JP2008230969A - Borate and visible light-absorbing material, luminous material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a visible light-absorbing material which improves the visible light-absorbing ability and light emitting intensity of pigments, and to provide a borate for luminous materials. <P>SOLUTION: A visible light-absorbing composition comprises a visible light-absorbing pigment and a borate to whose boron atom an aryl group having an electron-withdrawing group is bound, and a visible light-absorbing pigment. The composition has high absorbing ability in a visible light region and a light-emitting intensity, and is useful as an optical filter material for thin displays, an optical information-recording material, and a light-emitting material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a borate for a visible light absorbing material or a light emitting material, a visible light absorbing material containing the borate, or a light emitting material, and an optical filter using the visible light absorbing material, an optical information recording material, And a thin display using the optical filter. In particular, the present invention relates to a borate that improves the solubility and durability of the visible light absorbing dye, a borate that enhances the emission intensity of the luminescent dye, and a borate that suppresses deterioration of the near infrared absorbing dye due to the visible light absorbing dye. The present invention also relates to a visible light absorbing material containing the borate, an optical filter using the near infrared absorbing material, and a thin display using the optical filter.

  In recent years, thin displays such as liquid crystal displays and PDPs (Plasma Display Panels) that are thin and applicable to large screens have attracted attention. The thin display uses a dye that absorbs visible light to adjust the color of the display. Particularly, since PDP contains unnecessary light emission at 550 to 620 nm due to emission of rare gas, particularly neon contained in the panel, a dye that absorbs neon light emission is used.

  Conventional dyes that absorb visible light include cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, phthalocyanine dyes, subphthalocyanine dyes, rhodamine dyes, oxonol dyes, quinone dyes, and azo dyes. Dyes and xanthene dyes are used. Among them, cyanine dyes and porphyrin dyes are known to have a sharp absorption spectrum of visible light and selectively absorb specific wavelengths (for example, see Patent Documents 1 and 2).

Thin displays also generate near infrared light. Since this near infrared ray causes a malfunction of the remote control, it is necessary to remove the near infrared ray. As the near-infrared absorbing material, a material added with a dye that absorbs near-infrared rays is widely known. As the near-infrared absorbing dyes, cyanine-based, polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, diimonium-based, pyrylium-based pigments and the like are conventionally used. Among them, diimonium dyes are frequently used because they have a high near-infrared absorption ability at wavelengths of 850 to 1100 nm and high transparency in the visible light region. In addition, anti-reflection films are used for thin displays to suppress reflected light. Further, an anti-glare film (anti-glare film) is also necessary.

When the thin display is a PDP, a discharge is generated in a rare gas enclosed in the panel, particularly a gas mainly composed of neon, and the R provided in the cell inside the panel is generated by vacuum ultraviolet rays generated at that time. , G and B phosphors are caused to emit light. Therefore, electromagnetic waves unnecessary for the operation of the PDP are simultaneously emitted during this light emission process. It is necessary to shield this electromagnetic wave.
For this reason, an optical filter for a thin display can be produced by laminating a layer that selectively absorbs visible light, a near-infrared absorbing layer, an antireflection layer, and (optionally an electromagnetic shielding layer) on a support. It is common.

Moreover, the pigment | dye which absorbs visible light can be used also for optical information recording material uses, such as DVD-R. Among dyes that absorb visible light, those that emit light are attracting attention as backlights for electroluminescence displays and liquid crystal displays. (For example, see Patent Documents 3 and 4)
JP 2004-53799 A JP 2000-275432 A JP 2005-54150 A JP 2001-164245 A

  Among dyes that absorb visible light, cyanine dyes have a large extinction coefficient, but are generally difficult to dissolve in organic solvents such as ketones, esters, and aromatics, and are limited to use as coating agents. It had been. In addition, the cyanine dye may have poor durability. The decrease in visible light absorption ability can be a serious problem when used in optical semiconductor devices and thin display applications. Furthermore, even when the cyanine dye itself does not deteriorate, other coexisting dyes such as diimonium dye may be deteriorated, which is difficult to apply to the optical filter for PDP.

  Therefore, an object of the present invention is to provide a visible light absorbing material and a light emitting material which are excellent in durability and visible absorption ability by enhancing the durability and solubility of the visible light absorbing dye. Furthermore, an object of the present invention is to provide an optical filter for a thin display using the visible light absorbing material, and a thin display.

  As a result of intensive studies on the solubility and durability of the dye, the present inventors have found that a borate in which an aryl group having an electron-withdrawing group is bonded to a boron atom is the solubility and durability of a visible light absorbing dye. It has been found that a visible light absorbing material to which such a borate is added is excellent in durability, in the case of a luminescent material, the emission intensity is increased, and the deterioration of the diimonium dye is suppressed. It has also been found that by using this visible light absorbing material, a thin display optical filter, a thin display, an optical information recording material, and a light emitting material excellent in optical properties and durability can be obtained. Based on the above findings, the present invention has been completed.

  That is, the object is achieved by a borate for a visible light absorbing material having an anion represented by the following formula (1a).

ただし、式中、Ｒ１は電子吸引性基を有するアリール基を示し、Ｒ２は有機基、ハロゲン基または水酸基を示し、ｍは１〜４の整数である。

However, in formula, R1 shows the aryl group which has an electron withdrawing group, R2 shows an organic group, a halogen group, or a hydroxyl group, and m is an integer of 1-4.

  The other object is achieved by a visible light absorbing material including the borate of the present invention and a visible light absorbing dye.

  Still another object is achieved by an optical filter for thin display and a thin display using the visible light absorbing material of the present invention, an optical information recording material, and a light emitting material.

  Since the borate of the present invention improves the solubility and durability of the visible light absorbing dye, it can be suitably used for various visible light absorbing materials. In addition, when the visible light absorbing material containing the borate of the present invention is used for an optical filter for thin display, a thin display, an optical information recording material, and a light emitting material, excellent optical characteristics are maintained for a long period of time.

  Hereinafter, the present invention will be described in detail.

  The present invention provides the following formula (1):

In the formula, R ¹ represents an aryl group having an electron-withdrawing group, R ² represents an organic group, a halogen group or a hydroxyl group, and m is an integer of 1 to 4.
It is related with the borate for visible light absorption materials which has an anion shown by these.

(1) Borate anion The anion used in the present invention is a borate anion represented by the above formula (1), and by binding an aryl group having an electron-withdrawing group to a boron atom, Durability can be improved.

R ¹ in the above formula (1) represents an aryl group having an electron-withdrawing group, and is not particularly limited, but is an electron-withdrawing group bonded to an aryl group having 6 to 12 carbon atoms. Preferably, for example, those in which an electron-withdrawing group is bonded to a phenyl group, a naphthyl group, or a biphenyl group. Of the aryl groups exemplified above, those in which an electron-withdrawing group is bonded to a phenyl group (that is, R ¹ is a phenyl group having an electron-withdrawing group) are economical and preferable.

In addition, the electron-withdrawing group of R ¹ in the above formula (1) is not particularly limited, and specifically, —C _p F _{2p + 1} (p is a natural number), —NO ₂ , — It is preferably at least one substituent selected from the group consisting of CN, —F, —Cl and —Br, and at least one substituent selected from the group consisting of —CF ₃ , —C ₂ F ₅ and —F. Is more preferable, and -F is particularly preferable. When the aryl group includes a plurality of electron withdrawing groups, each electron withdrawing group may be the same or different. In the present invention, in particular, when -F is used, heat resistance and moist heat resistance can be improved. Therefore, in the above formula (1), R ¹ represents a pentafluorophenyl group (—C ₆ F ₅ ), —C ₆ HF ₄ , —C ₆ H ₂ F ₃ , —C ₆ H ₃ F ₂ , —C _{6. H 4 F, -C 6 F 4} CF 3, -C 6 F 3 (CF 3) 2, -C 6 F 2 (CF 3) 3, -C 6 F (CF 3) 4, -C 6 (CF 3 ) _{5 and the} like are preferable, and a pentafluorophenyl group is particularly preferable.

The substituent represented by R ² in the above formula (1) may be an organic group, a halogen atom or a hydroxyl group, and the organic group may have an electron-withdrawing group. Examples of the organic group include an aryl group having 6 to 12 carbon atoms (for example, a phenyl group, a naphthyl group, and a biphenyl group), and an alkyl group having 1 to 12 carbon atoms that may have a substituent. There is no particular limitation. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 1-ethyl Examples thereof include linear, branched, and alicyclic alkyl groups such as propyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, and cyclohexyl group. In particular, when the organic group is an alkyl group, it is more preferable to have an electron-withdrawing group, and it is more preferable that all or part of the hydrogen atoms are substituted with fluorine atoms. Specifically, trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, perfluoroethyl group, perfluoropropyl group And a perfluorobutyl group. Specific examples of the halogen atom include -F, -Cl, -Br, and -I, and -F is more preferable.

In the present invention, m in the formula (1) is not particularly limited as long as it is 1 to 4, but is preferably 4, that is, having a structure represented by [B (R ¹ ) ₄ ] ^−. is there. In the present invention, when m is 2 or more, a plurality of R ¹ are included in the borate anion. In this case, the plurality of R ¹ may be the same or different.

