JP2020132699A - Resin composition, ink and optical filter - Google Patents

Abstract

To provide a resin composition that contains a thermoplastic resin and an oxocarbon compound, and has excellent long-term storage stability.SOLUTION: A resin composition contains a thermoplastic resin, an oxocarbon compound, and a polyvalent mercaptan compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition containing an oxocarbon-based compound, an ink containing the resin composition, and an optical filter having the resin composition or a resin layer formed from 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 light 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 an oxocarbon-based compound is applied to such an application, it is desirable to handle the oxocarbon-based compound as a resin composition, whereby the handleability of the oxocarbon-based compound can be improved and the processability can be improved.

Patent Documents 1 to 3 disclose various resin compositions containing an oxocarbon-based compound. Patent Document 1 discloses a resin composition containing a specific oxocarbon-based compound, Patent Document 2 discloses a resin composition containing a specific squarylium compound, and Patent Document 3 discloses an oxocarbon-based compound. And a resin composition containing a curing catalyst and a mercapto group-containing compound are disclosed. In the resin composition disclosed in Cited Document 3, an epoxy resin which is a thermosetting resin is used as a base resin, and a curing catalyst is contained in order to cure the resin. Then, by incorporating the oxocarbon-based compound and the mercapto group-containing compound together with the curing catalyst in the resin composition, the oxocarbon-based compound is deteriorated by the epoxy resin or the curing catalyst when the resin is thermally cured to form a cured product. Is suppressed, and the light selective transmittance of the obtained cured product can be enhanced.

Japanese Unexamined Patent Publication No. 2016-0746949 Japanese Unexamined Patent Publication No. 2014-148567 Japanese Unexamined Patent Publication No. 2017-149896

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 the thermoplastic resin is used as the base resin, it is not necessary to contain the mercapto group-containing compound.

On the other hand, considering the industrial use of the resin composition containing an oxocarbon-based compound, it is preferable that the resin composition can be stored for a long period of time without strict temperature control, and for example, it is desirable that the resin composition 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 an object of the present invention is to obtain a resin composition containing a thermoplastic resin and an oxocarbon-based compound, which is excellent in long-term storage stability, and the resin. An object of the present invention is to provide an ink containing a 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 containing a thermoplastic resin, an oxocarbon-based compound, and a multivalent mercaptan compound.
[2] The resin composition according to [1], wherein the content of the multivalent 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-based compound is a squarylium compound represented by the following formula (1) and / or a croconium compound represented by the following formula (2). Composition.

[In the formulas (1) and (2), R ^{1 to} R ⁴ independently represent a group represented by the following formula (3) or the following formula (4). ]

[In equation (3),
Ring P represents an aromatic hydrocarbon ring that may have a substituent, an aromatic heterocycle, 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, and R ¹² and R ¹³ may be linked to each other to form a ring.
* Represents a binding site with a 4-membered ring in formula (1) or a 5-membered ring in formula (2). ]

[In equation (4),
R ^{14 to} R ¹⁸ independently represent a hydrogen atom, an organic group or a polar functional group, and R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ , respectively, respectively. They may be connected to form a ring,
* Represents a binding site with a 4-membered ring in formula (1) or a 5-membered ring in formula (2). ]
[4] The resin composition according to any one of [1] to [3], further containing 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], which further contains an ultraviolet absorber.
[6] An ink containing the resin composition according to any one of [1] to [5] and a solvent.
[7] It is characterized by having 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 image pickup device including the optical filter according to [7].

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

The transmission spectrum of the optical filter produced in the examples is shown.

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

In the resin composition of the present invention, (A) thermoplastic resin is used as the base resin. The thermoplastic resin used as the component (A) is not particularly limited as long as it is a resin that softens by heating. As the thermoplastic resin, it is preferable to use a highly transparent resin, for example, (meth) acrylic resin, (meth) acrylic urethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, and polyolefin resin (for example, Polyethylene resin, polypropylene resin), cycloolefin resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (for example, nylon), aramid resin, polyimide resin, polyamideimide resin, polyester resin (for example, polybutylene terephthalate (for example) (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 (for example) , Fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxyfluororesin (PFA), fluorinated polyaryl ether ketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorine (FPEN), etc.) and the like. Among these, from the viewpoint of excellent transparency and heat resistance, (meth) acrylic resin, cycloolefin resin, polyimide resin, polyamideimide resin, polyester resin, polyarylate resin, polyamide resin, polycarbonate resin, polysulfone resin, fluorine Chemicalized aromatic polymers are preferred.

The (meth) acrylic resin is a polymer having a repeating unit derived from (meth) acrylic acid or a derivative thereof, and for example, a repeating unit derived from (meth) acrylic acid ester such as a poly (meth) acrylic acid ester resin. The resin to have is preferably used. The (meth) acrylic resin preferably has a ring structure in the main chain, for example, a carbonyl group-containing ring structure such as a lactone ring structure, a glutaric anhydride structure, a glutalimido structure, a maleic anhydride structure, and a maleimide ring structure; oxetane. Examples thereof include a carbonyl group-free ring structure such as a ring structure, an azetidine ring structure, a tetrahydrofuran ring structure, a pyrrolidine ring structure, a tetrahydropyran ring structure, and a piperidine ring structure. The carbonyl group-containing ring structure also includes a structure containing a carbonyl group derivative group such as an imide group. Examples of the (meth) acrylic resin having a carbonyl group-containing ring structure are described in JP-A-2004-168882, JP-A-2008-179677, International Publication No. 2005/54311, JP-A-2007-31537 and the like. The ones described can be used.

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

The polyimide resin is a polymer containing an imide bond in the repeating unit of the main chain. For example, polycarboxylic acid dianhydride and diamine are polymerized to obtain polyamic acid, which is dehydrated and cyclized (imidized). It can be manufactured by allowing it to be produced. As the polyimide resin, it is preferable to use an aromatic polyimide in which aromatic rings are linked by an imide bond. Polyimide resins include, for example, Kapton (registered trademark) manufactured by DuPont, Aurum (registered trademark) manufactured by Mitsui Chemicals, Meldin (registered trademark) manufactured by Coralvan, and TPS (registered trademark) TI3000 series manufactured by Toray Plastics Precision Precision Co., Ltd. Etc. can be used.

The polyamide-imide resin is a polymer containing an amide bond and an imide bond in the repeating unit of the main chain. As the polyamide-imide resin, for example, Toron (registered trademark) manufactured by Solvay Advanced Polymers, Vilomax (registered trademark) manufactured by Toyobo, TPS (registered trademark) TI5000 series manufactured by Toray Plastics Precision Precision Co., Ltd., and the like can be used.

The polyester resin is a polymer containing an ester bond in the repeating unit of the main chain, and can be obtained, for example, by polycondensing a polyvalent carboxylic acid (dicarboxylic acid) and a polyalcohol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like. For example, OKP series manufactured by Osaka Gas Chemical Co., Ltd., TRN series manufactured by Teijin Co., Ltd., Theonex ( Registered trademark), Dupont's Lynite (registered trademark), Mitsubishi Chemical's Novapex (registered trademark), Mitsubishi Engineering Plastics' Novaduran (registered trademark), Toray's Lumirer (registered trademark), Trecon (registered trademark) Registered trademark) and the like can be used.

