JP6796443B2 - Light selective absorption resin laminate - Google Patents

Description

The present invention relates to a light selective absorption resin laminate, specifically, a light selective absorption resin laminate capable of absorbing light in the near infrared region.

In recent years, optical materials having a laminated structure composed of various layers have been widely used in various fields such as optical devices such as display elements and image pickup elements in order to achieve multi-functionality. Examples of the layer included in such a laminated structure include an antireflection layer that reduces the reflection of light on the substrate surface, a near-infrared absorbing layer that reduces optical noise in the image sensor, and the like. Various near-infrared absorbing structures (for example, near-infrared cut filters) that reduce noise in the near-infrared region are known, and as such near-infrared absorbing structures, for example, Patent Documents 1 to 5 describe oxocarbon. A near-infrared absorbing structure using a system compound as a light absorbing source in the near-infrared region is disclosed.

Japanese Unexamined Patent Publication No. 2012-8532 Japanese Unexamined Patent Publication No. 2014-59550 Japanese Unexamined Patent Publication No. 2014-63144 Japanese Unexamined Patent Publication No. 2014-126642 Japanese Unexamined Patent Publication No. 2014-148567

Some near-infrared absorbing dyes such as oxocarbon compounds are relatively easily decomposed depending on the conditions, but since the near-infrared absorbing structure is basically used by exposing it to light, the near-infrared absorbing structure is It is required to have sufficient light resistance. That is, it is required that the decomposition of the near-infrared absorbing dye under light irradiation is suppressed as much as possible. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a light selective absorption structure which selectively absorbs light in the near infrared region and has excellent light resistance.

［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、Ｒ⁵〜Ｒ⁹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、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸、Ｒ⁸とＲ⁹はそれぞれ、互いに結合して環を形成していてもよい。
式（４）中、Ｒ¹⁰〜Ｒ¹⁴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、Ｒ¹⁰とＲ¹¹、Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴はそれぞれ、互いに結合して環を形成していてもよい。
＊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。］ The present invention includes the following inventions.
[1] A light selective absorption resin laminate having at least a first resin layer containing a near-infrared absorbing dye and a second resin layer composed of the same or different resin as the first resin layer as a laminated structure. The second resin layer is a body, and is characterized by light selective absorption having an oxygen transmittance of 100 cc / m ² / day or less under dry conditions at 23 ° C. measured according to the JIS K 7126-2 method. Resin laminate.
[2] The light selective absorption resin laminate according to [1], wherein the ultraviolet absorber is contained in at least one layer constituting the laminate.
[3] The light selective absorption resin laminate according to [1] or [2], wherein the near-infrared absorbing dye is an oxocarbon-based compound.
[4] The light selective absorption resin laminate according to [3], wherein the oxocarbon-based compound is a squarylium compound represented by the following formula (1) 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 formula (3), R ^{5 to} R ⁹ independently represent a hydrogen atom, an organic group or a polar functional group, and R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ And R ⁹ may be coupled to each other to form a ring, respectively.
In formula (4), R ^{10 to} R ¹⁴ independently represent a hydrogen atom, an organic group or a polar functional group, and are R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ . Each of R ¹⁴ may be bonded 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 light selective absorption resin laminate of the present invention can selectively absorb light in the near infrared region by a first resin layer containing a near infrared absorbing dye, and the first resin layer has an oxygen transmittance. By laminating the lower second resin layer, the decomposition of the near-infrared absorbing dye contained in the first resin layer can be suppressed. Therefore, the light selective absorption resin laminate of the present invention has excellent light resistance.

The light selective absorption resin laminate of the present invention has a laminated structure of a first resin layer containing a near-infrared absorbing dye and a second resin layer composed of the same or different resin as the first resin layer. At least have as. The light selective absorption resin laminate of the present invention selectively absorbs light in the near infrared region (for example, at least a part of the wavelength range of 600 to 1100 nm) by the first resin layer containing the near infrared absorbing dye. can do. On the other hand, since the near-infrared absorbing dye tends to be decomposed by oxygen, it is contained in the first resin layer by laminating a second resin layer having a low oxygen transmittance on the first resin layer. Decomposition of near-infrared absorbing dye can be suppressed. Therefore, the light selective absorption resin laminate of the present invention has excellent light resistance. Hereinafter, the light selective absorption resin laminate of the present invention will be described in detail.

As the resin constituting the first resin layer and the second resin layer contained in the light selective absorption resin laminate, a known resin can be used. The resin constituting the first resin layer and the resin constituting the second resin layer may be the same as or different from each other. The resin constituting these resin layers is preferably 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, melamine resin, urethane resin, styrene resin, polyvinyl acetate, polyamide resin (for example, nylon), aramid resin, polyimide resin, polyamideimide resin, alkyd resin , Phenolic resin, epoxy resin, polyester resin (for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), etc.), butyral resin, polycarbonate resin, polyether resin, polysulfone resin, ABS resin (acrylic nitrile butadiene styrene resin) , AS resin (acrylonitrile-styrene copolymer), silicone resin, modified silicone resin (for example, (meth) acrylic silicone resin, alkylpolysiloxane resin, silicone urethane resin, silicone polyester resin, silicone acrylic resin, etc.), fluorine Based resins (for example, fluorinated aromatic polymer, polytetrafluoroethylene (PTFE), perfluoroalkoxyfluororesin (PFA), fluorinated polyaryl ether ketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid ( FPAA), fluorinated polyethylene nitrile (FPN), etc.) and the like. Among these, from the viewpoint of excellent transparency and versatility, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyolefin resin, cycloolefin resin, polyimide resin, polyamideimide resin, epoxy resin, polyester Resins, polycarbonate resins, polysulfone resins and fluorinated 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 a (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 glutarimide 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.

Polyvinyl chloride resins, [- CH ₂ -CHCl-] is a polymer having the repeating units, polyvinylidene chloride resins are polymers having the repeating unit _{[- - CH 2 -CCl 2]} . The polyolefin resin is a polymer obtained by polymerizing an alkene as a monomer, and examples thereof include polyethylene and polypropylene.

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 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, Viromax (registered trademark) manufactured by Toyobo, TPS (registered trademark) TI5000 series manufactured by Toray Plastics Precision Precision Co., Ltd., and the like can be used.

Epoxy resin is a resin that can be cured by cross-linking an epoxy compound (prepolymer) in the presence of a curing agent or a curing catalyst. Examples of the epoxy compound include aromatic epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, hydrogenated epoxy compounds and the like. For example, fluorene epoxy manufactured by Osaka Gas Chemical Co., Ltd. (Ogsol (registered trademark) PG-100). , Mitsubishi Chemical's bisphenol A type epoxy compound (JER (registered trademark) 828EL), hydrogenated bisphenol A type epoxy compound (JER (registered trademark) YX8000), and Daicel's alicyclic liquid epoxy compound (celloxide (registered)) Trademark) 2021P) 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 is obtained 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, TRN series manufactured by Teijin, Theonex (registered trademark), and Lynite manufactured by DuPont. (Registered trademark), Novapex (registered trademark) manufactured by Mitsubishi Chemical Corporation, Novaduran (registered trademark) manufactured by Mitsubishi Engineering Plastics, Lumirer (registered trademark) manufactured by Toray Industries, etc. can be used. ..

The 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 first resin layer contains a near-infrared absorbing dye. The near-infrared absorbing dye contained in the first resin layer may be an organic dye, an inorganic dye, or an organic-inorganic composite dye (for example, an organic compound in which a metal atom or an ion is coordinated). Well, the type is not particularly limited. The near-infrared absorbing dye preferably has a maximum absorption wavelength in the wavelength range of 650 nm to 1100 nm, whereby the light selective absorption resin laminate can be suitably applied to a near-infrared cut filter or the like. The wavelength range of the maximum absorption wavelength of the near-infrared absorbing dye is preferably 680 nm or more, more preferably 700 nm or more, preferably 1090 nm or less, and more preferably 1070 nm or less.