Examples of the borate anion represented by the above formula (1) include [B (C ₆ F ₅ ) ₄ ] ^- (tetrakis (pentafluorophenyl) borate), [B (C ₆ F ₄ CF ₃ ) ₄ ]- , [B (C ₆ F ₅ ) ₃ (C ₆ H ₅ )] ⁻ , [B (C ₆ F ₅ ) ₂ (C ₆ H ₅ ) ₂ ] ⁻ , [B (C ₆ F ₅ ) (C ₆ H ₅ ) ₃ ] ⁻ , [B (C ₆ F ₅ ) ₃ F] ⁻ , [B (C ₆ F ₅ ) ₂ F ₂ ] ⁻ , [B (C ₆ F ₅ ) F ₃ ] ⁻ , [B (C _{6 F 5) 3 (CF 3} )] -, [B (C 6 F 5) 2 (CF 3) 2] -, [B (C 6 F 5) (CF 3) 3] -, [B (C 6 _{F 5) 3 (C 6 F} 4 CF 3)] -, [B (C 6 F 5) 2 (C 6 F 4 CF 3) 2] -, [B (C 6 F 5) (C 6 F 4 CF ^{_{3) 3] -, [B}} (C 6 F 4 CF 3) 3 F] -, [B (C 6 F 4 CF 3) 2 F 2] -, [B (C 6 F 4 CF 3) F 3] ^{_{-, [B (C 6 F}} 4 CF 3) 3 (CF 3)] -, [B (C 6 F 4 CF 3) 2 (CF 3) 2] -, [B (C 6 F 4 CF 3) ( ^{_{CF 3) 3] -, [}} B (C 6 F 5) 3 (C 6 H 13)] -, [B (C 6 F 5) 2 (C 6 H 13) 2] -, [B (C 6 F _{5) (C 6 H 13)} 3] -, [B (C 6 H 4 CF 3) 4] -, and _{[B (C 6 H 3 F} 2) 4] - , and the like. In the present invention, among the exemplified borate anions, [B (C ₆ F ₅ ) ₄ ] ⁻ is more preferable. In addition, in this invention, the said borate anion may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

(2) Borate The salt containing the anion of the formula (1) contains the borate anion of the above formula (1) and a counter cation, but the counter cation may be a cation having no visible light absorption ability. It may be a cation having a visible light absorption ability. In the former case, since it does not have a visible light absorbing ability, it is used by mixing with a visible light absorbing dye. By adding the borate of the above formula (1), the solubility and durability of the visible light absorbing dye can be improved. In the latter case, the borate itself exhibits visible light absorbing ability, and becomes a visible light absorbing dye having good solubility and durability.

  Hereinafter, in the former case, that is, an embodiment in which the borate of the present invention is a salt of a borate anion of the above formula (1) and a cation having no visible light absorption ability will be described.

  The salt containing the anion of the formula (1) according to the present invention is an alkali metal salt of the borate anion such as lithium, sodium, potassium, rubidium and cesium; alkaline earth such as beryllium, magnesium, calcium, strontium and barium Metal salts; transition metal salts such as silver and copper; ammonium, n-butylammonium, dimethylammonium, trimethylammonium, triethylammonium, triisopropylammonium, tri-n-butylammonium, tetramethylammonium, tetraethylammonium, tetra-n- Ammonium salts such as butylammonium and N, N-dimethylcyclohexylammonium; N-methylanilinium, N, N-dimethylanilinium, N, N-dimethyl-4-methylanilinium, N, N-di Anilinium salts such as ethylanilinium, N, N-diphenylanilinium, N, N, N-trimethylanilinium; pyridinium, N-methylpyridinium, N-butylpyridinium, N-methyl-4-methyl-pyridinium, N- Benzylpyridinium, 3-methyl-N-butylpyridinium, 2-methylpyridinium, 3-methylpyridinium, 4-methylpyridinium, 2,3-dimethylpyridinium, 2,4-dimethylpyridinium, 2,6-dimethylpyridinium, 3, 4-dimethylpyridinium, 3,5-dimethylpyridinium, 2,4,6-trimethylpyridinium, 2-fluoropyridinium, 3-fluoropyridinium, 4-fluoropyridinium, 2,6-difluoropyridinium, 2,3,4,5 , 6-Pentaful Ropyridinium, 2-chloropyridinium, 3-chloropyridinium, 4-chloropyridinium, 2,3-dichloropyridinium, 2,5-dichloropyridinium, 2,6-dichloropyridinium, 3,5-dichloropyridinium, 3,5- Dichloro-2,4,6-trifluoropyridinium, 2-bromopyridinium, 3-bromopyridinium, 4-bromopyridinium, 2,5-dibromopyridinium, 2,6-dibromopyridinium, 3,5-dibromopyridinium, 2-cyano Pyridinium, 3-cyanopyridinium, 4-cyanopyridinium, 2-hydroxypyridinium, 3-hydroxypyridinium, 4-hydroxypyridinium, 2,3-dihydroxypyridinium, 2,4-dihydroxypyridinium, 2-methyl-5 Ethylpyridinium, 2-chloro-3-cyanopyridinium, 4-carboxamidopyridinium, 4-carboxaldehyde pyridinium, 2-phenylpyridinium, 3-phenylpyridinium, 4-phenylpyridinium, 2,6-diphenylpyridinium, 4-nitropyridinium, 4-methoxypyridinium, 4-vinylpyridinium, 4-mercaptopyridinium, 4-t-butylpyridinium, 2,6-dit-butylpyridinium, 2-benzylpyridinium, 3-acetylpyridinium, 4-ethylpyridinium, 2-carboxyl Pyridinium salts such as pyridinium acid, pyridinium 4-carboxylate, 2-benzoylpyridinium; imidazolium, 1-methyl-imidazolium, 1-ethyl-3-methylimidazolium, 1-propyl Ropyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-methyl-3-octylimidazolium, 1-methyl-N-benzylimidazolium, 1- Imidazolium salts such as methyl-3- (3-phenylpropyl) imidazolium, 1-butyl-2,3-dimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium; 1-ethyl-1-methyl- Pyrrolidinium salts such as pyrrolidinium and 1-butyl-1-methyl-pyrrolidinium; quinolinium salts such as quinolinium and isoquinolinium; carbenium salts such as triphenylcarbenium and tri-4-methoxyphenylcarbenium; dimethylphenylphosphonium and triphenyl Phosphonium, tetraethyl Osufoniumu, phosphonium salts such as tetraphenyl phosphonium; trimethyl sulfonium, triphenyl sulfonium, sulfonium salts and the like; diphenyl iodonium, etc. iodonium salts such as di-4-methoxyphenyl iodonium can be used. The borate may be used alone or in the form of a mixture of two or more.

  Next, in the latter case, that is, an aspect in which the borate of the present invention is a salt of the borate anion of the above formula (1) and a cation having a visible light absorption ability will be described.

The cation having a visible light absorption ability that forms a pair with the borate anion of the above formula (1) is a cation excellent in the absorption ability in the wavelength range of 400 to 800 nm. For example, polymethine cation, cyanine cation, rhodamine cation and the like can be mentioned.
Among these, cyanine-based cations have a high extinction coefficient, and sharp absorption can be obtained for a specific wavelength. In addition, many cyanine-based cations exhibit light emission and can be used as a light-emitting material.
There are cyanine-based cations having various structures, but indolium-based cations, benzoxazolium-based cations, benzimidazolium-based cations, and benzthiazolium-based cations can be preferably used. Specifically, cations represented by formulas (2) to (12) can be preferably used, but are not limited thereto.

(3) Visible light absorbing dye The borate of the present invention can improve the solubility and durability of the visible light absorbing dye. Visible light absorbing dye is not particularly limited, cyanine dye, polymethine dye, squarylium dye, porphyrin dye, phthalocyanine dye, subphthalocyanine, rhodamine dye, oxonol dye, quinone dye, azo dye, Conventionally known dyes such as xanthene dyes can be widely used.

  Among these, cyanine dyes have a high extinction coefficient, and sharp absorption can be obtained for a specific wavelength. In addition, many cyanine dyes emit light and can be used as light emitting materials. Specifically, S0232 (manufactured by FEW CHEMICALS: iodonium salt of formula 2), S0041 (manufactured by FEW CHEMICALS: iodonium salt of formula 3), S0290 (manufactured by FEW CHEMICALS: iodide salt of formula 4), S0390 (manufactured by FEW CHEMICALS: Perchlorate of formula 5), S0409 (manufactured by FEW CHEMICALS: perchlorate of formula 6), S0366 (manufactured by FEW CHEMICALS: hexafluorophosphate of formula 7), S0773 (manufactured by FEW CHEMICALS: of formula 8 Tetrafluoroborate), S0450 (manufactured by FEW CHEMICALS: chloride salt of formula 9) and the like.