The polyarylate resin is a polymer obtained by polycondensing a dihydric phenol compound and a dibasic acid (for example, an aromatic dicarboxylic acid such as phthalic acid), and has an aromatic ring and an ester bond in the repeating unit of the main chain. It has a repeating unit including and. As the polyarylate resin, for example, Vectran (registered trademark) manufactured by Kuraray, U polymer (registered trademark) manufactured by Unitika Ltd., Unifier (registered trademark), and the like can be used.

The polyamide resin is a polymer containing an amide bond in the repeating unit of the main chain, and can be obtained, for example, by polycondensing diamine and a dicarboxylic acid. The polyamide resin may have an aliphatic skeleton in the main chain, and as such an amide resin, for example, nylon can be used. 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. For example, Twaron (registered trademark) and Cornex (registered trademark) manufactured by Teijin, Kevlar (registered trademark) manufactured by DuPont, and Nomex. (Registered trademark) and the like can be used.

Polycarbonate resin is a polymer containing a carbonate group (-O- (C = O) -O-) as a repeating unit of the main chain. Polycarbonate resins include Panlite (registered trademark) manufactured by Teijin, Upiron (registered trademark), Novarex (registered trademark), Zanter (registered trademark) manufactured by Mitsubishi Engineering Plastics, and SD Polyca manufactured by Sumika Stylon Polycarbonate. (Registered trademark) and the like can be used.

The polysulfone resin is a polymer having a repeating unit containing an aromatic ring, a sulfonyl group (−SO ₂₋ ), and an oxygen atom. As the polysulfone resin, for example, Sumika Excel (registered trademark) PES3600P or PES4100P manufactured by Sumitomo Chemical Co., Ltd., UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers, etc. can be used.

The fluorinated aromatic polymer is a repeat containing an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of ether bonds, ketone bonds, sulfone bonds, amide bonds, imide bonds and ester bonds. 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 the thermoplastic resin, for example, the total light transmittance at a thickness of 0.1 mm is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more. The upper limit of the total light transmittance of the thermoplastic resin is not particularly limited, and the total light transmittance may be 100% or less, but may be, for example, 95% or less. Total light transmittance is measured based on JIS K 7105.

The thermoplastic resin preferably has a high glass transition temperature (Tg), which can enhance 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. The upper limit of the glass transition temperature of the thermoplastic resin is not particularly limited, but is preferably 380 ° C. or lower, for example, from the viewpoint of improving the molding processability of the resin composition.

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

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

The oxocarbon-based compound contained in the resin composition may be a squarylium compound, a croconium compound, or both may be contained. The oxocarbon-based compound contained in the resin composition may be only one kind or two or more kinds.

As the squarylium compound, a compound having a squarylium skeleton represented by the following formula (1) is specifically shown, and as a croconium compound, a compound having a croconium skeleton represented by the following formula (2) is specifically shown. Is done. In the following formulas (1) and (2), R ^{1 to} R ⁴ independently represent organic groups.

As the oxocarbon-based compound, those in which R ^{1 to} R ⁴ are independently represented by the following formula (3) or the following formula (4) in the above formulas (1) and (2) are preferable. .. The squarylium compound or croconium compound having a group represented by the following formula (3) has a wide absorption peak in the red to near infrared region, and can cut light in a relatively wide wavelength range. On the other hand, in the squarylium compound or croconium compound having a group represented by the following formula (4), the absorption peak in the red to near infrared region is formed sharply, so light in the wavelength range corresponding to this absorption peak is selected. It is possible to cut the target.

In the formula (3), ring P represents an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle, or a fused ring containing these ring structures, and R ^{11 to} R ¹³ are independent of each other. It represents a hydrogen atom, an organic group or a polar functional group, and R ¹² and R ¹³ may be linked to each other to form a ring. In formula (4), R ^{14 to} R ¹⁸ independently represent a hydrogen atom, an organic group or a polar functional group, and are R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ . Each of R ¹⁸ may be connected to each other to form a ring. * Represents a binding site with a 4-membered ring in formula (1) or a 5-membered ring in formula (2).

The squalylium compound and the croconium compound may have a compound having a resonance relationship, but the squalylium compound represented by the above formula (1) and the croconium compound represented by the above formula (2) have these Compounds that have a resonance relationship are also included.

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

Examples of the organic group of R ^{11 to} R ¹⁸ include 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 and an aryloxycarbonyl. Examples thereof include a group, an arylsulfonyl group, an arylsulfinyl group, a heteroaryl group, an amino group, an amide group, a sulfonamide group, a carboxy group (carboxylic acid group), a cyano group and the like. Examples of the polar functional groups of R ^{11 to} R ¹⁸ include a halogeno group, a hydroxyl group, a nitro group, a sulfo group (sulfonic acid group) and the like.

The alkyl groups of 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, nonadecil group, icosyl group and other linear or branched alkyl groups; cyclopropyl group, cyclobutyl Examples thereof include cyclic (aliphatic) alkyl groups such as groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclononyl groups and cyclodecyl groups. The alkyl group may have a substituent, and 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. And so on. Examples of the alkyl group having a halogeno group include a monohalogenoalkyl group, a dihalogenoalkyl group, an alkyl group having a trihalomethyl unit, a perhalogenoalkyl group and the like. 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 of the alkyl group (the number of carbon atoms excluding the substituent) is preferably 1 to 20, and specifically, if it is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 20 and more preferably 1 to 20. It is 10, more preferably 1 to 5, and if it is a cyclic alkyl group, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8.

For specific examples of the alkyl group contained in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfinyl group of R ^{11 to} R ¹⁸ , the above description regarding the alkyl group is referred to.

Examples of the aryl group of R ^{11 to} R ¹⁸ include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group and the like. The aryl group may have a substituent, and examples of the substituent contained in the aryl group 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 and an amino group. Examples thereof include a thiocyanate group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group. The number of carbon atoms of the aryl group (the number of carbon atoms excluding the substituent) is preferably 6 to 20, and more preferably 6 to 12.

Examples of the aralkyl group of R ^{11 to} R ¹⁸ include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a naphthylmethyl group and the like. The aralkyl group may have a substituent, and the substituents contained in the aralkyl group 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 carbon number of the aralkyl group (the number of carbon atoms excluding the substituent) is preferably 7 to 25, and more preferably 7 to 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 regarding the aryl group is referred to.

Examples of the heteroaryl group of R ^{11 to} R ¹⁸ include a thienyl group, a thiopyranyl group, an isothiochromenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyraridinyl group, a pyrimidinyl group, a pyridadinyl group, a thiazolyl group and an isothiazolyl group. Examples include a group, a furanyl group, a pyranyl group and the like. The heteroaryl group may have a substituent, and the substituents of the heteroaryl group 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 of the heteroaryl group (the number of carbon atoms excluding the substituent) is preferably 2 to 20, and more preferably 3 to 15.