As the near-infrared absorbing dye, for example, a cyclic tetrapyrrole dye (porphyrins, chlorin) which may have copper (for example, Cu (II)), zinc (for example, Zn (II)) or the like as a central metal ion. , Phthalocyanines, choline, etc.), oxocarbon dyes, cyanine dyes, quaterylene dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, diimmonium dyes, subphthalocyanine dyes, xanthene dyes. , Azo dyes, dipyrromethene dyes and the like. The first resin layer may contain only one type of near-infrared absorbing dye, or may contain two or more types. It is preferable to use an organic dye or an organic-infrared composite dye as the near-infrared absorbing dye because it is easy to design the molecule so as to exhibit desired optical characteristics. Among them, light in the near-infrared region is used. It is preferable to use an oxocarbon-based compound as the near-infrared absorbing dye because it can be effectively absorbed and the visible light transmittance can be easily increased. Since the oxocarbon-based compound is also relatively easily decomposed in the presence of oxygen, the near-infrared ray absorption by the second resin layer is performed by using the oxocarbon-based compound as the near-infrared ray absorbing dye contained in the first resin layer. The effect of suppressing the decomposition of the dye is more easily exerted.

The oxocarbon-based compound is not particularly limited as long as it is a compound containing a carbon oxide as a basic skeleton, but it is preferable to use a squarylium compound or a croconium compound which is widely known as a compound having an absorption wavelength in the near infrared region. 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.

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

In the above formula (1), the aromatic hydrocarbon compound has an aromatic hydrocarbon ring or an aromatic heterocycle in which at least one of R ¹ and R ² is connected to the squarylium skeleton in a π-conjugated system and may have a substituent. , Or those representing a fused ring containing these ring structures is preferable. In the above formula (2), the croconium compound has an aromatic hydrocarbon ring or an aromatic heterocycle in which at least one of R ³ and R ⁴ is connected to the croconium skeleton in a π-conjugated system and may have a substituent. , Or those representing a fused ring containing these ring structures is preferable. By using such a squarylium compound or a croconium compound, the π-conjugated system spreads from the squarylium skeleton or the croconium skeleton to the aromatic hydrocarbon ring or the aromatic heterocycle, and it is easy to selectively absorb light in the near infrared region. Become. More preferably, in the above formula (1), an aromatic hydrocarbon ring or an aromatic heterocycle in which both R ¹ and R ² are connected to the squarylium skeleton in a π-conjugated system and may have a substituent. Alternatively, it represents a fused ring containing these ring structures, and in the above formula (2), both R ³ and R ⁴ are aromatic hydrocarbons which may have a substituent connected to the croconium skeleton in a π-conjugated system. Represents a hydrogen ring, an aromatic heterocycle, or a fused ring containing these ring structures.

Examples of the aromatic hydrocarbon ring include those having 6 to 20 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, and a cyclotetradecaheptaene ring. Of these, a 5- or 6-membered aromatic hydrocarbon ring that may have a substituent is preferable.

As the aromatic heterocycle, for example, a 5- or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a 3- to 8-membered ring are condensed. Examples thereof include a fused aromatic heterocycle which is bicyclic or tricyclic and contains at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and specific examples thereof include a furan ring, a thiophene ring, and a pyrrol ring. , Pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, purine ring, pteridine ring and the like. Of these, a 5- or 6-membered aromatic heterocycle which may have a substituent is preferable.

Examples of the fused ring containing the aromatic hydrocarbon ring and the aromatic heterocycle include an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, a benzopyran ring, an acridine ring, a xanthene ring, and a carbazole ring.

The aromatic hydrocarbon ring, the aromatic heterocycle, or the fused ring containing these ring structures may be directly bonded to the squarylium skeleton or the croconium skeleton, and the squarylium skeleton or croconium via a linking group having a π-conjugated system. It may be associated with the skeleton. In either case, the π-conjugated system may be configured to extend from the squarylium skeleton or the croconium skeleton to these ring structures. Examples of the linking group having π-conjugation include −CR ^a1 =, − (CR ^a2 = CR ^a3 ) _h −, −N = CR ^a1 −, −NR ^a1 − (CR ^a2 = CR ^a3 ) _h −, ^−O. − (CR ^a2 = CR ^a3 ) _h −, −S− (CR ^a2 = CR ^a3 ) _h − (In the formula, R ^{a1 to} R ^a3 represent hydrogen atom, organic group or halogen atom, and R ^a2 and R ^a3 May be connected to each other to form a ring, and h represents an integer of 1 or more). ^Examples of the organic group of R ^{a1 to} R ^a3 include an alkyl group, an alkoxy group, an aryl group, an aralkyl group and the like.

The type of substituents that the aromatic hydrocarbon ring, the aromatic heterocycle, or the fused ring containing these ring structures may have is not particularly limited, and for example, a hydroxyl group, a carboxyl group, a nitro group, an alkyl group, etc. Examples thereof include an alkoxy group, an alkyloxycarbonyl group, an aryl group, an aralkyl group, an amide group, a sulfonamide group, a cyano group and a halogeno group. The substituent is preferably a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an aryl group, or a halogen atom, and the number of substituents is preferably 1 to 5, more preferably 1 to 3.

The oxocarbon-based compound is preferably a group in which R ^{1 to} R ⁴ are independently represented by the following formula (3) or formula (4) in the above formulas (1) and (2). In formula (3), R ^{5 to} R ⁹ independently represent a hydrogen atom, an organic group or a polar functional group, and are R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , and R ⁸ . Each of R ⁹ may be bonded to each other to form a ring. In formula (4), R ^{10 to} R ¹⁴ independently represent a hydrogen atom, an organic group or a polar functional group, and are R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ . Each of R ¹⁴ may be bonded 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 the formulas (3) and (4), examples of the organic group of R ^{5 to} R ¹⁴ include an alkyl group, an alkoxy group, an alkylthiooxy group (alkylthio group), an alkoxycarbonyl group, an alkylsulfonyl group, an aryl group and an aralkyl group. Group, aryloxy group, arylthiooxy group (arylthio group), aryloxycarbonyl group, arylsulfonyl group, arylsulfinyl group, heteroaryl group, amide group, sulfonamide group, carboxy group (carboxylic acid group), cyano group, Examples thereof include an ethylene-containing group and an imine-containing group. Examples of the polar functional groups of R ^{5 to} R ¹⁴ include a halogeno group, a hydroxyl group, a nitro group, an amino group, a sulfo group (sulfonic acid group) and the like.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and an undecyl group. Linear or branched alkyl groups such as group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, Examples thereof include alicyclic alkyl groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group and cyclodecyl group. The number of carbon atoms of the alkyl group 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, more preferably 1 to 10, and even more preferably 1. If it is an alicyclic alkyl group, the number of carbon atoms is preferably 4 to 10, and more preferably 5 to 8. The alkyl group may have a substituent, and examples of the substituent contained in the alkyl group 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 and an amino group. Examples include a sulfo group. 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.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group and a dodecyloxy group. , Tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadesyloxy group, icosyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group in the alkoxy group may be linear or branched.