When the visible light absorbing material of the present invention is used as an optical filter for PDP, it is preferable to use a visible absorbing dye having a maximum absorption wavelength of 550 to 650 nm in order to absorb unnecessary neon light emission. The type of the dye that absorbs neon light emission is not particularly limited, and a cyanine dye and a tetraazaporphyrin dye can be used.
Specific examples of cyanine dyes include S0290 (manufactured by FEW CHEMICALS: iodide salt of formula c), S0390 (manufactured by FEW CHEMICALS: perchlorate of formula d), S0409 (manufactured by FEW CHEMICALS: perchlorate of formula e). ADA5150 (manufactured by HW HANDS) Adeka Arcles TY-102 (manufactured by Asahi Denka Kogyo), Adeka Arcles TY-100 (manufactured by Asahi Denka Kogyo), Adeka Arcles TY-235 (manufactured by Asahi Denka Kogyo), Adeka Arcles TY-171 (Asahi Denka Kogyo), Adeka Arcles GPZ-101 (Asahi Denka Kogyo), NK-5451 (Hayashibara Biochemical Laboratory), NK-5532 (Hayashibara Biochemical Laboratory), NK -5450 (manufactured by Hayashibara Biochemical Research Institute), as a specific example of tetraazaporphyrin dye, TAP-2 (Yamada Chemical Industries ), TAP-18 (manufactured by Yamada Chemical Co.), and a TAP-45 (manufactured by Yamada Chemical Co.) and the like.

A visible light absorbing dye having a melting point of 200 ° C. or higher is excellent in durability. Specifically, ADA5150 (manufactured by HW HANDS, melting point: 259 ° C.) Adeka Arcles TY-102 (Asahi Denka Kogyo, melting point: 257 ° C.), Adeka Arcles TY-100 (Asahi Denka Kogyo, melting point: 300 ° C.) Adeka Arcs TY-235 (Asahi Denka Kogyo's melting point: 220 ° C), Adeka Arcles GPZ-101 (Asahi Denka Kogyo's melting point: 260 ° C), and the like.
(4) Visible light absorption composition The visible light absorber composition of the present invention is a composition containing a borate anion of formula (1) and a visible light absorbing dye, or a borate anion of formula (1) and visible light absorption performance. It is a composition containing the pigment | dye which consists of a cation which has. You may use together the salt which has a borate anion of Formula (1) further to the pigment | dye which consists of the borate anion of Formula (1) and the cation which has a visible light absorption ability.
Although the compounding quantity of the anion of Formula (1) in a visible light absorption composition can be suitably selected according to a use, Preferably it is 0.5-20 mol with respect to 1 mol of visible light absorption pigment | dyes used together. Preferably it is 1-15 mol. At this time, if the amount of the anion salt is less than 0.5 mol, sufficient solubility and durability cannot be improved, and if it exceeds 20 mol, an effect commensurate with the addition cannot be obtained and it is not economical. There is sex.

  The solution of the visible light absorbing composition of the present invention can be used as an optical information recording material by applying it to a disk substrate with a spin coater or the like.

  Moreover, the near-infrared absorption composition of this invention may contain resin further. The resin used in the present invention is not particularly limited as long as it can be generally used for an optical material, and is preferably as transparent as possible. More specifically, as preferred resins, polyethylene, polypropylene, carboxylated polyolefin, chlorinated polyolefin, polyolefin resins such as cycloolefin polymer, polystyrene, acrylate ester polymer, methacrylate ester polymer, vinyl acetate polymer, Preferred are vinyl halide polymers, vinyl polymers such as POVAL, polyamides such as nylon, polyurethanes, polyesters such as PET, polyvinyl acetals such as polycarbonates, epoxy resins and butyral resins.

  A particularly preferable resin is a polymer obtained by polymerizing (meth) acrylic acid ester, and this (meth) acrylic acid ester is a linear, branched, alicyclic, polycyclic having 1 to 10 carbon atoms. It is a polymer having an alicyclic alkyl group. Specific examples include methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, acrylic Examples thereof include polymers composed of octyl acid and the like. A monomer may use only 1 type or may copolymerize multiple types. The amount of each monomer used is not particularly limited.

  Of these, resins that can be melted or made into a solution are preferably used. At this time, if a high-Tg resin that can be melted is used, a near-infrared absorbing composition that can be molded is obtained. For example, a resin that can be melted and has a Tg of 80 ° C. or higher can be made into a molding material by kneading a near-infrared absorbing dye. Suitable resins include methacrylic polymers such as polymethyl methacrylate and α-hydroxymethyl acrylate copolymer, polycarbonate, butyral resin, cyclopolyolefin polymer, Arton (manufactured by Nippon Synthetic Rubber), Zeonore ( Nippon Zeon), O-PET (Kanebo), Sumipex (Sumitomo Chemical), Optrex (Hitachi Chemical Industries).

Moreover, the near-infrared absorbing composition can be made into a solution by using a resin that can be made into a solution. By this solution, the near-infrared absorbing composition can be a coating agent. From this viewpoint, preferred resins include methacrylic acid ester polymers, Arton (manufactured by Nippon Synthetic Rubber), Zeonore (manufactured by Nippon Zeon), and O-PET (manufactured by Kanebo).
Particularly preferred is a polymer obtained by polymerizing a methacrylic acid ester having a linear, branched, alicyclic or polycyclic alicyclic alkyl group which is an alkyl group having 1 to 10 carbon atoms. Examples of the methacrylic acid ester include methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. This polymer may be a polymer composed of one kind of methacrylic acid ester monomer, or may be a copolymer composed of a plurality of methacrylic acid ester monomers. Moreover, the polymer which copolymerized monomers other than said methacrylate ester and the said methacrylate ester may be sufficient. Other monomers include aromatic monomers such as styrene and methylstyrene; maleimide monomers such as phenylmaleimide and cyclohexylmaleimide; monomers having a carboxyl group such as methacrylic acid and acrylic acid; Examples thereof include acrylic acid esters having 15 alkyl groups; monomers having hydroxy groups such as hydroxyethyl methacrylate and hydroxyethyl acrylate. The amount of the monomer other than the methacrylic acid ester is preferably less than 50% by weight, more preferably less than 30% by weight, and still more preferably less than 10% by weight. Specific examples include Sumipex (manufactured by Sumitomo Chemical), Optrex (manufactured by Hitachi Chemical Co., Ltd.), and Hals Hybrid IR (manufactured by Nippon Shokubai). Moreover, resin whose glass transition temperature (Tg) is higher than 85 degreeC can suppress effectively deterioration of the pigment | dye by a heat | fever or a water | moisture content.

  A high Tg resin has extremely high durability, but has a drawback of being easily broken when used for a film. In order to suppress the cracking of the resin, the polystyrene equivalent weight average molecular weight is 50,000 or more, more preferably 100,000 or more.

  The near-infrared absorbing composition of the present invention has good durability even when Tg is 85 ° C. or lower. The kind in particular of resin is not restrict | limited, An acrylic resin, a polyester resin, etc. can be used. In order to achieve both high resistance to cracking and high durability, the Tg of the resin is preferably 65 to 85 ° C, and preferably 70 to 80 ° C.

  In order to make it difficult to break, the polymer structure of the resin is preferably branched rather than linear. When the branched structure is used, even when the molecular weight is increased, the viscosity of the resin is low and the handling becomes easy.

  In order to obtain a branched resin, a macromonomer, a polyfunctional monomer, a polyfunctional initiator, and a polyfunctional chain transfer agent can be used. As the macromonomer, AA-6, AA-2, AS-6, AB-6, AK-5 (all manufactured by Toagosei Co., Ltd.) and the like can be used. Examples of the polyfunctional monomer include LIGHT EG EG, LIGHT SEL 1,4BG, LIGHT ESTER NP, LIGHT ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the polyfunctional initiator include Pertetra A, BTTB-50 (all manufactured by NOF Corporation), Trigonox 17-40MB, Parkadox 12-XL25 (all manufactured by Explosive Akzo), and the like. As the polyfunctional chain transfer agent, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate) or the like can be used.

  On the other hand, this resin may be a pressure-sensitive adhesive or an adhesive, or a mixture of a pressure-sensitive adhesive and an adhesive. The resin that is an adhesive is also referred to as an adhesive resin below. Since the near-infrared absorbing composition of the present invention using a pressure-sensitive adhesive or adhesive as a resin can be bonded to another functional film, an optical filter can be easily and economically produced. Resins suitable as the pressure-sensitive adhesive include acrylics, silicons, SBRs, and the like. Particularly preferred is a polymer obtained by polymerizing ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate or the like as a main component. From the viewpoint of imparting adhesiveness to the adherend, the Tg of the resin is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower. The monomer used is not particularly limited as long as the glass transition temperature calculated using the Fox formula represented by the following formula satisfies a predetermined value.

1 / (Tg + 273) = Σ [Wi / (Tgi + 273)]: Fox formula Tg (° C.): glass transition temperature Wi: weight fraction of each monomer Tgi (° C.): homopolymer of each monomer component In the present invention, when the resin is composed of one kind of monomer, the glass transition temperature Tg of the resin is an actual measurement value. When the resin is a copolymer, the glass transition temperature Tg of the resin is calculated by the Fox equation.

  When the calculated solubility parameter of the pressure-sensitive adhesive resin is high, the durability of the dimonium dye may be inferior, so the solubility parameter is preferably 9.80 or less. The calculated solubility parameter is a value calculated by the method described on pages 147 to 154 of “POLYMER ENGINEERING AND SCIENCE” (1974, Vol. 14, No. 2). The method is outlined below.