The amino groups of R ^{11 to} R ¹⁸ are represented by the formula: −NR ^a1 R ^a2 , and R ^a1 and R ^a2 are independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and aralkyl groups. , Heteroaryl groups. Specific examples of the alkyl group, the aryl group, the aralkyl group, and the heteroaryl group refer to the description of these groups above, and the alkenyl group and the alkynyl group are one of the carbon-carbon single bonds of the alkyl group exemplified above. Examples include groups in which the moiety has been replaced with a double or triple bond. R ^a1 and R ^a2 may be connected to each other to form a ring.

Examples of the amide group of R ^{11 to} R ¹⁸ are represented by the formula: -NH-C (= O) -R ^a3 , and R ^a3 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups are referred to in the description of these groups above.

Examples of the sulfonamide groups of R ^{11 to} R ¹⁸ are represented by the formula: -NH-SO _2- R ^a4 , and R ^a4 is an alkyl group, an aryl group, an aralkyl group, or a heteroaryl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, and heteroaryl groups are referred to in the description of these groups above.

Examples of the halogeno group of R ^{11 to} R ¹⁸ include a fluoro group, a chloro group, a bromo group, an iodine group and the like.

Examples of the ring structure formed from R ^{12 to} R ¹⁸ include a hydrocarbon ring and a heterocycle, and these ring structures may or may not have aromaticity, but are non-aromatic. It is preferably a group hydrocarbon ring or a non-aromatic heterocycle. Examples of the non-aromatic hydrocarbon ring include cycloalkanes such as cyclopentane, cyclohexane and cycloheptane; cycloalkenes such as cyclopentene, cyclohexene and cyclohexadiene (for example, 1,3-cyclohexadiene), cycloheptene and cycloheptadiene. Can be mentioned. As the non-aromatic heterocycle, one or more 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). Examples include rings in which at least one atom selected from the above is replaced. Examples of the non-aromatic heterocycle include a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a tetrahydropyran ring, a tetrahydrothiopyran ring, a morpholin ring, a hexamethyleneimine ring, a hexamethylene oxide ring, and a hexamethylene sulfide ring. Examples thereof include a heptamethyleneimine ring.

Is a group R ¹¹ to R ¹³ in the formula (3) are independent, R ¹¹ to R ¹³ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, is an aryl group or an aralkyl group, It is preferable, and a hydrogen atom, an alkyl group, or an aryl group is more preferable. Preferred examples of the alkyl group and aryl group of R ^{11 to} R ¹³ include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group and a phenyl group.

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

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

Ring P may have a substituent, and examples of the substituent include the organic group and the polar functional group described above. When the ring P has a substituent, the number thereof is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. Ring P does not have to have a substituent.

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

Is a group R ¹⁴ to R ¹⁸ is independently in Formula (4), independently R ¹⁴ to R ¹⁸ are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, an amide group or a hydroxyl group, It is preferable to have. By appropriately selecting R ^{14 to} R ¹⁸ , it is possible to control the absorption maximum wavelength of the squarylium compound or the croconium compound to a desired value. Among them, from the viewpoint of stability and ease of production of the squarylium compound and the croconium compound, it is preferable that R ^{14 to} R ¹⁸ are independently hydrogen atoms, alkyl groups, or amide groups. The alkyl group in this case is preferably linear or branched, and the number of carbon atoms thereof is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3.

In the group represented by the formula (4), R ¹⁵ and R ¹⁶ are preferably connected to form a ring, and R ¹⁶ and R ¹⁷ may be further connected to form a ring. In this case, at least R ¹⁴ and R ¹⁸ are independent groups. If the group of the formula (4) is configured in this way, the absorption peak in the red to near infrared region becomes 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 than 10 or less. It is preferable, and 8 or less is more preferable.

In the group represented by the formula (4), or R ¹⁶ is an amino group, or R ¹⁶ is an amino group forms a ring with R ^15, form a ring further linked both R ¹⁷ It is preferable to do so. In this case, the absorption maximum wavelength can be shifted to the long wavelength side (for example, 685 nm or more) to increase the transmittance of light in the red region and bring the color of the transmitted light closer to the actual one. From the same viewpoint, it is preferable that R ¹⁴ or R ¹⁸ is an amide group.

In the squarylium compound and the croconium compound having a group represented by the formula (4), the benzene rings on both sides of the squarylium skeleton or the croconium skeleton may be linked by a linking group. As such a compound, for example, a squarylium compound disclosed in JP-A-2015-176046 is shown.

The content of the component (B) in the resin composition is preferably 0.01 part by mass or more, preferably 0.03 part by mass, based on 100 parts by mass of the solid content of the resin composition, from the viewpoint of exhibiting desired performance. More than parts are more preferable, and 0.1 parts by mass or more is further preferable. Further, from the viewpoint of improving the moldability and film forming property of the resin composition, the content of the component (B) in the resin composition is preferably 25 parts by mass or less based on 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 further preferable. The content of the component (B) in the resin composition means the total content of the plurality of oxocarbon compounds when a plurality of oxocarbon compounds are contained as the component (B).

The resin composition contains a multivalent mercaptan compound as the component (C). When the present inventors examined the storage stability of a resin composition containing a thermoplastic resin and an oxocarbon-based compound, although no particular deterioration was observed in a period of 1 to 2 months, room temperature (for example, When stored at about 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), or when it is formed into a film. It was confirmed that a slight haze occurred in the area. Therefore, when an optical filter or the like is formed using such a resin composition after long-term storage, the desired light selective transmission performance may not be obtained or the transparency may be lowered.

Therefore, in the present invention, in order to ensure long-term storage stability of the resin composition containing the thermoplastic resin and the oxocarbon-based compound, the resin composition contains a polyvalent mercaptan compound. By containing the polyvalent mercaptan compound, deterioration of the oxocarbon-based compound contained in the resin composition is suppressed, and the long-term storage stability of the resin composition is improved. It should be noted that such a deterioration-suppressing effect of the oxocarbon-based compound cannot be obtained even by adding a general antioxidant, and the use of the multivalent mercaptan compound makes it particularly effective for the oxocarbon-based compound. Deterioration can be suppressed. The multivalent mercaptan compound is preferable not only in that a plurality of mercapto groups that suppress the deterioration of the oxocarbon-based compound are present in one molecule, but also because the molecular weight is increased, it volatilizes from the resin composition even if it is stored for a long period of time. It is also preferable in that it easily remains without being left.

The polyvalent mercaptan compound is not particularly limited as long as it is a compound having two or more mercapto groups in one molecule, and for example, 1,2-ethanedithiol, 1,2-propanedithiol, and bis (2-mercaptoethyl). For alkanepolythiols such as ether, bis (2-mercaptoethyl) sulfide, 1,3-bis (2-mercaptoethylthio) propane, 2,3-bis (2-mercaptoethylthio) propane-1-thiol, or alkanepolythiol. Polythiol in which a part of −CH ₂ − contained is replaced with −O−, −S−; trimethylolpropantrimercaptoacetate, trimethylolpropanthris (3-mercaptopropionate), tris-[(3-mercapto). Propionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis mercaptoacetate, dipentaerythritol hexakis (3-mercaptopropionate), etc. Examples of an esterified product of mercaptoalkylcarboxylic acid and a polyol (for example, an alkane polyol, a polyol in which a part of −CH ₂ − contained in an alkane polyol is replaced with −O—, and tris (hydroxyalkyl) isocyanurate). Be done. The polyvalent mercaptan compound contained in the resin composition may be only one kind or two or more kinds. Among these, an esterified product of a mercaptoalkylcarboxylic acid and a polyol is preferable because it is easy to obtain a multivalent mercaptan compound having a larger number of mercapto groups. Further, since such a mercaptan compound has a relatively large molecular weight, it does not volatilize even after long-term storage and tends to remain in the resin composition.