Examples of the alkylthiooxy group (alkylthio group) include a methylthiooxy group (methylthio group), an ethylthiooxy group (ethylthio group), a propylthiooxy group (propylthio group), a butylthiooxy group (butylthio group), and a pentylthio. Oxy group (pentylthio group), hexylthiooxy group (hexylthio group), heptylthiooxy group (heptylthiooxy group), octylthiooxy group (octylthio group), nonylthiooxy group (nonylthio group), decylthiooxy group (decylthio group) ), Undecylthiooxy group (Undecylthiooxy group), Dodecylthiooxy group (Dodecylthiooxy group), Tridecylthiooxy group (Tridecylthiooxy group), Tetradecylthiooxy group (Tetradecylthiooxy group), Pentadecylthiooxy group (Penta) Decylthio group), hexadecylthiooxy group (hexadecylthio group), heptadecylthiooxy group (heptadecylthio group), octadecylthiooxy group (octadecylthio group), nonadesylthiooxy group (nonadecilthiooxy group), icosylthiooxy group (Icosylthio group) and the like. The number of carbon atoms of the alkylthiooxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group in the alkylthiooxy group may be linear or branched.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, and a decyloxycarbonyl group. Examples thereof include an unsubstituted alkoxycarbonyl group such as an octadecyloxycarbonyl group and a substituted alkoxycarbonyl group such as a trifluoromethyloxycarbonyl group. Here, examples of the substituent include a halogeno group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. The alkyl group in the alkoxycarbonyl group may be linear or branched.

Examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, octylsulfonyl group and methoxymethylsulfonyl group. Examples thereof include a group, a cyanomethylsulfonyl group, a substituted or unsubstituted alkylsulfonyl group of a trifluoromethylsulfonyl group, and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group in the alkylsulfonyl group may be linear or branched.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, an azulenyl group, a fluorenyl group, a terphenyl group, a quarterphenyl group, a pentarenyl group, a heptalenyl group and a biphenylenyl group. Examples thereof include a group, an indacenyl group, an acenaphthylenyl group, a phenylenyl group and the like. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. 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 hydroxyl group, a cyano group, a nitro group, an amino group and a thiocyanate group. Examples thereof include 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 aryl group may be fused with a heteroaryl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group and the like. The aralkyl group may have a substituent, and examples of the substituent contained in the aralkyl group include an alkyl group, an alkoxy group, a halogeno group, a cyano group, a nitro group, a thiocianate group, an acyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group, a carbamoyl group, a sulfo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group. The carbon number of the aralkyl group is preferably 7 to 25, more preferably 7 to 15.

Examples of the aryloxy group include a phenyloxy group, a biphenyloxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a pyrenyloxy group, an indenyloxy group, an azurenyloxy group, a fluorenyloxy group, and a tar. Examples thereof include a phenyloxy group, a quarterphenyloxy group, a pentarenyloxy group, a heptalenyloxy group, a biphenylenyloxy group, an indacenyloxy group, an acenaphtylenyloxy group and a phenalenyloxy group. The aryloxy group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms.

Examples of the arylthiooxy group (arylthiooxy group) include a phenylthiooxy group, a biphenylthiooxy group, a naphthylthiooxy group, an anthrylthiooxy group, a phenanthrylthiooxy group, a pyrenylthiooxy group, and an indenylthio. Oxy group, azulenylthiooxy group, fluorenylthiooxy group, terphenylthiooxy group, quarterphenylthiooxy group, pentalenylthiooxy group, heptalenylthiooxy group, biphenylenylthiooxy group, indacenylthiooxy group , Asenaftyrenylthiooxy group, phenalenylthiooxy group and the like. The number of carbon atoms of the arylthiooxy group is preferably 6 to 25, more preferably 6 to 15.

Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 4-dimethylaminophenyloxycarbonyl group, a 4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group and a 2-methoxyphenyl group. Oxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxy Substituent or unsubstituted phenyloxycarbonyl group such as carbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group; substituted or unsubstituted 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, etc. Naftyloxycarbonyl group; etc. The aryloxycarbonyl group preferably has 7 to 25 carbon atoms, more preferably 7 to 15 carbon atoms.

Examples of the arylsulfonyl group include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and a 2-butoxyphenylsulfonyl group. Group, 2-fluorophenylsulfonyl group, 3-methylphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 3-fluorophenylsulfonyl group Substituted or unsubstituted phenylsulfonyl groups such as groups, 4-methylphenylsulfonyl groups, 4-fluorophenylsulfonyl groups, 4-cyanophenylsulfonyl groups, 4-methoxyphenylsulfonyl groups, 4-dimethylaminophenylsulfonyl groups; 1- Examples thereof include substituted or unsubstituted naphthylsulfonyl groups such as naphthylsulfonyl groups and 2-naphthylsulfonyl groups. The arylsulfonyl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms.

Examples of the arylsulfinyl group include phenylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 2-fluorophenylsulfinyl group and 3-methyl. Phenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-methylphenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyano Substituent or unsubstituted phenylsulfinyl groups such as phenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group; substituted or unsubstituted naphthylsulfinyl groups such as 1-naphthylsulfinyl group and 2-naphthylsulfinyl group. And so on. The arylsulfinyl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms.

Examples of the heteroaryl group include thienyl group, thiopyranyl group, isothiochromenyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyraridinyl group, pyrimidinyl group, pyridadinyl group, thiazolyl group, isothiazolyl group and furanyl group. Examples thereof include a pyranyl group. The heteroaryl group preferably has 2 to 20 carbon atoms, more preferably 3 to 15 carbon atoms. The heteroaryl group may have a substituent, and the substituent of the heteroaryl group includes an alkyl group, an alkoxy group, an aryl group, a halogeno group, a hydroxyl group, a cyano group, an amino group, a nitro group and a 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 heteroaryl group may be fused with an aryl group.

Examples of the amide group include those represented by the formula: -NHCOR ^b1 in which R ^b1 is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group and the like. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group include the substituents exemplified above, and a part of the hydrogen atom may be substituted with a halogen atom.

Examples of the sulfonamide group include those represented by the formula: -NHSO ₂ R ^b2 , wherein R ^b2 is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group and the like. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group include the substituents exemplified above, and a part of the hydrogen atom may be substituted with a halogen atom.

Examples of the ethylene-containing group include those represented by the formula: -CH = CH-R ^b3 in which R ^b3 is an aliphatic hydrocarbon group, an aryl group or a heteroaryl group. The aliphatic hydrocarbon group of R ^b3 may be saturated or unsaturated, but is preferably unsaturated. As such an aliphatic hydrocarbon group, a group having a repeating unit represented by − (CH = CH) _k − (k is an integer of 1 to 10, preferably an integer of 1 to 5) is used. Preferably, for example, a vinyl group is mentioned. As the aliphatic hydrocarbon group, for example, those having 1 to 20 carbon atoms are preferable, and those having 1 to 10 carbon atoms are more preferable. ^Examples of the aryl group of R ^b3 include a phenyl group, a biphenyl group and a naphthyl group, and examples of the heteroaryl group include a thienyl group, a thiopyranyl group, an isothiochromenyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group and a pyridyl group. Examples thereof include pyraridinyl group, pyrimidinyl group, pyridadinyl group, thiazolyl group, isothiazolyl group, furanyl group, pyranyl group and the like.

Examples of the imine-containing group include those represented by the formula: -CH = N-R ^b4 , in which R ^b4 is an amino group which may have a substituent. The amino group of R ^b4 may be substituted or unsubstituted. Examples of the amino group having a substituent include a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, a monoalkyl monoarylamino group and the like. Specific examples of the alkyl group and aryl group bonded to the amino group of R ^b4 include the alkyl group and the aryl group exemplified above.

Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, an iodine group and the like.

The amino group is represented by the formula: -NR ^b5 R ^b6 , and R ^b5 and R ^b6 are independently represented by a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and a heteroaryl group. Some things are mentioned. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group include the substituents exemplified above, and the alkenyl group and alkynyl group include a part of the carbon-carbon single bond of the alkyl group exemplified above. Examples thereof include substituents in which is replaced with a double bond or a triple bond, and these substituents may be partially substituted with a halogen atom. Further, R ^b5 and R ^b6 may be connected to each other to form a ring.