  The solubility parameter (δ) of the homopolymer is calculated by the following formula based on the evaporation energy (Δei) and molar volume (Δvi) of the structural unit forming the polymer.

δ = (ΣΔei / ΣΔvi) ^1/2
Δei: Evaporation energy of atom or atomic group of component i Δvi: Molar volume of atom or atomic group of component i The solubility parameter of the copolymer is determined by the above formula according to each constituent unit constituting the copolymer. The solubility parameter of each homopolymer of the body is calculated, and the solubility parameter is multiplied by the mole fraction of each constituent monomer.

A more preferable adhesive resin is a resin obtained by polymerizing a monomer mixture containing the monomers represented by the following (m1), (m2) and (m3) in the following ratio.
(M1) (meth) acrylic acid ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic cyclic alkyl group; 5 to 40% by weight
(M2) (Meth) acrylic acid ester having a linear or branched alkyl group having 1 to 10 carbon atoms; 60 to 95% by weight
(M3) Other copolymerizable monomers: 0 to 30% by weight
Specific examples of the monomer (m1) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Etc.

  Specific examples of the monomer (m2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, etc. are mentioned.

  Specific examples of the monomer (m3) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, and the like. (Meth) acrylates; styrene monomers represented by α-methylstyrene, vinyl toluene, styrene, etc .; vinyl ether monomers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc .; fumaric acid, fumaric acid Monoalkyl ester of fumaric acid; maleic acid; monoalkyl ester of maleic acid; dialkyl ester of maleic acid; itaconic acid; monoalkyl ester of itaconic acid; dialkyl ester of itaconic acid ; (Meth) acrylonitrile; and the like vinylcarbazole, vinyl chloride, vinylidene chloride; vinyl acetate; vinyl ketones, vinyl pyridine. In addition, monomers having a functional group such as a carboxyl group, an oxazolinyl group, a pyrrolidonyl group, and a fluoroalkyl group may be copolymerized within a range that does not impair the object of the present invention.

  Commercially available initiators such as peroxides and azos can be used for the polymerization. Peroxide-based initiators include peroxyesters such as perbutyl O and perhexyl O (both manufactured by NOF); peroxydicarbonates such as PERROYL L and PEROIL O (both manufactured by NOF); Diacyl peroxides such as BW and Nyper BMT (both manufactured by NOF); Peroxyketals such as perhexa 3M and perhexa MC (both manufactured by NOF); perbutyl P, park mill D (all manufactured by NOF) And hydroperoxides such as Park Mill P and Permenter H (both manufactured by NOF Corporation). Examples of the azo initiator include ABN-E, ABN-R, and ABN-V (all manufactured by Nippon Hydrazine Kogyo Co., Ltd.).

  In the polymerization of the resin, a chain transfer agent may be used as necessary. The chain transfer agent is not particularly limited as long as it can be adjusted to a predetermined molecular weight, and thiol compounds such as normal dodecyl mercaptan, dithioglycol, octyl thioglycolate, and mercaptoethanol can be used.

  Further, the polymerization of the resin may be performed without a solvent or may be performed in an organic solvent. When polymerizing in an organic solvent, aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; other known organic solvents are used. it can. The type of organic solvent to be used is determined in consideration of the solubility of the obtained resin and the polymerization temperature, but the boiling point of toluene, ethyl acetate, methyl ethyl ketone, etc. is 120 ° C. or less in terms of the difficulty of remaining the residual solvent during drying. Organic solvents are preferred.

Further, the resin may have a single composition, or may be a polymer alloy or a polymer blend in which polymers having different compositions are combined.
The amount of the visible light absorbing dye added to the resin can be arbitrarily selected according to the type, film thickness, and purpose of the dye. If the purpose is to absorb neon emission of PDP, it is preferable to add such that the transmittance at the maximum absorption wavelength is about 20 to 80%.
When the borate and the visible light absorbing material of the present invention are used for thin display applications, not only the visible light absorbing ability but also the near infrared absorbing ability is required. In order to impart near-infrared absorbing ability, a near-infrared absorbing dye may be used in combination with a visible light absorbing dye and a friend. As the near-infrared absorbing dyes, cyanine-based, polymethine-based, squarylium-based, porphyrin-based, dithiol metal complex-based, phthalocyanine-based, diimonium-based, pyrylium-based pigments and the like are conventionally used. Of these, diimonium dyes, phthalocyanine dyes, and cyanine dyes are frequently used.

  Diimonium-based dyes are characterized by high near-infrared absorptivity with a wavelength of 850 to 1100 nm and high transparency in the visible light region. The diimonium dye that can be used in the present invention is not particularly limited, but is a salt composed of a diimonium cation represented by the formula (a) and an anion.

R ^{1 to} R ⁸ in the formula (a) each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent. R ^{1 to} R ⁸ may be different or the same.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Linear, branched, alicyclic alkyl such as 1-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, cyclohexyl group, etc. Groups and the like.

  Examples of the substituent that can be bonded to the optionally substituted alkyl group having 1 to 10 carbon atoms include cyano group; hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom; methoxy group; C1-C6 alkoxy groups such as ethoxy group, n-propoxy group, n-butoxy group; methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group An alkoxyalkoxy group having 2 to 8 carbon atoms, such as a methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, or the like; an allyloxy group; a phenoxy group; Tolyloxy group, xylyloxy group, naphthylo group An aryloxy group having 6 to 12 carbon atoms such as a cis group; an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and an n-butoxycarbonyl group; C2-C7 alkylcarbonyloxy groups such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyl Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an oxy group and an n-butoxycarbonyloxy group.

The counter anion of the diimonium dye is not particularly limited, and chloride ion, bromide ion, iodide ion, perchlorate ion, nitrate ion, benzenesulfonate ion, P-toluenesulfonate ion, methylsulfate ion, ethylsulfate ion Ion, propyl sulfate ion, tetrafluoroborate ion, tetraphenylborate ion, tetrakis (pentafluorophenyl) borate ion, 4-morpholinosulfonyl-1,2-benzenedithiol copper complex anion, tris (trifluoromethanesulfonyl) methide ion Bis (trifluoromethanesulfonyl) imide ion, bis (fluorosulfonyl) imide ion, 2,2,2-trifluoro-N- (trifluoromethanesulfonyl) acetamide ion, hexafluorophosphate ion, benzene Ruffinate ion, acetate ion, trifluoroacetate ion, propionate acetate ion, benzoate ion, oxalate ion, succinate ion, malonate ion, oleate ion, stearate ion, citrate ion, monohydrogen diphosphate ion , Dihydrogen monophosphate ion, pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion, trifluoromethanesulfonate ion, hexafluoroarsenate ion, hexafluoroantimonate ion, molybdate ion, tungstate ion, Titanate ion, zirconate ion, sulfate ion, vanadate ion, borate ion and the like can be used.
Among these, an organic anion having a molecular weight of 250 or more is preferable because the solubility and durability of the dye are good. Specifically, tetrakis (pentafluorophenyl) borate ion (molecular weight 679.0), 4-morpholinosulfonyl-1,2-benzenedithiol copper complex anion (molecular weight 642.4), tris (trifluoromethanesulfonyl) methide ion (molecular weight) 411.2), bis (trifluoromethanesulfonyl) imide ion (molecular weight 280.1), imide ion, and the like.

  In the case of a diimonium dye having a melting point of 200 ° C. or higher, the durability is further improved. As such a diimonium dye, specifically, CIR-RL (Nippon Carlit bis (trifluoromethanesulfone) imide salt, melting point: 235 ° C.), CIR-1085F (Nippon Carlit bis (trifluoromethanesulfone) imide salt, melting point : 210 ° C).

  Phthalocyanine dyes are characterized by a high near-infrared absorptivity of 800 to 1000 nm and good durability. The phthalocyanine compound that can be used in the present invention is not particularly limited, but known phthalocyanine compounds can be used. Preferable phthalocyanine compounds include compounds represented by the following formula (b) or compounds represented by the following formula (c).