The polyvalent mercaptan compound preferably has 3 or more mercapto groups, and more preferably 4 or more, from the viewpoint of further enhancing the deterioration suppressing effect of the oxocarbon-based compound. On the other hand, from the viewpoint of availability and production of the polyvalent mercaptan compound, the number of mercapto groups contained in the polyvalent mercaptan compound is preferably 10 or less, more preferably 8 or less.

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

The content of the 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 further preferable. On the other hand, even if the component (C) is excessively contained in the resin composition, the effect of enhancing the long-term storage stability is not improved so much. Therefore, in 100 parts by mass of the solid content of the resin composition, (C) The content of the component is preferably 8 parts by mass or less, more preferably 7 parts by mass or less, and further 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-based compound of the component (B) from the viewpoint of suppressing the decomposition of the oxocarbon-based compound during long-term storage of the resin composition. It is preferably times by mass or more, more preferably 1.2 times by mass or more, further preferably 1.5 times by mass or more, and even more preferably 2.0 times by mass or more. On the other hand, even if the component (C) is excessively contained in the resin composition, the effect of suppressing the decomposition of the oxocarbon-based compound during long-term storage is not improved so much, so that the component (C) in the resin composition is not improved. The content is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and further preferably 5.0% by mass or less of the content of the component (B).

The resin composition preferably contains at least one selected from a silane coupling agent, a hydrolyzate of the silane coupling agent, and a hydrolyzed condensate of the silane coupling agent as the component (D). When the resin composition contains the component (D), when the resin layer is formed on the substrate by using the resin composition, 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 may be used. preferable. The silane coupling agent may contain only one of the above functional groups, may contain a plurality of the above functional groups, or may contain only one alkoxysilyl group, or may contain a plurality of the above-mentioned functional groups. May be good.

When the silane coupling agent contains only one alkoxysilyl group, the alkoxysilane represented by the following formula (5) is preferably used as the silane coupling agent. Therefore, as the component (D), it is preferable to use at least one selected from the silane coupling agent represented by the following formula (5), its hydrolyzate, and its hydrolyzed condensate.
SiR ²¹ _k R ²² _m (OR ²³ ) _n (OH) _4-kmn (5)

In formula (5), R ²¹ represents an epoxy group-containing group, an amino group-containing group, a mercapto group-containing group or a polymerizable double bond-containing group, and R ²² and R ²³ each independently represent an alkyl group. 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, the plurality of R ^21s may be the same or different from each other, and when m is 2, the plurality of R ^22s may be the same or different from each other, and n is 2. In the above case, the plurality of OR ²³ may be the same as or different from each other. R ²¹ , R ²² , OR ^23, and OH are groups that directly bond 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 a glycidoxy group-containing group and a cycloalkene oxide (alicyclic epoxy group) -containing group. The glycidoxy group and the cycloalkene oxide may be bonded to the silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). R ²¹ preferably contains only one epoxy group. As the epoxy group-containing group of R ²¹ , glycidoxy group, 3-glycidoxypropyl group, 8- (glycidoxy) -n-octyl group, 3,4-epoxycyclohexyl group, 2- (3,4-epoxycyclohexyl) Ethyl groups and the like can be mentioned.

The amino group-containing group of R ²¹ is not particularly limited as long as it has an amino group, and may have a primary amino group, a secondary amino group, or a tertiary amino group. 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 a silicon atom via a linking group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). Examples of the amino group-containing group of R ²¹ include 3-aminopropyl group, 3- (2-aminoethyl) aminopropyl group, 3- (6-aminohexyl) aminopropyl group, and 3- (N, N-dimethylamino). Examples thereof include a propyl group, an N-phenylaminomethyl group, an N-phenyl-3-aminopropyl group, an N-benzyl-3-aminopropyl group, an N-cyclohexylaminomethyl group and the like.

The mercapto group-containing group of R ²¹ is not particularly limited as long as it has a mercapto group, but a mercaptoalkyl group is preferable. The alkyl group in the mercaptoalkyl group may be linear or branched, and the number of carbon atoms thereof is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 6. R ²¹ preferably contains only one mercapto group. Examples of the mercapto group-containing group of R ²¹ include a 3-mercaptopropyl group, a 2-mercaptoethyl group, a 2-mercaptopropyl group, and a 6-mercaptohexyl group.

The polymerizable double bond-containing group of R ²¹ is not particularly limited as long as it has a polymerizable double bond group, and the polymerizable double bond group includes a vinyl group, a styryl group, a (meth) acrylic group and the like. Can be 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 of R ²¹ include a vinyl group, a 2-propenyl group, a styryl group, a 3- (meth) acryloxypropyl group and the like.

From the viewpoint of enhancing the adhesion of the resin layer to the substrate, it is preferable that the epoxy group, amino group, mercapto group or polymerizable double bond group contained in R ²¹ is not too far from the silicon atom. The group 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 further preferably 1 to 3 carbon atoms. Preferred examples of R ²² include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Preferred examples of OR ²³ include a methoxy group, an ethoxy group, an n-propoxy group and an isopropoxy group.

In the 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. The polymer-type polyfunctional silane coupling agent has a structure in which a group and an alkoxysilyl group-containing group are bonded to an organic polymer chain, contains a plurality of alkoxysilyl groups in one molecule, and has an epoxy group, an amino group, and a mercapto. A plurality of functional groups such as a group and a polymerizable double-bonding group can also be included. The organic chain of the polymer-type polyfunctional silane coupling agent does not contain polysiloxane. By constructing 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 the component (D) can be obtained by converting the alkoxysilyl group contained in the silane coupling agent into a silanol group by hydrolysis. The hydrolyzed condensate of the silane coupling agent can be obtained by dehydrating and condensing the silanol groups contained in the hydrolyzate of the silane coupling agent to form a siloxane bond (-Si-O-Si-). Can be done. Usually, when a silane coupling agent is hydrolyzed, a hydrolyzate of the silane coupling agent is obtained, and a dehydration condensation reaction of silanol groups contained in the hydrolyzate also occurs, so that the hydrolysis condensation of the silane coupling agent occurs. Things can be easily obtained. The hydrolyzate of the silane coupling agent may be a dehydration condensate of the hydrolyzate of the same type of silane coupling agent, or may be a dehydration condensate of the hydrolyzate of a different type of silane coupling agent. ..

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

The resin composition may contain only one type (D) component, 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), whereby the adhesion of the resin layer to the substrate is particularly severe. Adhesion after boiling in water, which is a condition, can be improved. More preferably, the component (D) contains at least a hydrolyzate or a hydrolyzed condensate of an epoxy group-containing silane coupling agent.