Examples of the ring structure formed from R ^{5 to} R ¹⁴ include a hydrocarbon ring and a heterocycle, and these ring structures may or may not have aromaticity. Examples of the aromatic hydrocarbon ring include an aromatic ring having 6 to 20 carbon atoms such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, and a cyclotetradecaheptaene ring. Examples of the alicyclic hydrocarbon ring include monocyclic cycloalkanes having 3 to 10 carbon atoms such as cyclopentane, cyclohexane, and cycloheptane; cyclopentene, cyclopentadiene, cyclohexen, and cyclohexadiene (for example, 1,3-cyclohexadiene). ), Cycloheptane, cycloheptadiene, etc., monocyclic cycloalkenes having 3 to 10 carbon atoms; bicyclo [2.2.1] pentane, bicyclo [2.2.1] penta-2-ene, bicyclo [2. 2.2] An example of a ring-type alkane having a bridge such as octane and bicyclo [2.2.2] octa-2-ene. Among them, aromatic rings having 6 to 10 carbon atoms, monocyclic cycloalkanes having 5 to 7 carbon atoms, monocyclic cycloalkanes having 5 to 7 carbon atoms, and cyclic alkanes having 5 to 9 carbon atoms having a bridge are included. preferable. In the heterocycle, one or more carbon atoms constituting the aromatic hydrocarbon ring or the alicyclic hydrocarbon ring described above are N (nitrogen atom), S (sulfur atom) and O (oxygen atom). A ring structure in which at least one atom selected from the above is replaced with, for example, a furan ring, a thiophene ring, a pyrrol ring, a pyrazole ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine. Examples include a ring, a purine ring, and a pteridine ring. These aromatic hydrocarbon rings, alicyclic hydrocarbon rings, and heterocycles may be fused with other rings, and such ring structures include, for example, indole ring, isoindole ring, and benzimidazole. Examples thereof include a ring, a quinoline ring, a benzpyran ring, an acridine ring, a xanthene ring, and a carbazole ring. By condensing the other rings, the wavelength of the obtained oxocarbon-based compound can be lengthened, which facilitates molecular design according to the color tone of the compound. Each ring structure formed from R ^{5 to} R ¹⁴ may have an organic group or a polar functional group described above as a substituent.

As the organic group of the formula (3), a group represented by the following formula (3-1) is one of the preferred embodiments. In formula (3-1), ring A represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing these ring structures, which may have a substituent. R ^{7 to} R ⁹ are as described above. In the case of an oxocarbon-based compound in which a group represented by the formula (3-1) is bonded to a squarylium skeleton or a croconium skeleton, the absorption wavelength of the oxocarbon-based compound can be easily set by appropriately setting the π-conjugated system of ring A. Can be adjusted. The oxocarbon-based compound to which the group represented by the formula (3-1) is bonded can adjust the maximum absorption wavelength to, for example, about 650 nm in the short wavelength region, and increases the number of π electrons in ring A (π conjugation). By expanding the system), the maximum absorption wavelength can be shifted by a long wavelength, and the maximum absorption wavelength can be adjusted to about 1100 nm, for example.

Specific examples of an aromatic hydrocarbon ring, an aromatic heterocycle, or a fused ring containing these ring structures, which may have a substituent of ring A, are ring structures formed from the above R ^{5 to} R ^14. As explained in. Examples of the substituent bonded to the ring A include an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms), an aryl group, an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms), and an alkylthio. Electron donation of a group (preferably 1-2 carbon atoms), a heteroaryl group, an amino group, an amide group, a sulfonamide group, a hydroxyl group, a thiol group, a benzothiazole group, the above ethylene-containing group, the above imine-containing group, etc. Groups and; halogeno groups (preferably fluoro groups, chloro groups, bromo groups), halogenoalkyl groups (preferably perhalogenoalkyl groups having 1-3 carbon atoms), cyano groups, alkoxycarbonyl groups (ester groups), carboxy groups. An electron-withdrawing group such as (carboxylic acid group), carboxylic acid ester group, carboxylic acid amide group, sulfo group (sulfonic acid group) and nitro group is preferable. Among these, an electron-withdrawing group is more preferable, and a halogeno group is particularly preferable. When the ring A has a substituent, the number thereof is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. When ring A has a plurality of substituents, the plurality of substituents may be the same or different. The ring A does not have to have a substituent.

R ^{7 to} R ⁹ of the formula (3-1) are independent hydrogen atoms, alkyl groups which may have a substituent, or aryl groups which may have a substituent. This makes it easy to increase the solvent solubility of the oxocarbon-based compound and to finely control the maximum absorption wavelength to a desired wavelength range. Further, an effect that the production of the oxocarbon-based compound becomes easy can be obtained. Examples of the alkyl group which may have a substituent of R ^{5 to} R ⁷ include the alkyl groups exemplified above, and the number of carbon atoms thereof is 1 to 6 as long as it is a linear or branched alkyl group. Is preferable, it is more preferably 1 to 4, and if it is an alicyclic alkyl group, it is preferably 4 to 7, and more preferably 5 to 6. Examples of the aryl group which may have a substituent of R ^{5 to} R ⁷ include the aryl group exemplified above, and the number of carbon atoms thereof is preferably 6 to 10, and more preferably 6 to 9. Preferred examples of these alkyl groups and aryl groups include methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, cyclopentyl group, cyclohexyl group and phenyl group.

The organic group of the formula (3) is also preferably a group represented by the following formula (3-2). In formula (3-2), ring B represents a 4- to 9-membered unsaturated hydrocarbon ring that may have a substituent. Rings A and R ⁷ are as described above.

Ring B has a double bond between the carbon atom bonded to the squarylium skeleton or the croconium skeleton and the carbon atom at the α-position of the pyrrole ring, and is composed of the carbon at the α-position and the carbon at the β-position of the pyrrole ring. Will be done. Ring B may have an unsaturated bond (preferably a double bond) in addition to the double bond, and preferably has only one unsaturated bond (double bond). Ring B is preferably a 5-8 membered ring, more preferably a 6-8 membered ring. Rings A and R ⁷ are as described above. If the oxocarbon-based compound has a ring B, the shoulder peak of the absorption waveform can be significantly reduced, and the optical characteristics in the visible light region can be improved. Furthermore, the bandgap of the π-π ^* transition is narrowed by the molecular strain caused by having the ring B, and the π electron system is widened by the ring A, so that the absorption wavelength can be easily lengthened. it can.

The structure of ring B includes, for example, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononene, cyclononadiene, cyclononatriene, and the like. Cycloalkene structures such as cyclononatetraene can be mentioned. Of these, cycloalkanemonoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are preferable.

Ring B may have a substituent, and examples of such a substituent include the organic group and the polar functional group described above. Among them, as the substituent bonded to the ring B, an alkyl group, an alkoxy group, a halogeno group, an aryl group, an alkoxycarbonyl group (ester group), an amide group, a sulfonamide group and a hydroxyl group are preferable, and an alkyl group or a hydroxyl group is more preferable. This makes it easier to increase the solubility of the oxocarbon-based compound in the organic solvent. In this case, the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 to 2 carbon atoms. When the ring B has a substituent, the number thereof is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2. However, the number of substituents on ring B is preferably equal to or less than the number of members of ring B minus 3. When ring B has a plurality of substituents, the plurality of substituents may be the same or different, and the plurality of substituents may be bonded to different carbon atoms, respectively, in one carbon atom. It may be combined. Ring B does not have to have a substituent.