  [Phthalocyanine compound represented by the formula (b)]

In the above formula ^{(b), A} 1 ^{~A 16} represents a functional group. In the formula (b), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, or an optionally substituted carbon atom having 1 to 20 carbon atoms. Alkyl groups, optionally substituted alkoxy groups having 1 to 20 carbon atoms, optionally substituted aryl groups having 6 to 20 carbon atoms, optionally substituted carbon atoms 6 to 20 Aryloxy groups, optionally substituted aralkyl groups having 7 to 20 carbon atoms, optionally substituted aralkyloxy groups having 7 to 20 carbon atoms, and optionally substituted carbon atoms 1-20 alkylthio groups, optionally substituted arylthio groups having 6-20 carbon atoms, optionally substituted aralkylthio groups having 7-20 carbon atoms, substituted An optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, and an optionally substituted aralkylsulfonyl group having 7 to 20 carbon atoms Group, an optionally substituted acyl group having 1 to 20 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms, and an optionally substituted carbon atom having 6 to 20 carbon atoms An aryloxycarbonyl group, an optionally substituted aralkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms, and optionally substituted. Arylcarbonyloxy group having 6 to 20 carbon atoms, optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms, substituted Carbon atoms optionally 2-20 heterocyclic group, a substituted amino group which may be, optionally substituted aminosulfonyl group or an optionally substituted aminocarbonyl group. The functional groups of A ^{1 to} A ¹⁶ may be the same type or different types, and may be the same or different in the same type, and the functional groups may be connected via a linking group. In the formula (b), M ¹ represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal. In the present specification, the “acyl group” has the same definition as that described on page 17 of the third edition of the Dictionary of Science and Technology Terms published by the Nikkan Kogyo Shimbun. It is a group from which a group has been removed, and is a group represented by the formula: RCO— (where R is an aliphatic group, an alicyclic group or an aromatic group).
(When the terminal is a functional group other than an amino group)
In the above formula (b), examples of the halogen atom of the functional groups A ^{1 to} A ¹⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. It is not limited to these. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic Although the alkoxy group of this is mentioned, it is not limited to these. Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include phenoxy group and naphthoxy group, but are not limited thereto. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group and the like, but are not limited thereto. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group and 2-ethylhexylthio group. However, it is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group, but are not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylthio group, a phenethylthio group, a diphenylmethylthio group and the like. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl. Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. Examples include, but are not limited to, linear, branched, or cyclic alkylsulfonyl groups. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include, but are not limited to, a phenylsulfonyl group and a naphthylsulfonyl group. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but are not limited thereto. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include, but are not limited to, branched or cyclic alkylcarbonyl groups; arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups; and aralkylcarbonyl groups such as benzoyl groups. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Examples thereof include, but are not limited to, a carbonyl group and a 2-ethylhexyloxycarbonyl group. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, phenoxycarbonyl and naphthylcarbonyl groups. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like. . Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned, However, It is not limited to these. Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzoyloxy group. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylcarbonyloxy group. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, and a morpholine group.

In the above formula (b), the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group of the functional groups A ^{1 to} A ¹⁶ An arylsulfonyl group, an aralkylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an aralkylcarbonyloxy group or a heterocyclic group As the substituents present in these functional groups A ^{1 to} A ¹⁶ , for example, halogen atoms, acyl groups, alkyl groups, phenyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, Alkyria Group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic group However, it is not limited to these. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.
(When the terminal is an amino group)
In the above formula (b), as the substituents on the optionally substituted amino group, the optionally substituted aminosulfonyl group or the optionally substituted aminocarbonyl group of the functional groups A ^{1 to} A ¹⁶ , Hydrogen atom: linear, branched or cyclic such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group and cyclohexyl group Alkyl group; aryl group such as phenyl group and naphthyl group; aralkyl group such as benzyl group and phenethyl group; acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso- Butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexyl Linear, branched or cyclic alkylcarbonyl groups such as carbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group and n-octylcarbonyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; benzyl Examples thereof include, but are not limited to, an aralkylcarbonyl group such as a carbonyl group, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2, and when 2 are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, the substituents may be connected via a linking group.

  Alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl which is a substituent to the above-mentioned optionally substituted amino group, optionally substituted aminosulfonyl group or optionally substituted aminocarbonyl group Group, aralkylcarbonyl group and the like, which may be further present as a substituent, for example, halogen atom, acyl group, alkyl group, phenyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, nitro group, amino group, Alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic ring Etc. The, but not limited thereto. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

Examples of the divalent metal as the metal M ¹ include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and Rh (II). , Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II) , Pb (II), Sn (II) and the like, but are not limited thereto. Examples of trivalent substituted metal atoms as the metal M ¹ include Al—F, Al—Cl, Al—Br, Al—I, Fe—Cl, Ga—F, Ga—Cl, Ga—I, and Ga—. Br, In-F, In- Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5, Al-C 6 H 4 (CH 3 _{), In-C 6 H 5} , In-C 6 H 4 (CH 3), In-C 6 H 5, Mn (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Examples thereof include, but are not limited to, Ru-Cl. Examples of tetravalent substituted metal atoms as the metal M ¹ include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl _{2 2} , SnBr ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , Ge (OH) ₂ , Mn (OH) ₂ , Si (OH) ₂ , Sn (OH) ₂ , Zr (OH) ₂ , Cr (R ^x ) ₂ , Ge (R ^x ) ₂ , Si (R ^x ) ₂ , Sn (R ^x ) ₂ , Ti (R ^x ) ₂ {R ^x represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof} Cr ( OR ^y ) ₂ , Ge (OR ^y ) ₂ , Si (OR ^y ) ₂ , Sn (OR ^y ) ₂ , Ti (OR ^y ) ₂ , {R ^y is an alkyl group, phenyl group, naphthyl group, trialkylsilyl Group, a dialkylalkoxysilyl group or a derivative thereof}, Sn (SR ^z ) ₂ , Ge (SR ^z ) ₂ {R ^z represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof} However, it is not limited to these. Examples oxy metal as the metal M ¹ is, VO, MnO, does not but such as TiO and the like is not limited thereto.

  [Phthalocyanine compound represented by formula (c)]

In the above formula ^{(c), B} 1 ^{~B 24} represents a functional group. B ^{1 to} B ²⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or a substituted group. An optionally substituted alkoxy group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, and substitution An aralkyl group having 7 to 20 carbon atoms which may be substituted, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, and an alkylthio group having 1 to 20 carbon atoms which may be substituted , An optionally substituted arylthio group having 6 to 20 carbon atoms, an optionally substituted aralkylthio group having 7 to 20 carbon atoms, and an optionally substituted carbon atom 1-20 alkylsulfonyl groups, optionally substituted arylsulfonyl groups having 6-20 carbon atoms, optionally substituted aralkylsulfonyl groups having 7-20 carbon atoms, optionally substituted Good acyl group having 1 to 20 carbon atoms, optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms, optionally substituted aryloxycarbonyl group having 6 to 20 carbon atoms, substitution An aralkyloxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted, and 6 to 20 carbon atoms which may be substituted Arylcarbonyloxy group, optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms, optionally substituted carbon atom Represents a 2-20 heterocyclic group, optionally substituted aminosulfonyl be also an amino group or a substituted optionally alkylsulfonyl group or an optionally substituted aminocarbonyl group. The functional groups of B ^{1 to} B ²⁴ may be the same or different, and may be the same or different in the same type, and the functional groups may be linked via a linking group. M ² represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal.

(When the terminal is a functional group other than an amino group)
In the above formula (c), examples of the halogen atom of the functional groups B ^{1 to} B ²⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like can be mentioned. It is not limited to. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic Although an alkoxy group is mentioned, it is not limited to these. Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include phenoxy group and naphthoxy group, but are not limited thereto. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group and the like, but are not limited thereto. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group and 2-ethylhexylthio group. However, it is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group, but are not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylthio group, a phenethylthio group, a diphenylmethylthio group and the like. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl. Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. Examples include, but are not limited to, linear, branched, or cyclic alkylsulfonyl groups. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include, but are not limited to, a phenylsulfonyl group and a naphthylsulfonyl group. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but are not limited thereto. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include, but are not limited to, branched or cyclic alkylcarbonyl groups; arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups; and aralkylcarbonyl groups such as benzoyl groups. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Examples thereof include, but are not limited to, a carbonyl group and a 2-ethylhexyloxycarbonyl group. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, phenoxycarbonyl and naphthylcarbonyl groups. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like. . Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned, However, It is not limited to these. Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzoyloxy group. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylcarbonyloxy group. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, and a morpholine group.

In the above formula (c), the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group, aryl of the functional groups B ^{1 to} B ²⁴ When a sulfonyl group, aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group or heterocyclic group is substituted, these Examples of the substituent present in the functional groups B ^{1 to} B ²⁴ include a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, an amino group, and an alkylamino group. , Examples include alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, and heterocyclic group. However, it is not limited to these. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

(When the terminal is an amino group)
In the above formula (c), the substituents on the optionally substituted amino group, the optionally substituted aminosulfonyl group or the optionally substituted aminocarbonyl group of the functional groups B ^{1 to} B ²⁴ are as follows: Hydrogen atom: linear, branched or cyclic such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group and cyclohexyl group Alkyl group; aryl group such as phenyl group and naphthyl group; aralkyl group such as benzyl group and phenethyl group; acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso- Butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexyl Linear, branched or cyclic alkylcarbonyl groups such as carbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group and n-octylcarbonyl group; arylcarbonyl groups such as benzoyl group and naphthylcarbonyl group; benzyl Examples thereof include, but are not limited to, an aralkylcarbonyl group such as a carbonyl group, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2, and when 2 are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, the substituents may be connected via a linking group.