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

The content of the component (D) in the resin composition is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further 1 part by mass or more, based on 100 parts by mass of the solid content of the resin composition. It is preferable, 20 parts by mass or less is preferable, 10 parts by mass or less is more preferable, and 5 parts by mass or less is further preferable. If the component (D) is contained in a content of 0.1 part by mass or more in 100 parts by mass of the solid content of the resin composition, when the resin layer is formed on the substrate using the resin composition, the resin layer is formed. 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 enhancing the adhesion of the resin layer to the substrate is not improved so much, so that the solid content of the resin composition is 100 parts by mass. , The content of the component (D) is preferably 20 parts by mass or less. The content of the component (D) based on the thermoplastic resin of the component (A) is preferably 0.5 parts by mass or more, preferably 1 part by mass or more, based on 100 parts by mass of the thermoplastic resin of the component (A). Is more preferable, 3 parts by mass or more is further preferable, 30 parts by mass or less is preferable, 20 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.

The resin composition may have an ultraviolet absorber as the component (E). When the resin composition contains an ultraviolet absorber, deterioration of the resin composition due to light in the ultraviolet to purple region can be suppressed. Further, by curing the resin composition to form a resin molded body or forming a resin layer on the substrate, it is possible to form an optical filter that cuts light in the ultraviolet to purple region. Furthermore, even if exposed to ultraviolet light during storage of the resin composition or during manufacturing / processing of an optical filter (for example, vapor deposition or mounting), other components contained in the resin component or the resin composition from the ultraviolet light. It is possible to protect the component, particularly the component (B), and suppress the deterioration of these components.

Examples of the ultraviolet absorbing dye include known ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazine compounds, cyanoacrylate compounds, benzoxazole compounds, merocyanine compounds, and triazine compounds. Can be used. As the ultraviolet absorber, only one kind may be used, or two or more kinds may be used. As the ultraviolet absorber, a commercially available substance may be used. For example, ADEKA's ADEKA STAB (registered trademark) series, BASF's TINUVIN (registered trademark) series, and Sankyo Kasei's dyslyzer (registered trademark) series. , Sumitomo Chemical's Sumisorb (registered trademark) series, Kyodo Yakuhin's Biosorb (registered trademark) series, Cipro Kasei's Seasorb (registered trademark) series, and the like can be used.

As the ultraviolet absorber, it is also preferable to use a styrene compound represented by the following formula (6). The styrene-based 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 is defined. Can be formed sharply.

In the above formula (6), R ³¹ represents a cyano group, an acyl group, a carboxylic acid ester group or an amide group, and R ³² is a hydrogen atom, a cyano group, an acyl group, a carboxylic acid ester group, an amide group, a hydrocarbon group or Representing a heteroaryl group, where R ³¹ and R ³² are both acyl groups, carboxylic acid ester groups or amides, R ³¹ and R ³² may be linked to each other to form a ring, where R ³³ is a hydrogen atom. Or an alkyl group, R ³⁴ represents a hydrogen atom, an organic group or a polar functional group, multiple R ^34s may be the same or different from each other, X represents a sulfur or oxygen atom, L represents a hydrogen atom or Representing a divalent or higher linking group, a represents an integer of 1 or more, and when a is 2 or more, the plurality of groups bonded to L may be the same or different from each other. In equation (6), R ³¹ (or R ³² ) may be in the cis or trans position with respect to R ³³ .

The acyl groups (alkanoyl groups) of R ³¹ and R ³² include a methanoyl group, an etanoyl group, a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoil group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group and a dodecanoyl group. , Tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyyl group, eikosanoyl group and the like. A part of the hydrogen atom 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 of the acyl group (the number of carbon atoms excluding the substituent) is preferably 2 to 21, more preferably 2 to 11, and further preferably 2 to 6.

^Examples of the carboxylic acid ester groups of R ³¹ and R ³² are those represented by the formula: -C (= O) -OR ^b1 in which R ^b1 is an alkyl group, an aryl group, or an aralkyl group. For specific examples of alkyl groups, aryl groups, and aralkyl groups, the description of these groups of R ^{11 to} R ¹⁸ above is referred to.

The amide groups of R ³¹ and R ³² are 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. Alternatively, it may be an aralkyl group. Specific examples of the alkyl group, aryl group, and aralkyl group of R ^b2 and R ^b3 refer to the above description of these groups of R ^{11 to} R ¹⁸ , and specific examples of the acyl group of R ^b3 are described above in R ^31. And the description of the acyl group of R ³² .

When R ³¹ and R ³² are both acyl groups and they are connected to each other to form a ring, the group formed from R ³¹ and R ³² is of the formula: -C (= O) -R ^b4- C ( The group represented by = O)-is shown. When both R ³¹ and R ³² are carboxylic acid ester groups and they are linked to each other to form a ring, the group formed from R ³¹ and R ³² is of the formula: -C (= O) -OR. ^{b5 The} group represented by ^−OC (= O) − is shown. When both R ³¹ and R ³² are amide groups and they are connected to each other to form a ring, the group formed from R ³¹ and R ³² is of the formula: -C (= O) -NR ^b6 -R ^b7. The group represented by −NR ^b8 −C (= O) − is shown. In these equations, R ^b4 , R ^b5 and R ^b7 independently represent linear or branched alkylene groups, and R ^b6 and R ^b8 independently represent hydrogen atoms or hydrocarbon groups, respectively. , 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). In the alkylene group of R ^b4 , R ^b5 and R ^b7 , a part of the hydrogen atom may be substituted with an aryl group, an alkoxy group, a cyano group, a halogeno group, a hydroxyl group, a nitro group or the like. The carbon number of the alkylene group of R ^b4 , R ^b5 and R ^b7 (the number of carbon atoms excluding the substituent) is preferably 2 to 10 and more preferably 3 to 8. Preferred examples of the hydrocarbon group of R ^b6 and R ^b8 include an alkyl group, an aryl group or an aralkyl group, and specific examples of these groups include the above-mentioned alkyl groups, aryl groups and aralkyl groups of R ^{11 to} R ¹⁸ . See description.

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

For details of the organic group and polar functional group of R ³⁴ of the formula (6), refer to the above description of the organic group and polar functional group of R ^{11 to} R ¹⁸ . The 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, and is preferably a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. Among the four R ^34s bonded to the benzene ring of the formula (6), two or more are preferably hydrogen atoms, three or more are more preferably hydrogen atoms, and all four are hydrogen atoms. It is particularly preferable to have.

In the formula (6), X may be bonded to the ortho position, the meta position, or the para position with respect to the ethylene structural portion containing R ^{31 to} R ^33. May be good. From the viewpoint of ease of production of the styrene compound, it is preferable that X is bonded to the ethylene structure at the para position.