R ⁷ of the formula (3-2) is as described above, and among them, a hydrogen atom, an alkyl group, an alkoxycarbonyl group, and an aryl group are preferable, and an alkyl group or an aryl group is more preferable, thereby oxocarbon-based. It becomes easy to increase the solubility of the compound in an organic solvent. In this case, the number of carbon atoms of the alkyl group is preferably 1 to 6 if it is a linear or branched alkyl group, more preferably 1 to 4, and 4 to 7 if it is an alicyclic alkyl group. It is preferable, more preferably 5 to 6. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. When R ⁷ is an alkyl group or an aryl group, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and the like are preferably mentioned.

In the organic group of the above formula (4), R ^{11 to} R ¹³ are independent of each other, and they are a hydrogen atom, an alkyl group, an alkoxycarbonyl group, an aryl group, an amino group or a hydroxy group, or R ¹¹ and R ¹² are each other. It is preferable that R ¹² and R ¹³ are bonded to each other to form a ring, or R ¹⁰ and R ¹⁴ are independently bonded to each other to form a hydrogen atom, an alkyl group, and an alkoxycarbonyl group. , Aryl group, amide group or hydroxy group is preferable. Such squarylium compounds produced is relatively easy, by selecting the substituents R ¹⁰ to R ¹⁴ as appropriate, and controls the maximum absorption wavelength in a desired wavelength region, to increase the solubility in a solvent it can. Above all, R ¹² is preferably an amino group from the viewpoint that the π-conjugated system of the squarylium compound can be stably expanded over a wide range.

As the organic group of the formula (4), the group represented by the following formula (4-1) is one of the preferable embodiments. In formula (4-1), R ^{10 to} R ¹¹ and R ^{13 to} R ¹⁴ are as described above, and from the viewpoint of stability and ease of manufacture of the scudylium compound, they are independent hydrogen atoms and alkyl groups, respectively. Alternatively, it is preferably an aryl group. R ¹⁵ and R ^{16 in} formula (4-1) independently represent a hydrogen atom, an alkyl group or an aryl group, and R ¹¹ and R ¹⁵ , R ¹⁶ and R ¹³ , and R ¹⁵ and R ¹⁶ , respectively, respectively. They may be combined to form a ring.

As a ring structure in which R ¹¹ and R ¹⁵ and R ¹⁶ and R ^{13 of the} formula (4-1) are linked to each other, one end of a linear alkylene group having 2 to 8 carbon atoms is of the formula (4-1). A structure in which the other end is bonded to the carbon atom of the benzene ring of the formula (4-1), which is bonded to the nitrogen atom, and a part of −CH ₂ − contained in the alkylene group is −O−, −CO−, Examples thereof include structures substituted with −S− and −NH−. The ring structure in which R ¹⁵ and R ¹⁶ of the formula (4-1) are linked to each other includes a structure in which both ends of a linear alkylene group having 2 to 8 carbon atoms are bonded to a nitrogen atom of the formula (4-1). , A structure in which a part of −CH ₂ − contained in the alkylene group is substituted with −O−, −CO−, −S−, −NH−. In these ring structures, a part of the hydrogen atom is replaced with, for example, an alkyl group, 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, a sulfo group and the like. May be.

The organic group of the formula (4) is also preferably a group represented by the following formula (4-2). In formula (4-2), R ^{10 to} R ¹¹ and R ^{14 to} R ¹⁵ are as described above. R ^{17 to} R ²⁰ of the formula (4-2) are independently alkyl group, aryl group, heteroaryl group, halogeno group, hydroxyl group, carboxy group, alkoxy group, cyano group, nitro group, amino group or sulfo group. , Preferably an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms), an aryl group (preferably an aryl group having 6 to 10 carbon atoms), a halogeno group, a carboxy group, an alkoxy group. (Preferably an alkoxy group having 1 to 4 carbon atoms) or a hydroxyl group. If the oxocarbon-based compound has a group represented by the formula (4-2), the molecular flatness is high due to the structure in which the amino group is fused with the benzene ring, and it is regular when the molecules are assembled. It becomes easy to take a highly crystalline aggregate structure gathered in.

The oxocarbon-based compound having an organic group of the formula (3) or the formula (4) is synthesized by appropriately adopting a known synthetic method of reacting a pyrrole ring-containing compound or a benzene ring-containing compound with squaric acid or croconic acid. it can. Squalylium compounds can be synthesized, for example, by the synthetic method described in the following paper: Serguei Miltsov et al., “New Cyanine Dyes: Norindosquarocyanines”, Tetrahedron Letters, Vol.40, Issue 21, p.4067. -4068 (1999). The croconium compound can be synthesized by the methods described in, for example, JP-A-2002-286931, JP-A-2007-31644, JP-A-2007-31645, and JP-A-2007-169315. it can.

The oxocarbon-based compound obtained by the above reaction can be appropriately purified by a known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation, recrystallization, and crystallization, if necessary. The chemical structure of the obtained oxocarbon-based compound can be analyzed by known analytical methods such as mass spectrometry, single crystal X-ray structure analysis, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy.

The amount of the near-infrared absorbing dye contained in the first resin layer may be appropriately adjusted according to the desired optical performance. For example, the content of the near-infrared absorbing dye in 100% by mass of the first resin layer is It is preferably 0.01% by mass or more, more preferably 0.3% by mass or more, further preferably 0.8% by mass or more, still preferably 25% by mass or less, more preferably 20% by mass or less, and 15% by mass. % Or less is more preferable. When the oxocarbon-based compound is contained as the near-infrared absorbing dye in the first resin layer, the content of the oxocarbon-based compound is preferably in the above range. When the first resin layer contains an oxocarbon-based compound and another near-infrared absorbing dye, the total content of the oxocarbon-based compound and the other near-infrared absorbing dye is preferably in the above range. ..

When the first resin layer contains an oxocarbon-based compound and another near-infrared absorbing dye, the content of the other near-infrared absorbing dye is 100% by mass in total of the oxocarbon-based compound and the other near-infrared absorbing dye. On the other hand, it is preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 20% by mass or less, and particularly preferably substantially free of other near-infrared absorbing dyes.

The second resin layer may contain at least a resin. The second resin layer is provided to suppress the decomposition of the near-infrared absorbing dye contained in the first resin layer, and for this purpose, the second resin layer is set to have a low oxygen transmittance. Specifically, the second resin layer has an oxygen permeability of 100 cc / m ² / day or less under dry conditions at 23 ° C. measured according to the JIS K 7126-2 method. By laminating the second resin layer having a low oxygen transmittance on the first resin layer, the chance that the near-infrared absorbing dye contained in the first resin layer comes into contact with oxygen is reduced, and the second resin layer is contained in the first resin layer. It is possible to suppress the decomposition of the near-infrared absorbing dye. Oxygen permeability of the second resin layer is preferably not more than 70 cc / m ² / day, more preferably not more than 50 cc / m ² / day, more preferably less 35cc / m ² / day. The lower limit of the oxygen permeability of the second resin layer is not particularly limited, and may be 0 cc / m ² / day. The oxygen permeability is measured by introducing oxygen gas into the chamber on one side of the test piece and introducing nitrogen gas into the chamber on the other side.

The oxygen permeability of the second resin layer can be reduced by appropriately selecting the type of resin constituting the second resin layer or increasing the thickness of the second resin layer. Further, even if an inorganic thin-film resin layer (inorganic thin-film film) is used as the second resin layer, the oxygen transmittance can be lowered. For example, the oxygen transmittance of the second resin layer can be lowered by using a resin layer having a metal oxide such as aluminum oxide or silicon oxide or a vapor-deposited film of carbon (amorphous carbon or the like) formed therein. When the second resin layer is an inorganic vapor-deposited resin layer, the thickness of the second resin layer can be made thin while keeping the oxygen transmittance low.