  The above-mentioned amino group which may be substituted, aminosulfonyl group which may be substituted, alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl which is a substituent to the optionally substituted aminocarbonyl group Group, aralkylcarbonyl group and the like, which may be further present as a substituent, for example, halogen atom, acyl group, alkyl group, phenyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, nitro group, amino group, Alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic ring Base Including but not limited to. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

Examples of the divalent metal as the metal M ² include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and Rh (II). , Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II) , Pb (II), Sn (II) and the like, but are not limited thereto. Examples of trivalent substituted metal atoms as the metal M ² include Al—F, Al—Cl, Al—Br, Al—I, Fe—Cl, Ga—F, Ga—Cl, Ga—I, Ga— Br, In-F, In- Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5, Al-C 6 H 4 (CH 3 _{), In-C 6 H 5} , In-C 6 H 4 (CH 3), In-C 6 H 5, Mn (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Examples thereof include, but are not limited to, Ru-Cl. Examples of the tetravalent substituted metal atom as the metal M ² include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ . ₂ , SnBr ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , Ge (OH) ₂ , Mn (OH) ₂ , Si (OH) ₂ , Sn (OH) ₂ , Zr (OH) ₂ , Cr (R ^x ) ₂ , Ge (R ^x ) ₂ , Si (R ^x ) ₂ , Sn (R ^x ) ₂ , Ti (R ^x ) ₂ {R ^x represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof}, Cr (OR ^y ) ₂ , Ge (OR ^y ) ₂ , Si (OR ^y ) ₂ , Sn (OR ^y ) ₂ , Ti (OR ^y ) ₂ {R ^y is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group Group, a dialkylalkoxysilyl group or a derivative thereof}, Sn (SR ^z ) ₂ , Ge (SR ^z ) ₂ {R ^z represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof} However, it is not limited to these. Examples oxy metal as the metal M ² are, VO, MnO, does not but such as TiO and the like is not limited thereto.

  Specific examples of the phthalocyanine compound represented by the formula (b) include trade names EEXCOLOR IR-10A, EEXCOLOR IR-12, EEXCOLOR IR-14, TX-EX-906B, TX-EX-910B, TX-EX-902K, TX-EX-817 (both manufactured by Nippon Shokubai) are listed.

  Cyanine dyes are characterized by high near-infrared absorptivity of 800 to 1100 nm and high transparency in the visible light region. The cyanine dye that can be used in the present invention is not particularly limited, but salts of indolium cation, benzoxazolium cation, benzimidazolium cation, and benzthiazolium cation can be preferably used. The salt which consists of a cation shown by (d)-(o) is mentioned. As the counter anion, the same anion as that of the diimonium dye can be used.

  The commercial item illustrated below can be used as a pigment | dye containing the cation shown by said formula (d)-(o). Specifically, ADS812MI (counter anion is iodide ion) manufactured by American Dye Source Co., Ltd. can be used as a cyanine dye containing a cation represented by the above formula (d). As a cyanine dye containing a cation represented by the above formula (e), S0712 (counter anion is hexafluorophosphate ion) manufactured by FEW Chemical Co. may be used. As a cyanine dye containing a cation represented by the above formula (f), S0726 (counter anion is chloride ion) manufactured by FEW Chemical Co. may be used. As a cyanine dye containing a cation represented by the above formula (g), ADS780MT (counter anion is p-toluenesulfonic acid ion) manufactured by American Dye Source may be used. As a cyanine dye containing a cation represented by the above formula (h), S0006 (counter anion is perchlorate ion) manufactured by FEW Chemical Co. may be used. As a cyanine dye containing a cation represented by the above formula (i), S0081 (counter anion is perchlorate ion) manufactured by FEW Chemical Co. may be used. As a cyanine dye containing a cation represented by the above formula (j), S0773 (counter anion is tetrafluoroborate ion) manufactured by FEW Chemical Co. may be used. As a cyanine dye containing a cation represented by the above formula (k), trade name S0772 (counter anion is tetrafluoroborate ion) manufactured by FEW Chemical Co., Ltd. may be used. As a cyanine dye containing a cation represented by the above formula (l), trade name S0734 (counter anion is tetrafluoroborate ion) manufactured by FEW Chemical Co., Ltd. may be used. As a cyanine dye containing a cation represented by the above formula (m), trade name S0813 (counter anion is tetrafluoroborate ion) manufactured by FEW Chemical Co., Ltd. may be used. As a cyanine dye containing a cation represented by the above formula (n), trade name S0889 (counter anion is tetrafluoroborate ion) manufactured by FEW Chemical Co., Ltd. may be used. As a cyanine dye containing a cation represented by the above formula (o), trade name IR140 manufactured by Exciton (counter anion is perchlorate ion) may be used. By using a cyanine dye, a near-infrared absorbing composition having high transparency in the visible region can be obtained.

  The addition amount of the visible light absorbing dye of the present invention can be appropriately selected depending on the kind, film thickness and purpose of the dye. In the case of absorbing near infrared rays generated from a thin display, the transmittance of near infrared rays having a wavelength of 800 to 1100 nm may be 50% or less, preferably 30% or less, and most preferably 10% or less.

  Moreover, in order to adjust the color tone of the coating film, a visible light absorbing dye for toning may be added to the visible light absorbing composition of the present invention. There are no particular limitations on the type of coloring pigment, but 1: 2 chromium complex, 1: 2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole, and the like can be used. Specifically, Orazol Blue GN (manufactured by Ciba Specialty Chemicals), Orazol Blue BL (manufactured by Ciba Specialty Chemicals), Orazol Red 2B (manufactured by Ciba Specialty Chemicals), Orazol Red G (Ciba)・ Specialty Chemicals), Orazole Black CN (Ciba Specialty Chemicals), Orasol Yellow 2GLN (Ciba Specialty Chemicals), Orazole Yellow 2RLN (Ciba Specialty Chemicals), Microlith DPP Red BK (manufactured by Ciba Specialty Chemicals), and the like.

  Furthermore, the visible light absorbing composition of the present invention may contain one or more solvents, additives, and curing agents as long as the performance is not lost.

  The visible light absorbing composition of the present invention may be a composition in which a near-infrared absorbing dye is mixed in the form of a solid (for example, powder) in a resin, but in a solvent when coated on a film and used. Further, it is preferably in a dissolved, dispersed or suspended form.

  Examples of solvents that can be used in this case include aliphatic systems such as cyclohexane and methylcyclohexane; aromatic systems such as toluene and xylene; ketone systems such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester systems such as ethyl acetate and butyl acetate; Nitriles such as acetonitrile; alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as tetrahydrofuran and dibutyl ether; glycol ethers such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether and propylene glycol monomethyl ether acetate Systems; Amides such as formamide and N, N-dimethylformamide; Halogens such as methylene chloride and chloroform can be used. These may be used alone or in combination. In order to improve the durability of the dye, a solvent having a boiling point of 100 ° C. or less, such as methyl ethyl ketone and ethyl acetate, is suitable. Moreover, in order to improve the coating film appearance at the time of coating, a solvent having a boiling point of 100 to 150 ° C. such as toluene, methyl isobutyl ketone, and butyl acetate is suitable. In order to improve the crack resistance of the coating film, a solvent having a boiling point of 150 to 200 ° C. such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, and propylene glycol monomethyl ether acetate is preferable.

  The viscosity of the coating agent is appropriately selected depending on the type of coating machine, but when coating is performed by a small-diameter gravure kiss reverse method such as a micro gravure coater, the coating is performed by an extrusion method such as a die coater. In this case, 100 to 10,000 mPa · s is common. The solid content of the coating agent is adjusted according to the viscosity of the paint.

  Moreover, as an additive, the conventionally well-known additive used for the resin composition which forms a film, a coating film, etc. can be used, a dispersing agent, a leveling agent, an antifoamer, a viscosity modifier, a matting agent, Examples include tackifiers, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, quenchers, curing agents, and antiblocking agents. In addition, an isocyanate compound, a thiol compound, an epoxy compound, an amine compound, an imine compound, an oxazoline compound, a silane coupling agent, a UV curing agent, and the like can be used as the curing agent.

The visible light absorbing composition of the present invention can also be used for optical filters for thin displays such as liquid crystal displays and PDPs, and optical information recording materials such as DVD-Rs. In particular, even when a diimonium dye is added to the visible light absorbing composition of the present invention, since the diimonium dye is not easily deteriorated, a material having both visible light absorption ability and near infrared absorption ability can easily absorb visible light. Those that emit light can also be used in backlights of electroluminescence displays and liquid crystal displays. The visible light absorbing composition of the present invention is particularly suitable for use in a film or sheet form.
(5) Visible Light Absorbing Material The visible light absorbing material of the present invention may be a film formed from the visible light absorbing composition of the present invention, or the visible light absorbing composition may be formed on a transparent substrate. What laminated | stacked the coating film containing may be sufficient.

  The transparent substrate is generally usable for optical materials and is not particularly limited as long as it is substantially transparent. Specific examples include glass; olefin polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl polymers such as vinyl acetate and vinyl halides; polyesters such as PET; polycarbonate and butyral. Examples thereof include polyvinyl acetals such as resins; polyaryl ether resins. Further, the transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, and coating such as an anchor coating agent and a primer. May be applied. The base resin constituting the transparent base material can be blended with known additives, heat aging inhibitors, lubricants, antistatic agents, and the like. The transparent substrate is formed into a film or a sheet using a known method such as injection molding, T-die molding, calendar molding, compression molding, or a method of casting by melting in an organic solvent. The base material constituting the transparent base material may be unstretched or stretched, and may be laminated with another base material. The thickness of the visible light absorbing material is generally about 0.1 μm to 10 mm, but is appropriately determined according to the purpose.