In the formula (6), when L is a divalent or higher valent linking group, the linking group includes an alkylene group, an arylene group, a heteroarylene group, -O-, -CO-, -S-, -SO-, Divalent linking group such as −SO ₂ −, −NH −; trivalent linking group such as methine group (−C <) and −N <which may have an alkyl group;> C <etc. 4 Linking groups of valence; and linking groups that combine them. The alkylene group may be linear, branched or cyclic. Further, 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 linking group of divalent or more. Further, the linking group L is an alkylene group in which a part of the hydrogen atom may be replaced with a hydroxyl group and / or a thiol group, and an arylene group in which a part of the hydrogen atom may be replaced with a hydroxyl group and / or a thiol group. , -O-, -S-, and a linking group combining these groups are preferred (although the ether and thioether bonds are not continuous). The number of carbon atoms (consecutive carbon atoms) of the linear or branched alkylene group is preferably 6 or less, more preferably 4 or less, still 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 carbon number of the arylene group is preferably 5 or more, more preferably 6 or more, preferably 10 or less, and more preferably 8 or less.

As the styrene-based compound, the styrene-based compound represented by the following formula (7) is particularly preferably shown. Such a styrene compound has, for example, a peak having an absorption maximum in the wavelength range of 300 nm to 420 nm, can effectively absorb light in the ultraviolet (UVA) to violet region, and has excellent stability. Becomes easier. In the following equation (7), the description of R ^31a and R ^31b refers to the description of R ³¹ above, the description of R ^32a and R ^32b refers to the description of R ³² above, and the description of R ^33a and R ^33b . Refers to the description of R ³³ above, and the description of X ^a and X ^b refers to the description of X above.

For details of the styrene-based compound represented by the formula (6) and the formula (7), refer to the description of International Publication No. 2019/09093.

The content of the component (E) in the resin composition is preferably 0.01 part by mass or more, preferably 0.03 part by mass, based on 100 parts by mass of the solid content of the resin composition, from the viewpoint of exhibiting desired performance. More than parts are more preferable, and 0.1 parts by mass or more is further preferable. Further, from the viewpoint of improving the moldability, film forming property, etc. of the resin composition, the content of the component (E) in the resin composition is preferably 20 parts by mass or less based on 100 parts by mass of the solid content of the resin composition. It is more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. When the resin composition contains a styrene-based compound as the component (E), it is also preferable that the content of the styrene-based compound is in the above range. The total content of the component (B) and the component (E) is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and 15 parts by mass, based on 100 parts by mass of the solid content of the resin composition. The following is more preferable.

The resin composition may further contain a near-infrared absorbing dye and / or a visible light absorbing dye other than the oxocarbon-based compound. The near-infrared absorbing dye and the visible light absorbing dye are particularly organic dyes, inorganic dyes, and organic-inorganic composite dyes (for example, organic compounds coordinated with metal atoms or ions). Not limited. Examples of the near-infrared absorbing dye and the visible light absorbing dye other than the oxocarbon compound include copper (for example, Cu (II)) and zinc (for example, Zn (II)) as the central metal ion. Good cyclic tetrapyrrole dyes (porphyrins, chlorins, phthalocyanines, naphthalocyanines, cholines, etc.), cyanine dyes, azo dyes, quinone dyes, xanthene dyes, indolin 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 coloring 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, preferably 60 parts by mass or less, based on 100 parts by mass of the total of the oxocarbon-based compound of the component (B) and the other dyes. It is more preferably parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably substantially free of other dyes. Further, the total content of the component (B) and other dyes is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and 15 parts by mass or less based on 100 parts by mass of the solid content of the resin composition. More preferred. When the resin composition contains the ultraviolet absorber of the component (E), it is preferable that the total content including the ultraviolet absorber of the component (E) is within the above range.

The resin composition may contain a solvent. For example, when the resin composition is a paint-based resin composition, the inclusion of a solvent facilitates the coating of the resin composition. The resin composition containing a solvent can be used as an ink composition.

The solvent may function as a solvent for dissolving each component contained in the resin composition, or may function as a dispersion medium. Examples of the solvent 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. Classes (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). Pyrrolidones such as −methyl-2-pyrrolidone); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane and heptane; ethers such as tetrahydrofuran, dioxane, diethyl ether and dibutyl ether; etc. Can be mentioned. Only one of these solvents may be used, or two or more of these solvents may be used in combination.

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, 95 parts by mass, based on 100 parts by mass of the resin composition (or ink composition). Less than a part 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 conditioner, which suppresses appearance defects such as striations and dents in the resin layer when the resin composition is cured to form the resin layer. can do. The type of the surface conditioner is not particularly limited, and a siloxane-based surfactant, an acetylene glycol-based surfactant, a fluorine-based surfactant, an acrylic-based leveling agent, and the like can be used. As the surface conditioner, for example, BYK (registered trademark) series manufactured by Big Chemie, KF series manufactured by Shin-Etsu Chemical Co., Ltd., and the like can be used.

The resin composition may contain a dispersant, which can stabilize the dispersibility of the resin composition and suppress reaggregation. The type of dispersant is not particularly limited, and is EFKA series manufactured by Fuka Additives, BYK (registered trademark) series manufactured by Big Chemie, Solsperse (registered trademark) series manufactured by Japan Lubrizol, and Disparon manufactured by Kusumoto Kasei. (Registered Trademark) Series, Ajinomoto Fine-Techno's Ajispar (Registered Trademark) Series, Shinetsu Chemical Industry's KP Series, Kyoeisha Chemical's Polyflow Series, DIC's MegaFuck (Registered Trademark) Series, A Dispar Aid series manufactured by San Nopco can be used.

The resin composition may contain various additives such as a plasticizer, a surfactant, a viscosity regulator, a defoamer, a preservative, a resistivity regulator, and an adhesion improver, if necessary. ..

The resin composition can be made into a cured product by curing. The resin composition can be made into a cured product by, for example, injection molding, extrusion molding, vacuum forming, compression molding, blow molding or the like. In this case, the resin composition may be molded by heating to, for example, about 150 ° C. to 350 ° C. to melt it. The shape of the molded product is not particularly limited, but plate-like, sheet-like, granular, powder-like, lump-like, particle-aggregate-like, spherical, elliptical-spherical, lenticular, cubic, columnar, rod-like, and conical, Examples include a tubular shape, a needle shape, a fibrous shape, a hollow thread shape, and a porous shape. Further, when kneading the resin, an additive used for ordinary resin molding such as a plasticizer may be added.

The resin composition is a paint that can be applied by spin coating method, solvent casting method, roll coating method, spray coating method, bar coating method, dip coating method, slit coating method, screen printing method, flexographic printing method, inkjet method, etc. It may be a modified product. When the resin composition is an ink composition, it can be applied to any base material by such a method. In this case, a liquid or paste-like resin composition is applied onto 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 thus obtained can be handled integrally with the base material.

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

The optical filter preferably has a resin layer obtained by curing the resin composition of the present invention formed on the 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 on only one side of the substrate, or may be provided on both sides.

The thickness of the resin layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 1 μm or more, for example, 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 the coated resin composition is applied onto the substrate by the spin coating method, the thickness of the resin layer can be further reduced, and from the viewpoint of forming a thinner optical filter, the resin layer is 20 μm or less. Is preferable, 10 μm or less is more preferable, 5 μm or less is further preferable, 3 μm or less is even more preferable, and 2 μm or less is particularly preferable.