The second resin layer may also contain the near-infrared absorbing dye as described above, but in view of the purpose of installing the second resin layer, the second resin layer contains the near-infrared absorbing dye. It is preferable that the amount is not large, and it is preferable that the amount of the oxocarbon-based compound that is easily decomposed in the presence of oxygen is not large. For example, the concentration of the near-infrared absorbing dye in the second resin layer is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less of the concentration of the near-infrared absorbing dye in the first resin layer. It is particularly preferable that the second resin layer substantially does not contain a near-infrared absorbing dye. The concentration of the oxocarbon-based compound in the second resin layer is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, of the concentration of the oxocarbon-based compound in the first resin layer. It is particularly preferable that the second resin layer does not substantially contain an oxocarbon-based compound.

The first and second resin layers may contain any organic or inorganic fine particles. The organic fine particles or the inorganic fine particles are used, for example, to impart functions related to the refractive index, conductivity, etc. to the resin layer. Specific examples of fine particles useful for increasing the refractive index and imparting conductivity of the resin layer include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, tin oxide, tin-doped indium oxide, antimony-doped tin oxide, indium-doped zinc oxide, and oxidation. Examples thereof include indium and antimony oxide. On the other hand, specific examples of the fine particles useful for lowering the refractive index of the resin layer include magnesium fluoride, silica, hollow silica and the like. Specific examples of fine particles useful for imparting antiglare include, in addition to the above fine particles, inorganic fine particles such as calcium carbonate, barium sulfate, talc, and kaolin: silicone resin, melamine resin, benzogamine resin, acrylic resin, polystyrene resin, and these. Examples include organic fine particles such as the copolymer resin of. The resin layer may contain only one kind of these fine particles, or may contain two or more kinds of these fine particles.

The resin layer may contain plasticizers, surfactants, dispersants, surface tension regulators, viscosity regulators, defoamers, preservatives, specific resistance regulators, pH regulators, adhesion improvers, etc., as required. Various additives may be contained. Further, the resin layer may contain a curing catalyst and a curing rate adjusting agent for curing the resin constituting the resin layer.

The resin layer can be formed from a resin composition containing at least a resin component. The first resin layer can be formed from a resin composition further containing a near-infrared absorbing dye. The resin composition may be a thermoplastic resin composition that can be used for molding such as injection molding, or may be a resin composition that has been made into a paint so that it can be coated by a spin coating method, a solvent casting method, or the like. Good. The resin component is not only a resin whose polymerization has been completed, but also a resin raw material (including a resin precursor, a raw material of the precursor, a monomer constituting the resin, etc.), and when molding a resin composition. It is also possible to use a resin which is incorporated into a resin by a polymerization reaction or a cross-linking reaction.

When the resin composition is a thermoplastic resin composition, the resin layer can be formed by subjecting the resin composition to injection molding, extrusion molding, vacuum molding, compression molding, blow molding, or the like. In this method, a resin layer can be formed by using a thermoplastic resin as a resin component, blending a near-infrared absorbing dye with the thermoplastic resin as needed, and heat-molding the resin. For example, it is preferable to add a near-infrared absorbing dye to the powder or pellet of the base resin as needed, heat it to about 150 ° C. to 350 ° C. to dissolve it, and then mold it. Further, when kneading the resin, various additives may be added as needed. When the first resin layer and the second resin layer are heat-molded at the same time, the resin composition giving the first resin layer and the resin composition giving the second resin layer may be co-extruded.

When the resin composition is a paint-based resin composition, a liquid or paste-like resin composition is applied onto a substrate (for example, a first or second resin layer, another resin plate, a glass plate, etc.). By working, a resin layer can be formed on the substrate. Examples of the paint-based resin composition containing the near-infrared absorbing dye include those in which the near-infrared absorbing dye is dissolved in a solvent containing a resin, and the near-infrared absorbing dye is atomized to several μm or less. Examples thereof include those dispersed in a resin emulsion. Examples of the coating method for the paint-based resin composition include a spin coating method, a solvent casting method, a roll coating method, a spray coating method, a bar coating method, a dip coating method, a screen printing method, a flexographic printing method, and an inkjet method. It is preferably used.

The resin composition may contain a solvent (solvent). For example, when the resin composition is a paint-based resin composition, the resin composition can be easily coated by containing the solvent. become. As the solvent, it is preferable to use an organic solvent, for example, ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), cyclohexanone; PGMEA (2-acetoxy-1-methoxypropane). ), Glycol derivatives such as ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); amides such as N, N-dimethylacetamide; acetic acid Esters such as ethyl, propyl acetate and butyl acetate; Pyrrolidones such as N-methyl-pyrrolidone (specifically, 1-methyl-2-pyrrolidone); Aromatic hydrocarbons such as toluene and xylene; Cyclohexane, Examples thereof include aliphatic hydrocarbons such as heptane; ethers such as tetrahydrofuran, dioxane, diethyl ether and dibutyl ether; and the like.

The content of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably less than 100% by mass, and more preferably 95% by mass or less in 100% by mass of the resin composition. By adjusting the content of the solvent within such a range, it becomes easy to obtain a resin composition having a high concentration of near-infrared absorbing dye.

The thickness of each of the first resin layer and the second resin layer is not particularly limited, and may be appropriately adjusted according to the desired performance and strength of each resin layer. The thickness of each resin layer is, for example, preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, preferably 500 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less. When the resin layer is formed by applying a paint-based resin composition on the substrate, the strength of the light selective absorption resin laminate can be ensured by the substrate, so that the thickness of the resin layer is further reduced. can do. The thickness of the resin layer when the resin layer is formed on the substrate may be, for example, 100 μm or less, 50 μm or less, or 30 μm or less. The first resin layer can be formed to have a relatively thin thickness as long as it can exhibit the desired light selective absorption performance, and the thickness is preferably 0.5 μm or more, more preferably 1 μm or more. Further, 30 μm or less is preferable, 25 μm or less is more preferable, and 20 μm or less is further preferable. The thickness of the second resin layer is preferably 6 μm or more, more preferably 8 μm or more, still more preferably 10 μm or more, from the viewpoint that the oxygen transmittance can be easily suppressed to be low.

The first resin layer and the second resin layer may be provided with an adhesive layer between them to improve the adhesiveness. The adhesive layer can be formed from a known adhesive, for example, it can be formed using a polyester resin, an acrylic resin, a urethane resin, a cellulose resin, a polyol resin, a polycarboxylic acid resin, and a composite resin thereof. Only one type of these resins may be used, or two or more types may be used in combination. For example, when the adhesive layer is formed from urethane resin, the types of polyisocyanate and polyol forming the urethane resin are not particularly limited, and the polyol may be any of polyacrylic polyol, polyester polyol, polyether polyol, and the like. ..

The thickness of the adhesive layer is not particularly limited, and for example, 0.01 μm or more is preferable, 0.05 μm or more is more preferable, 0.1 μm or more is further preferable, 50 μm or less is preferable, 10 μm or less is more preferable, and 5 μm or less is preferable. More preferred.

The method for forming the adhesive layer is not limited, and a known method may be used. The adhesive layer was formed, for example, by applying an adhesive composition containing a resin having adhesiveness to the first resin layer and / or the second resin layer to form a coating film of the composition. It can be formed by drying the coating film. After that, by laminating the first resin layer and the second resin layer via the adhesive layer, a laminated structure having the first resin layer, the adhesive layer, and the second resin layer can be formed.

The light selective absorption resin laminate is preferably formed so that the second resin layer is located closer to the light receiving side than the first resin layer. That is, it is preferable that each layer is arranged so that the transmitted light of the second resin layer passes through the first resin layer.

