or adhesion after the boiling test, high temperature and high humidity test, heat cycle test, and sunlight exposure test.

By coating the resin composition of the present invention on a substrate to form a resin layer, it can be used for optical filters useful for applications such as optical devices, display devices, mechanical parts, electric/electronic parts, and the like. .

Claims (8)

A resin composition containing a thermoplastic resin, an oxocarbon compound, and a polyhydric mercaptan compound,
The content of the polyhydric mercaptan compound is 1.0 to 8.0 times by mass the content of the oxocarbon compound,
The resin composition, wherein the oxocarbon compound is a squarylium compound represented by the following formula (1) and/or a croconium compound represented by the following formula (2).

[In Formulas (1) and (2), R ¹ to R ⁴ each independently represent a group represented by Formula (3) or Formula (4) below. ]

[In formula (3),
Ring P represents an optionally substituted aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures,
R ¹¹ to R ¹³ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an aryloxy a carbonyl group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amido group, a sulfonamide group, a carboxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or a ^sulfo group ^; may be linked together to form a ring,
* represents a binding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2). ]

[In formula (4),
R ¹⁴ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfinyl group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an aryloxy a carbonyl group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amido group, a sulfonamide group, a carboxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group, or a ^sulfo group ^; , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ may be linked to each other to form a ring,
* represents a binding site to the 4-membered ring in formula (1) or the 5-membered ring in formula (2). ] The resin composition according to claim 1, wherein the content of said polyhydric mercaptan compound is 0.5 parts by mass or more and 8 parts by mass or less in 100 parts by mass of the solid content of the resin composition. In the formula (3), R ¹¹ ～R ¹³ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group; ¹² and R ¹³ may be linked together to form a ring,
In the formula (4), R ¹⁴ ～R ¹⁸ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, an amide group, an amino group, or a hydroxyl group; ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ 3. The resin composition according to claim 1 or 2, which may be linked to each other to form a ring. The resin composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a hydrolyzed condensate thereof. The resin composition according to any one of claims 1 to 4, further comprising an ultraviolet absorber. An ink comprising the resin composition according to any one of claims 1 to 5 and a solvent. An optical filter comprising: a substrate; and a resin layer formed on the substrate and formed from the resin composition according to any one of claims 1 to 5 or the ink according to claim 6. . An imaging device comprising the optical filter according to claim 7 .

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