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. In the optical filter thus obtained, for example, the optical filter can be mounted on an electronic component by solder reflow, and the size of the electronic component can be reduced. Further, since the glass substrate is less likely to crack or warp even when exposed to a high temperature, it becomes easy to secure the adhesion with the resin layer. In particular, when the resin composition contains the component (D), the action of the component (D) makes it easy to improve the adhesion between the resin layer and the glass substrate.

As the glass used for the glass substrate, known glass such as silicate glass, borosilicate glass, borate glass, and phosphoric acid glass can be used. 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, and in addition to these atoms, sodium, potassium, calcium, etc. Atoms or ions such as magnesium, barium, aluminum, iron, silver, copper, cobalt, nickel, lead, zinc and fluorine may be present. The glass may be colorless and transparent, and colored glass such as blue glass may be used depending on the application.

The thickness of the substrate is, for example, preferably 0.05 mm or more, more preferably 0.1 mm or more, and more preferably 0.4 mm or less, more preferably 0.3 mm or less, from the viewpoint of ensuring strength. ..

On the resin layer formed from the resin composition of the present invention, a protective layer made of the same or different resin as the resin layer may be laminated as the second resin layer. 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 on only one side of the resin layer, or may be provided on both sides.

The optical filter has a layer having antireflection and antiglare properties (antireflection film) for reducing reflection of fluorescent lamps, a layer having scratch prevention performance, a transparent base material having other functions, and the like. You 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 reflecting film and the near infrared reflecting film are provided on the light receiving side of the resin layer. If the optical filter is provided with an ultraviolet reflecting film or a near-infrared reflecting film, ultraviolet rays and near-infrared rays can be further cut from the transmitted light of the optical filter. The ultraviolet reflecting film and the near-infrared reflecting film may be one having an ultraviolet reflecting function and a near-infrared reflecting 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 the optical filter, it is preferable that the optical filter has a dielectric multilayer film. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index in the range of 1.7 to 2.5 is usually selected. Examples of the material 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. Nitridees such as; the oxides and mixtures of the nitrides, and those obtained by doping them with metals such as aluminum and copper or carbon (for example, tin-doped indium oxide (ITO), antimonated tin oxide (ATO)) and the like. Be done. As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index in the range of 1.2 to 1.6 is usually selected. Examples of the material constituting the low refractive index material layer include silicon dioxide (silica), alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoride, and the like.

The optical filter may also have an aluminum vapor 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.

The thickness of the optical filter is preferably 1 mm or less, for example. Thereby, for example, it is possible to sufficiently meet the demand for miniaturization of the image sensor. The thickness of the optical filter is more preferably 500 μm or less, still more preferably 300 μm or less, even more preferably 150 μm or less, still more preferably 30 μm or more, still more preferably 50 μm or more.

The optical filter of the present invention is particularly suitable for an image sensor application. The present invention also includes an image pickup device having an optical filter. The image sensor, also called a solid-state image sensor or an image sensor chip, is an electronic component that converts the light of a subject into an electric signal and outputs it as an electric signal. The image pickup device usually has a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor), and may have a lens. The image sensor is used, for example, in a mobile phone camera, a digital camera, an in-vehicle camera, a surveillance camera, a display element (LED or the like), or the like. The image pickup device may include one or two or more optical filters of the present invention, and may further include other members, if 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 is carried out with appropriate modifications to the extent that it can be adapted to the gist of the above and the following. It is also possible, and all of them are included in the technical scope of the present invention.

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

(1-2) Synthesis Example 2: Synthesis of near-infrared absorbing dye B In a 300 mL 4-neck flask, 110 g of chloroform, 1.8 g of acetic acid, and 5.4 g of 7-nitro-1,2,3,4-tetrahydroquinoline ( 0.0303 mol), 12.84 g (0.0606 mol) of sodium triacetoxyborohydride was added, and 4.37 g (0.0606 mol) of isobutyraldehyde was added under nitrogen flow (10 mL / min) while stirring using a stirring blade. Dropped over a minute. After completion of the dropping, the obtained reaction solution 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 the solid matter (inorganic component) is filtered off from this organic phase, the solvent is concentrated using an evaporator, and then silica gel column chromatography (developing solvent: chloroform) is appropriately used, and concentration and vacuum drying are performed. -Isobutyl-7-nitro-1,2,3,4-tetrahydroquinoline was obtained.

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 the mixture was subjected to nitrogen flow (5 mL). / Min), while stirring with a magnetic stirrer, add a little solution containing 9.1 g of tin chloride dihydrate and 9.1 g of concentrated hydrochloric acid (hydrochloric acid concentration 36% by weight), 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. Then, the obtained reaction solution was added to a beaker containing 100 g of pure water and 100 g of ethyl acetate with stirring. Potassium hydroxide solution is added little by little, and after stirring for a while when the pH of the aqueous solution becomes around 10, the organic phase is extracted with a separating funnel, and magnesium sulfate (anhydrous) is added to the extracted organic phase. And dehydrated. After the solid matter (inorganic component) is filtered off from this organic phase, the solvent is concentrated using an evaporator, and then silica gel column chromatography (developing solvent: chloroform) is appropriately used, and concentration and vacuum drying are performed. -Isobutyl-7-amino-1,2,3,4-tetrahydroquinoline was obtained.

Next, 2.86 g (0.0143 mol) of 1-isobutyl-7-amino-1,2,3,4-tetrahydroquinoline and 50 g of super-dehydrated chloroform were placed in a 100 mL three-necked flask under nitrogen flow (5 mL / 5 mL /). Min), while stirring with a magnetic stirrer, add 4.34 g (0.0429 mol) of triethylamine and 7.86 g (0.0286 mol) of palmitoyl chloride (n-hexadecanoyl chloride) for 12 hours at room temperature. It was reacted. After completion of the reaction, the obtained 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 the solid matter (inorganic component) is filtered off from this organic phase, the solvent is concentrated using an evaporator, and then silica gel column chromatography (developing solvent: chloroform) is appropriately used, and concentration and vacuum drying are performed. -Isobutyl-7- (N-palmitoylamino) -1,2,3,4-tetrahydroquinoline was obtained.

Then, in a 300 mL two-necked flask, 6.3 g (0.0143 mol) of 1-isobutyl-7- (N-palmitoylamino) -1,2,3,4-tetrahydroquinoline and 0.82 g of squaric acid (0. 0072 mmol), 30 g of 1-butanol, and 30 g of toluene were added, and the mixture was stirred with a magnetic stirrer under nitrogen flow (10 mL / min), and the reflux conditions were adjusted while removing the eluted water using a Dean-Stark apparatus. It was allowed to react for 3 hours. After completion of the reaction, the mixture was cooled to room temperature and the precipitate was filtered off. The filtered precipitate was washed with methanol, and only the precipitate was filtered again, and the obtained cake (solid) was purified by column chromatography with alumina (developing solvent: chloroform). 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 absorption maximum 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 and 3.57 g (0) of ethylene glycol bis (2-mercaptoethyl) ether. .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) while stirring with a stirring blade. After completion of the reaction, the insoluble matter was filtered off by vacuum filtration, and then the solvent was distilled off using an evaporator. The obtained concentrate was placed in a 200 mL 4-neck flask, 11.09 g (0.079 mol) of isobutyl cyanoacetate, 3.32 g (0.039 mol) of piperidine, and 68 g of methanol were added thereto, and the mixture was reacted under reflux conditions for 4 hours. I let you. After completion of the reaction, the solvent was distilled off using an evaporator, and the obtained concentrate was purified by column chromatography (developing solvent: chloroform) to obtain an ultraviolet absorber A shown in Table 1. When the transmission spectrum of the ultraviolet absorber A in toluene was measured, the maximum absorption wavelength was 364 nm.