  As a transparent base material for obtaining a visible light absorbing film by a coating method, a PET film is preferable, and a PET film subjected to an easy adhesion treatment is particularly preferable. Specifically, Cosmo Shine A4300 (manufactured by Toyobo), Lumirror U34 (manufactured by Toray), Melinex 705 (manufactured by Teijin DuPont) and the like can be mentioned. Functional films such as a TAC (triacetylcellulose) film, an antireflection film, an antiglare film, an impact absorbing film, an electromagnetic wave shielding film, and an ultraviolet absorbing film can also be used as the transparent substrate. Thereby, the optical filter for thin displays can be produced simply. The transparent substrate is preferably a film.

  Of these, glass, PET film, easy-adhesive PET film, TAC film, antireflection film and electromagnetic wave shielding film are preferably used as the transparent substrate. When an inorganic base material such as glass is used as the transparent base material, one having a small alkali component is preferable from the viewpoint of the durability of the dye.

  Although it does not specifically limit as a method of producing the visible light absorber of this invention, For example, the following method can be utilized. For example, (I) a method of producing a resin plate or film by kneading the near-infrared absorbing material of the present invention into a resin and thermoforming; (II) presence of a polymerization catalyst for the visible light absorbing material of the present invention and a monomer or oligomer A method of producing a resin plate or film by cast polymerization below; (III) a method of coating the visible light absorbing material of the present invention on the transparent substrate, and the like.

  As a production method of (I), the processing temperature, filming (resin plate) conditions, etc. are slightly different depending on the resin used, but usually the visible light absorbing composition of the present invention is added to the resin powder or pellets, Examples thereof include a method of heating and dissolving at 150 to 350 ° C. and then molding to produce a resin plate, a method of forming a film (resin plate) with an extruder, and the like.

  As the preparation method of (II), the visible light absorbing composition of the present invention and the monomer or oligomer are cast-polymerized in the presence of a polymerization catalyst, and the mixture is injected into a mold and reacted and cured, or Pour into a mold and solidify until a hard product is formed in the mold. Many resins can be molded in this process, and specific examples of such resins include acrylic resins, diethylene glycol bis (allyl carbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like. Among them, the casting method by bulk polymerization of methyl methacrylate, which can obtain an acrylic sheet excellent in hardness, heat resistance, and chemical resistance, is preferable.

  As the polymerization catalyst, a known radical thermal polymerization initiator can be used, and examples thereof include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide and diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. . The amount used is generally from 0.01 to 5% by weight, based on the total amount of the mixture. The heating temperature in thermal polymerization is generally 40 to 200 ° C., and the polymerization time is generally about 30 minutes to 8 hours. In addition to thermal polymerization, a method of photopolymerization by adding a photopolymerization initiator or a sensitizer can also be used.

  Examples of the method (III) include a method of coating the visible light absorbing composition of the present invention on a transparent substrate, a method in which the visible light absorbing composition of the present invention is fixed to fine particles, and the paint in which the fine particles are dispersed is a transparent base. There is a method of coating on the material.

  When applying the visible light absorbing composition to the substrate, a known coating machine can be used. Examples thereof include knife coaters such as comma coaters, fountain coaters such as slot die coaters and lip coaters, kiss coaters such as micro gravure coaters, roll coaters such as gravure coaters and reverse roll coaters, flow coaters, spray coaters and bar coaters. Prior to coating, the substrate may be surface treated by a known method such as corona discharge treatment or plasma treatment. As a drying / curing method, a known method such as hot air, far-infrared ray or UV curing can be used. You may wind up with a well-known protective film after drying and hardening.

  The drying method is not particularly limited, and hot air drying or far infrared drying can be used. The drying temperature may be determined in consideration of the length of the drying line, the line speed, the coating amount, the residual solvent amount, the type of substrate, and the like. If the substrate is a PET film, the general drying temperature is 50 to 150 ° C. When there are a plurality of dryers in one line, each dryer may be set to a different temperature and wind speed. In order to obtain a coating film having a good coating appearance, it is preferable that the drying condition on the inlet side is mild.

The visible light absorbing material of the present invention can be a constituent material of an excellent optical filter having high absorbability in the visible region. Since the visible light absorbing material of the present invention has higher durability, particularly heat resistance and moisture and heat resistance, compared to conventional visible light absorbing materials, the appearance and near infrared absorbing ability are maintained even during long-term storage and use.
The visible light absorbing composition material of the present invention can also be used for optical filters for thin displays such as liquid crystal displays and PDPs, and optical information recording materials such as DVD-Rs. Among the dyes that absorb visible light, those that emit light can also be used for backlights of electroluminescence displays and liquid crystal displays.
(6) Optical filter The optical filter of the present invention uses the visible light absorbing material of the present invention. Such an optical filter can adjust the color tone by absorbing visible light having a specific wavelength, and thus is suitable for a thin display. The image quality of the display can be improved by the optical filter of the present invention. In particular, when used in an optical filter for PDP, unnecessary light emission at 550 to 620 nm can be removed by light emission such as neon.

  In the optical filter of the present invention, in addition to the visible light absorbing layer composed of the above visible light absorbing material, a near infrared absorbing layer, an electromagnetic wave shielding layer, an antireflection layer, an antiglare layer (antiglare) layer, a scratch preventing layer, A color adjusting layer, a support such as glass, and the like may be provided.

  The configuration of each layer of the optical filter may be arbitrarily selected, and preferably an optical filter in which at least one of an antireflection layer and an antiglare layer is combined with at least three layers of a visible light absorbing layer and a near infrared absorbing layer. When the thin display is a PDP, an optical filter having at least four layers combined with an electromagnetic wave shielding layer is more preferable.

  The antireflection layer or the glare prevention layer is preferably the outermost layer on the human side. The order in which the visible light absorbing layer, near-infrared absorbing layer, and electromagnetic wave shielding layer are laminated is arbitrary. In addition, other layers such as a scratch-preventing layer, a toning layer, a shock absorbing layer, a support, and a transparent substrate may be inserted between the four layers.

When laminating each layer, physical treatment such as corona treatment and plasma treatment may be performed, and a known high-polarity polymer such as polyethyleneimine, oxazoline-based polymer, polyester or cellulose is used as an anchor coating agent. Also good.
The thin display optical filter is preferably provided with a near-infrared absorbing layer in order to cut off near-infrared rays generated from the panel. As an optical filter having two layers of a visible light absorbing layer and a near infrared absorbing layer, the visible light absorbing material and the near infrared absorbing material of the present invention may be bonded with an adhesive or the like. Moreover, it is good also as a visible light near-infrared absorption layer by adding a near-infrared absorption pigment | dye to the visible light absorption composition of this invention, and using it for the same layer.

In order to make the optical filter for thin display easy to see, it is preferable to provide an antireflection layer or an antiglare layer on the outermost layer on the human side.
The antireflection layer is for suppressing reflection of the surface and preventing reflection of external light such as a fluorescent lamp on the surface. The antireflection layer consists of a single layer of a resin with a different refractive index, such as an acrylic resin or a fluororesin, when it is made of an inorganic thin film such as a metal oxide, fluoride, silicide, boride, carbide, nitride, or sulfide. Alternatively, it may be composed of multi-layers, and as a manufacturing method in the former case, there is a method of forming an antireflection coating on a transparent substrate in the form of a single layer or a multilayer using vapor deposition or sputtering. is there. Further, as a manufacturing method in the latter case, on a transparent film, a knife coater such as a comma coater, a fountain coater such as a slot coater and a lip coater, a gravure coater, a flow coater, a spray coater, and a bar coater are used. There is a method of applying an antireflection coating to the surface.

  The glare-preventing layer is formed by converting fine powders of silica, melamine resin, acrylic resin, etc. into ink, applying it on any layer of the filter of the present invention by a conventionally known coating method, and curing it by heat or photocuring. Is done. An antiglare-treated film may be attached on the filter.

  In addition, the scratch-preventing layer is a coating solution prepared by dissolving or dispersing an acrylate such as urethane acrylate, epoxy acrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent by a conventionally known coating method, and any of the filters of the present invention. On this layer, it is formed by coating, drying and photocuring.

The optical filter having the antireflection layer or antiglare layer and the visible light absorption layer can be obtained by laminating the layer made of the visible light absorber of the present invention on the back surface of the antireflection film or antiglare film. As a method of laminating, the visible light absorbing material of the present invention formed into a film and the antireflection film or the anti-glare film may be laminated with an adhesive, or the solution of the visible light absorbing composition of the present invention is reflected. You may apply | coat directly to the back surface of a prevention film or a glare prevention film. Further, a near infrared absorbing dye may be added to the visible light absorbing composition.
When providing a visible light absorption layer or a visible light near infrared absorption layer on the back surface of the antireflection film or antiglare film, an ultraviolet absorption film may be used as a transparent substrate in order to suppress deterioration of the pigment due to ultraviolet rays. preferable.

The optical filter for plasma display is preferably provided with an electromagnetic wave shielding layer in order to remove electromagnetic waves generated from the panel.

  The electromagnetic wave shielding layer is a film in which a metal mesh is patterned on a film by etching, printing, etc., or a film in which a metal is deposited on a fiber mesh and embedded in a resin. used.