It is preferable that both one side surface and the other side surface of the first resin layer are covered with a layer having a low oxygen permeability. For example, the light selective absorption resin laminate has a laminated structure in which second resin layers are provided on both side surfaces of the first resin layer, or a second resin layer is provided on one surface of the first resin layer. It is preferable to have a laminated structure in which a glass substrate is provided on the other side surface.

From the viewpoint of suppressing the decomposition of the near-infrared absorbing dye contained in the first resin layer, it is preferable that at least one layer constituting the light selective absorbing resin laminate contains an ultraviolet absorber. More preferably, the ultraviolet absorber is contained in a layer other than the first resin layer. The ultraviolet absorber is preferably contained in, for example, a second resin layer or, when the light selective absorption resin laminate has an adhesive layer, in the adhesive layer.

Examples of the ultraviolet absorber include benzophenone compounds, salicate compounds, benzoate compounds, triazole compounds, triazine compounds and the like. Examples of the benzophenone compound include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 4-n-octyloxy-2-hydroxybenzophenone and the like. Examples of the silicate-based compound include phenyl salicylate and pt-butyl phenyl silicate. Examples of the benzoate compound include 2,4-di-t-butylphenyl-3', 5'-di-t-butyl-4'-hydroxybenzoate and the like.

Examples of the triazole-based compound include 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (3). , 5-Di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole-2-yl) -p-cresol, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-benzotriazole-2-yl-4,6-di-t-butylphenol, 2- [5-chloro (2H) -benzotriazole- 2-Il] -4-methyl-6- (t-butyl) phenol, 2- (2H-benzotriazole-2-yl) -4,6-di-t-butylphenol, 2- (2H-benzotriazole-2) -Il) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazole-2-yl) -4-methyl-6- (3,4,5,6-tetrahydro) Examples thereof include phthalimidylmethyl) phenol and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole.

Triazine-based compounds include, for example, 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxy). Phenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxy) Phenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy) -4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl- 6- (2-Hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-Diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-) Dibutoxyphenyl) -1,3-5-triazine, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like can be mentioned.

As the ultraviolet absorber, a commercially available substance may be used, and for example, ADEKA's ADEKA STAB (registered trademark) series, BASF's Chinubin (registered trademark) series, and the like can be used.

The content of the ultraviolet absorber may be appropriately adjusted according to the desired performance, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the layer containing the ultraviolet absorber. 1, 1% by mass or more is further preferable, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 15% by mass or less is further preferable.

The light selective absorption resin laminate of the present invention may have another layer (film) in addition to the first resin layer, the second resin layer, the adhesive layer, and the glass substrate. Examples of other layers (films) include a dielectric multilayer film, a layer having antiglare properties, a layer having scratch prevention performance, a metal film, and a transparent base material having other functions.

Since the light selective absorption resin laminate of the present invention has high light resistance, it can be used for various purposes as a resin laminate that selectively absorbs near infrared rays. For example, an optical filter for a semiconductor light receiving element that has a function of absorbing and cutting near infrared rays, a near infrared ray absorbing film or a near infrared ray absorbing plate that blocks heat rays for energy saving, and an information display material as security ink or invisible bar code ink. Materials for solar cells using visible light and near-infrared light, specific wavelength absorption filters for plasma display panels (PDPs) and CCDs; photothermal conversion materials for laser welding, light that is less likely to cause problems due to pressurization or heating It can be used as a material for an optical fixing method (a toner for electrostatic charge development for a flash fixing method) or the like.

The thickness of the light selective absorption resin laminate is preferably 1 mm or less, for example. As a result, it is possible to sufficiently meet the demand for miniaturization of the image pickup device when the light selective absorption resin laminate is applied to the image pickup device. The thickness of the light selective absorption resin laminate is more preferably 500 μm or less, further 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.

Hereinafter, the present invention will be described in more detail by showing examples, but the scope of the present invention is not limited thereto.

(1) Synthesis of near-infrared absorbing dye (1-1) Synthesis of croconium A According to Synthesis Example 2 described in Japanese Patent Application No. 2016-034756, croconium A shown in Table 1 below was synthesized as a near-infrared absorbing dye.

(1-2) Synthesis of Squalylium A Squalylium A shown in Table 1 below was synthesized as a near-infrared absorbing dye according to Example 1-18 described in JP-A-2016-74649.

(1-3) Synthesis of squarylium B Squalylium B shown in Table 1 below was synthesized as a near-infrared absorbing dye according to Examples 1-10 described in JP-A-2016-74649.

(1-4) Synthesis of Squalylium C According to Preparation Example 4 described in Japanese Patent Application No. 2016-176990, Squalylium C shown in Table 1 below was synthesized as a near-infrared absorbing dye.

(2) Preparation of resin laminate (2-1) Production example 1
A dye-containing resin composition was obtained by mixing 2 parts by mass of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000), 0.02 parts by mass of croconium A, and 18 parts by mass of chloroform. .. This dye-containing resin composition was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a first resin layer having a film thickness of about 20 μm. On the first resin layer formed on the glass substrate, 1.8 parts by mass of an ester-urethane resin solution-based adhesive (Seikabond (registered trademark) A-601E manufactured by Dainichi Seika Kogyo Co., Ltd.), an isocyanate-based curing agent ( An adhesive composition consisting of 0.3 parts by mass of Seikabond (registered trademark) C-84) and 8.4 parts by mass of ethyl acetate manufactured by Dainichi Seika Kogyo Co., Ltd. was applied with a spin coater, dried at 90 ° C., and about. A 1 μm adhesive layer was formed. A PET film having a thickness of 50 μm and an oxygen transmittance of 27 cc / m ² / day (manufactured by Toray Industries, Inc., Lumirror S10) was placed on the adhesive layer thus formed as a second resin layer at a nip roll temperature of 70 ° C. By laminating, a resin laminate 1 was produced.

(2-2) Production Example 2
Resin lamination in the same manner as in Production Example 1 except that a PET film having a thickness of 100 μm and an oxygen transmittance of 15 cc / m ² / day (manufactured by Toray Industries, Inc., Lumirror T60) was used as the second resin layer in Production Example 1. Body 2 was made.

(2-3) Production Example 3
In Production Example 1, as the second resin layer, an aluminum oxide-deposited PET film having a thickness of 12 μm and an oxygen permeability of 2.1 cc / m ² / day (manufactured by Toray Industries, Inc., Barrierox 1011HG; in Table 2, “Al-deposited PET” is used. The resin laminate 3 was produced in the same manner as in Production Example 1 except that (notation) was used.

(2-4) Production Example 4
In Production Example 1, as the adhesive composition, 1.8 parts by mass of an ester urethane resin solution-based adhesive (manufactured by Dainichi Seika Kogyo Co., Ltd., Seika Bond (registered trademark) A-601E), an isocyanate-based curing agent (Dainichi Seika Kogyo Co., Ltd.) Adhesive composition consisting of 0.3 parts by mass of Seikabond (registered trademark) C-84), 8.4 parts by mass of ethyl acetate, and 0.25 parts by mass of benzotriazole-based ultraviolet absorber (Tinubin P, manufactured by BASF). The resin laminate 4 was produced in the same manner as in Production Example 1 except that the product was used.

(2-5) Production Example 5
In Production Example 4, a PET film having a thickness of 100 μm and an oxygen transmittance of 15 cc / m ² / day (manufactured by Toray Industries, Inc., Lumirror T60) was used as the second resin layer, but the resin was laminated in the same manner as in Production Example 4. Body 5 was made.

(2-6) Production Example 6
In Production Example 4, as the second resin layer, an aluminum oxide-deposited PET film having a thickness of 12 μm and an oxygen permeability of 2.1 cc / m ² / day (manufactured by Toray Industries, Inc., Barrierox 1011HG; in Table 2, “Al-deposited PET” is used. The resin laminate 6 was produced in the same manner as in Production Example 4 except that (notation) was used.