(2) Preparation of resin composition In a reaction vessel having a capacity of 2 liters equipped with a stirring blade, 10.01 g (0.044 mol) of 2,2'-bis (4-hydroxyphenyl) propane and 3.59 g of sodium hydroxide ( 0.090 mol), 300 g of ion-exchanged water was 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 this was attached to the reaction vessel. The solution in the reaction vessel was stirred while maintaining the temperature at 20 ° C., and the methylene chloride solution was added dropwise from the dropping funnel over 60 minutes. Further, a solution prepared by dissolving 0.71 g (0.005 mol) of benzoyl chloride in 10 g of methylene chloride was added thereto, and the mixture was stirred for 60 minutes. An aqueous acetic acid solution was added to the obtained reaction solution for neutralization to bring the pH of the aqueous phase to 7, and then the oil phase and the aqueous phase were separated using a separating funnel. The obtained oil phase was added dropwise to methanol under stirring to reprecipitate the polymer, and the precipitate was recovered by filtration and dried in an oven at 80 ° C. to obtain a white solid polyarylate resin (PAR resin). The polystyrene-equivalent weight average molecular weight (Mw) was 33,780 and the number average molecular weight (Mn) was 8,130 as measured by gel permeation chromatography of the obtained polyarylate resin.

9.9 parts by mass of the polyallylate resin obtained above was added to a mixed solvent of 34.5 parts by mass of toluene and 52.5 parts by mass of o-xylene, and 0.8 parts by mass of near infrared absorbing dye A was added thereto. , 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 Big Chemie as a surface conditioner. , Mixed uniformly. The base resin composition thus obtained was uniformly used at 25 ° C. in a mass ratio of a hydrolyzed solution of an epoxy group-containing silane coupling agent and a base resin composition: silane coupling agent hydrolyzed solution = 99: 1. 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 Science Co., Ltd., non-aqueous 13N) to remove foreign substances. The hydrolyzed solution of the epoxy group-containing silane coupling agent was 4.0 parts by mass of 3-glycidoxypropyltrimethoxysilane (OFS-6040 manufactured by Toray Dowcorning Co., Ltd.) and 5.7 parts by mass of 2-propanol. And 0.1 part by mass of distilled water were mixed and mixed uniformly at 25 ° C., then 0.2 part by mass of formic acid was added and mixed for 90 minutes to hydrolyze 3-glycidoxypropyltrimethoxysilane. Prepared by advancing.

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

The results are shown in Table 2. When PEMP was not added, 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 after storage at 25 ° C. for 6 months. This indicates that the squarylium compound of the near-infrared absorbing dye 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 reduced as compared with the case where it was stored at 25 ° C. for 6 months without adding PEMP, but even in that case, PEMP was added. The result was that the storage stability was better when stored at 25 ° C.

(3-2) Optical Characteristics of Optical Filter Made from Resin Composition After Storage Add Resin Composition A, PEMP before storage and store at 25 ° C. for 6 months. Add Resin Composition A, PEMP. Optical filters were prepared using the resin composition A after storing at 25 ° C. for 6 months and the resin composition A after storing at 10 ° C. for 6 months without adding PEMP.

The optical filter was prepared as follows. After dropping 1 cc of the resin composition on a glass substrate (D263Teco manufactured by Schott), use a spin coater (1HD7 manufactured by Mikasa) to make 1900 rotations over 0.3 seconds, and then at that rotation speed for 1 second. It was held and formed on a glass substrate. The glass substrate on which the resin composition was formed was subjected to nitrogen substitution at 50 ° C. for 30 minutes using an inert oven (manufactured by Yamato Scientific Co., Ltd., DN610I), and then the temperature was raised to 190 ° C. in about 15 minutes, and under a nitrogen atmosphere, 190. A resin layer (absorption layer) was formed on the glass substrate by drying at ° C. for 60 minutes. The thickness of the resin layer formed on the glass substrate was 1.6 μm. The thickness of the resin layer was determined by measuring the thickness of the glass substrate on which the resin layer was formed and the thickness of the glass substrate alone with a micrometer, and determining the difference between the two.

Optical formed from the resin composition A before storage, the resin composition A after adding PEMP and storing at 25 ° C. for 6 months, and the resin composition A after storing at 10 ° C. for 6 months without adding PEMP. None of the filters showed any defects even when irradiated with a strong light source (polarion light), and had excellent transparency. 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 produced using the resin composition A after adding PEMP and storing at 25 ° C. for 6 months (this is referred to as "optical filter 1") and an AR film (deposited film) on the resin layer side of the optical filter 1. By the method, the transmission spectrum of the optical filter 2 in which the TiO ₂ film and the SiO ₂ film were alternately laminated (5 layers) was measured. The results are shown in FIG. 1. The optical filter 2 had high visible light transmittance and a wide absorption band in the near infrared region. It was found that the optical filter 2 has high durability without any change in optical spectrum, appearance, or adhesion even after the boiling test, high temperature and high humidity test, heat cycle test, and sunlight exposure test.

The resin composition of the present invention can be used for an optical filter or the like useful for applications such as optical devices, display devices, mechanical parts, electrical / electronic parts, etc. by coating on a substrate to form a resin layer. ..

Claims (8)

A resin composition containing a thermoplastic resin, an oxocarbon-based compound, and a multivalent mercaptan compound. The resin composition according to claim 1, wherein the content of the multivalent 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. The resin composition according to claim 1 or 2, wherein the oxocarbon-based compound is a squarylium compound represented by the following formula (1) and / or a croconium compound represented by the following formula (2).

[In the formulas (1) and (2), R ^{1 to} R ⁴ independently represent a group represented by the following formula (3) or the following formula (4). ]

[In equation (3),
Ring P represents an aromatic hydrocarbon ring that may have a substituent, an aromatic heterocycle, 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, and R ¹² and R ¹³ may be linked to each other to form a ring.
* Represents a binding site with a 4-membered ring in formula (1) or a 5-membered ring in formula (2). ]

[In equation (4),
R ^{14 to} R ¹⁸ independently represent a hydrogen atom, an organic group or a polar functional group, and R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , and R ¹⁷ and R ¹⁸ , respectively, respectively. They may be connected to form a ring,
* Represents a binding site with a 4-membered ring in formula (1) or a 5-membered ring in formula (2). ] The resin composition according to any one of claims 1 to 3, further containing 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 containing an ultraviolet absorber. An ink containing the resin composition according to any one of claims 1 to 5 and a solvent. An optical filter having 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 image pickup device comprising the optical filter according to claim 7.

Images