(2-7) Production Example 7
In Production Example 2, as the dye-containing resin composition, 2 parts by mass of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Upiron (registered trademark) E-2000), 0.02 parts by mass of croconium A, and benzotriazole-based ultraviolet absorption are absorbed. A resin laminate 7 was produced in the same manner as in Production Example 2 except that a mixture of 0.02 parts by mass of an agent (Tinubin P manufactured by BASF) and 18 parts by mass of chloroform was used.

(2-8) Production Example 8
The dye-containing resin solution prepared in Production Example 7 was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a resin layer having a film thickness of about 20 μm, which was used as the resin laminate 8. ..

(2-9) Production Example 9
The dye-containing resin solution prepared in Production Example 1 was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a resin layer having a film thickness of about 20 μm, which was used as the resin laminate 9. ..

(2-10) Production Example 10
A resin laminate 10 was obtained in the same manner as in Production Example 5, except that squarylium A was used instead of croconium A in Production Example 5.

(2-11) Production Example 11
A resin laminate 11 was obtained in the same manner as in Production Example 9 except that squarylium A was used instead of croconium A in Production Example 9.

(2-12) Production Example 12
A resin laminate 12 was obtained in the same manner as in Production Example 5, except that squarylium B was used instead of croconium A in Production Example 5.

(2-13) Production Example 13
A resin laminate 13 was obtained in the same manner as in Production Example 9 except that squarylium B was used instead of croconium A in Production Example 9.

(2-14) Production Example 14
A resin laminate 14 was obtained in the same manner as in Production Example 5, except that squarylium C was used instead of croconium A in Production Example 5.

(2-15) Production Example 15
A resin laminate 15 was obtained in the same manner as in Production Example 9 except that squarylium C was used instead of croconium A in Production Example 9.

(2-16) Production Example 16
Polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000) by 2 parts by mass, croconium A by 0.02 parts by mass, light stabilizer (manufactured by ADEKA, ADEKA STAB (registered trademark) LA-57) ) By 0.02 parts by mass and 18 parts by mass of chloroform to obtain a dye-containing resin composition. This dye-containing resin composition was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a resin layer having a film thickness of about 20 μm, which was used as a resin laminate 16.

(2-17) Production Example 17
Polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000) by 2 parts by mass, croconium A by 0.02 parts by mass, and ADEKA manufactured by ADEKA (registered trademark) PEP-36 as an antioxidant. Adecastab (registered trademark) AO-412S and Sumirizer (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd. were mixed by 0.01 part by mass and 18 parts by mass of chloroform, respectively, to obtain a dye-containing resin composition. This dye-containing resin composition was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a resin layer having a film thickness of about 20 μm, which was used as a resin laminate 17.

(2-18) Production Example 18
Polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000) is 2 parts by mass, chloroform A is 0.02 parts by mass, and bis (dithiobenzyl) nickel (II) is 0. 02 parts by mass and 18 parts by mass of chloroform were mixed to obtain a dye-containing resin composition. This dye-containing resin composition was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a resin layer having a film thickness of about 20 μm, which was used as a resin laminate 18.

(2-19) Production Example 19
Polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000) is 2 parts by mass, croconium A is 0.02 parts by mass, β-carotene as an antioxidant is 0.02 parts by mass, and chloroform is 18 parts by mass. The parts were mixed to obtain a dye-containing resin composition. This dye-containing resin composition was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a resin layer having a film thickness of about 20 μm, which was used as a resin laminate 19.

(2-20) Production Example 20
Polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark) E-2000) is 2 parts by mass, chloroform A is 0.02 parts by mass, and 7,7,8,8-tetracyanokinoji as a light stabilizer. 0.02 parts by mass of methane and 18 parts by mass of chloroform were mixed to obtain a dye-containing resin composition. This dye-containing resin composition was applied onto a glass substrate using a 300 μm applicator and then dried at 50 ° C. to form a resin layer having a film thickness of about 20 μm, which was used as the resin laminate 20.

(3) Analysis / test method (3-1) Oxygen permeability Using an oxygen permeability measuring device (Model 8001 manufactured by Irinoi Co., Ltd.), the second resin is used at 23 ° C. in dry conditions according to the JIS K 7126-2 method. The oxygen transmittances of the PET film used for the layer and the aluminum oxide vapor-deposited PET film were measured. The oxygen transmission rate was measured by introducing oxygen gas into the chamber on one side of each film and introducing nitrogen gas into the chamber on the other side.

(3-2) Light resistance test Using a xenon weather meter (Suga Test Instruments Co., Ltd., X75SC), each resin laminate was irradiated with light for 24 hours under the conditions of 60 W / m ² and 53 ° C. 60% RH, and light resistance. The test was conducted. The absorbance of each resin laminate before and after the test was measured with a spectrophotometer (UV-1800 manufactured by Shimadzu Corporation) to determine the absorbance of the maximum absorption wavelength in the wavelength range of 400 nm to 1100 nm, and the absorbance retention rate before and after the test. Was calculated.

(4) Results Table 2 shows the results of the light resistance test of the resin laminates 1 to 20 produced in Production Examples 1 to 20. Regardless of which dye is used as the near-infrared absorbing dye, by providing a second resin layer having an oxygen transmittance of 100 cc / m ² / day or less, a light resistance test is performed as compared with the case where the second resin layer is not provided. The absorbance retention rate after 24 hours was improved (resin laminates 1 to 3, 9 to 15). Further, by adding an ultraviolet absorber to the adhesive layer or the first resin layer, the absorbance retention rate was further increased (resin laminates 4 to 7). On the other hand, when the second resin layer is not provided, the second resin layer is provided even if an ultraviolet absorber, a light stabilizer or an antioxidant is added to the first resin layer as a light-resistant additive. Compared with the case, no significant improvement in the absorbance retention rate was observed (resin laminates 8, 16 to 20).

Since the light selective absorption resin laminate of the present invention has high light resistance, it can be used for various purposes as a resin laminate that selectively absorbs near infrared rays. For example, an optical filter for a semiconductor light receiving element that has a function of absorbing and cutting near infrared rays, a near infrared ray absorbing film or a near infrared ray absorbing plate that blocks heat rays for energy saving, and an information display material as security ink or invisible bar code ink. Materials for solar cells using visible light and near-infrared light, specific wavelength absorption filters for plasma display panels (PDPs) and CCDs; photothermal conversion materials for laser welding, light that is less likely to cause problems due to pressurization or heating It can be used as a material for an optical fixing method (a toner for electrostatic charge development for a flash fixing method) or the like.

Claims (2)

A first resin layer containing a croconium compound represented by the following formula (2) as a near-infrared absorbing dye , a second resin layer composed of the same or different resin as the first resin layer, and the first resin layer. A light selective absorption resin laminate having at least one resin layer and an adhesive layer provided between the second resin layers as a laminated structure.
The adhesive layer contains an ultraviolet absorber and
The second resin layer is a light selective absorption resin laminate having an oxygen transmittance of 100 cc / m ² / day or less under dry conditions at 23 ° C. measured according to the JIS K 7126-2 method.

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

[In formula (3), R ^{5 to} R ⁹ independently represent a hydrogen atom, an organic group or a polar functional group, and R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ And R ⁹ may be coupled to each other to form a ring, respectively.
In formula (4), R ^{10 to} R ¹⁴ independently represent a hydrogen atom, an organic group or a polar functional group, and are R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , and R ¹³ . Each of R ¹⁴ may be bonded to each other to form a ring.
* Represents the binding site with the 5-membered ring in formula (2). ] The light selective absorption resin laminate according to claim 1, wherein the second resin layer is an inorganic vapor-deposited resin layer.