  An optical filter having two layers of a visible light absorbing layer and an electromagnetic wave shielding layer can be obtained by combining an electromagnetic wave preventing material and a visible light absorbing material. As a method of compounding, the visible light absorbing material of the present invention formed into a film and the electromagnetic wave shielding film may be bonded with an adhesive, or the solution of the visible light absorbing material of the present invention is directly applied to the electromagnetic wave shielding film. May be. Moreover, when smoothing the metal mesh on a film, the visible light absorption composition of this invention can also be used. Moreover, when embedding the fiber which vapor-deposited the metal, the visible light absorption material of this invention can also be used. A near infrared absorbing dye may be added to the visible light absorbing layer.

  As an optical filter having four layers of a visible light absorbing layer, a near infrared absorbing layer, a reflection or glare prevention layer, and an electromagnetic wave shielding layer, a visible light absorbing film, a near infrared absorbing film, a reflection made of the visible light absorbing material of the present invention are used. Alternatively, it is possible to use a film obtained by bonding four sheets of an anti-glare film and an electromagnetic wave shielding film with an adhesive. If necessary, a support such as glass or a functional film such as a color adjusting film may be laminated.

  In order to simplify the manufacturing process and film configuration of the optical filter, it is preferable to use a composite film having a plurality of functions. For example, an optical filter in which a composite film including a visible light near infrared absorption layer and an antireflection layer or an antiglare layer is bonded to an electromagnetic wave shielding film with an adhesive, or a composite including a visible light near infrared absorption layer and an electromagnetic wave shielding layer An optical filter in which a film is bonded to an antireflection film or an antiglare film with an adhesive, and an optical filter in which a composite film including an electromagnetic wave shielding layer and an antireflection layer or an antiglare layer is bonded to a visible near-infrared absorbing film with an adhesive Is mentioned.

The thin display optical filter of the present invention may be installed away from the display device or may be directly attached to the display device. When installing away from the display device, it is preferable to use glass as the support. In the case of directly bonding to a display device, an optical filter that does not use glass is preferable. When bonding directly, you may bond using the visible light absorption material of this invention made into adhesive.
(7) Thin display The thin display of the present invention is a thin display using the optical filter of the present invention. A thin display equipped with the optical display of the present invention maintains good image quality over a long period of time. In addition, a thin display in which an optical filter is bonded directly to the display screen can provide clearer image quality. When the optical filter is directly attached, it is preferable to use tempered glass as the glass of the display body or to provide an impact absorbing layer on the optical filter.

  As an adhesive when the optical filter of the present invention is attached to a display device, rubber such as styrene butadiene rubber, polyisoprene rubber, polyisobutylene rubber, natural rubber, neoprene rubber, chloroprene rubber, butyl rubber, polymethyl acrylate, Examples include polyacrylic acid alkyl esters such as ethyl polyacrylate and butyl polyacrylate, and these may be used alone, or further added with piccolite, polyvale, rosin ester, etc. as a tackifier. It may be used. Moreover, although the adhesive which has an impact absorption capability can be used as shown by Unexamined-Japanese-Patent No. 2004-263084, it is not limited to this.

  The thickness of this adhesive layer is usually 5 to 2000 μm, preferably 10 to 1000 μm. A release film is provided on the surface of the pressure-sensitive adhesive layer, and this release film protects the pressure-sensitive adhesive layer and prevents dust from adhering to the pressure-sensitive adhesive layer until the optical filter is attached to the surface of the thin display. Also good. In this case, a non-adhesive part is formed by forming a part where the adhesive layer is not provided or a non-adhesive film between the adhesive layer and the release film at the edge of the filter. If the adhesive part is used as a peeling start part, the work at the time of sticking is easy to do.

  The shock absorbing layer is for protecting the display device from external impact. It is preferably used in an optical filter that does not use a support. As the shock absorber, ethylene-vinyl acetate copolymer, acrylic polymer, polyvinyl chloride, urethane-based, silicon-based resin as disclosed in JP-A-2004-246365 and JP-A-2004-264416 However, it is not limited to these.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all. In addition, a part shows a mass part. Moreover, evaluation of visible light absorptivity, near-infrared absorptivity, luminous intensity, and heat resistance was as follows.
(1) Measurement of visible light-near infrared absorption spectrum For measurement of visible light-near infrared spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used, and a transmission spectrum of 350 to 1250 nm was measured. Visible light absorption ability was evaluated by the transmittance at the maximum absorption wavelength of the dye used. Near-infrared absorptivity was evaluated by transmittance at 1090 nm.

(2) Measurement of emission spectrum A fluorescence spectrophotometer FP-777 (manufactured by JASCO) was used for measurement of the emission spectrum. An emission spectrum was measured when light having a wavelength of 550 nm was used as excitation light.

(3) Evaluation of heat resistance The test body was left still in a 100 degreeC hot air dryer for 120 hours, and the transmission spectrum of 350-1250 nm before and behind a test was measured. For the measurement of the transmission spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used, and the change in transmittance at a wavelength of 1090 nm was evaluated. In addition, a color difference was calculated from the obtained transmission spectra before and after the test, and the change in b * was evaluated.
(Example 1-1)
As a monomer, 371.5 g of methyl methacrylate, 59 g of normal butyl acrylate, and 69.5 g of butyl acrylate were mixed to obtain a monomer mixture 1. 6 g of Parkadox 12XL25 (manufactured by gunpowder Akzo) and 100 g of toluene were mixed to obtain an initiator solution 1. 350 g of this monomer mixture 1 and 225 g of toluene were placed in a flask, and a thermometer, a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel were set in the flask. 150 g of monomer mixture 1 and 31.8 g of initiator solution 1 were mixed and placed in the dropping funnel. While flowing nitrogen gas at a rate of 20 ml / min, the flask was heated to an internal temperature of 100 ° C. 74.2 g of initiator solution 1 was added to the flask to initiate the polymerization reaction. Ten minutes after the introduction of the polymerization initiator, the mixture in the dropping funnel (mixture of the monomer mixture 1 and the initiator solution 1) was added to the flask over 60 minutes. After the addition, the dropping funnel was washed with 75 g of toluene, and the washing solution was added to the flask. Thereafter, aging was performed for 60 minutes, and 150 g of toluene as a diluent solvent was added into the flask. The mixture was further aged for 60 minutes, and 150 g of toluene as a diluent solvent was added to the flask. The mixture was further aged for 60 minutes, and 150 g of toluene as a diluent solvent was added to the flask. It was aged for another 60 minutes. Thereafter, the temperature was raised to 108 ° C. and aged for 300 minutes. Furthermore, after adding 185.7 g of diluting solvent, it cooled to room temperature and obtained the resin solution 1. The solid content was 32.4%, Tg was 75 ° C., and the weight average molecular weight in terms of polystyrene was 220,000.
(Example 1-2)
Visible light absorbing dye solution 1 was obtained by adding 0.5 part of S0290 (manufactured by FEW CHEMICALS: iodide salt of formula 4) and 99.5 parts of methyl ethyl ketone as a visible light absorbing dye. A borate solution 1 was obtained by adding 5 parts of sodium salt of tetrakis (pentafluorophenyl) borate and 95 parts of methyl ethyl ketone. 6.1 parts of resin solution 1, 1.0 part of visible light absorbing dye solution 1, 0.5 part of borate solution 1 and 2.2 parts of methyl ethyl ketone were mixed to obtain a visible light absorbing composition A1. .
(Example 1-3)
The visible light absorbing composition A1 was coated on a 100 μm thick easy-adhesion treated PET film (Toyobo Cosmo Shine A4300) with a bar coater (No. 34) and dried in a hot air dryer at 120 ° C. for 3 minutes. A visible light absorbing material A1 was obtained. The visible light-near infrared absorption spectrum is shown in FIG. 1, and the fluorescence spectrum is shown in FIG. The heat resistance test of the visible light absorbing material A1 was performed, and the visible light transmittance at a wavelength of 580 nm, the initial value of the color difference value b *, and the degree of change (difference between the value after the test and the value before the test) are shown in Table 1.
(Example 2-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.
(Example 2-2)
A visible light absorbing dye solution 2 was obtained by adding 0.5 parts of Adeka Arcles TY-102 (manufactured by Adeka) and 99.5 parts of methyl ethyl ketone as a visible light absorbing dye. 6.1 parts of resin solution 1, 1.0 part of visible light absorbing dye solution 1, 0.5 part of borate solution 1 and 2.2 parts of methyl ethyl ketone were mixed to obtain a visible light absorbing composition A2. .
(Example 2-3)
A visible light absorbing material A2 was obtained in the same manner as in Example 1-3 using the visible light absorbing composition A2. This visible light-near infrared absorption spectrum is shown in FIG. 3, and the fluorescence spectrum is shown in FIG. The heat resistance test of the visible light absorbing material A2 was performed, and the visible light transmittance at a wavelength of 590 nm, the initial value of the color difference value b *, and the degree of change (difference between the value after the test and the value before the test) are shown in Table 1.
(Comparative Example 1-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.
(Comparative Example 1-2)
6.1 parts of the resin solution 1, 1.0 part of the visible light absorbing dye solution 1 and 2.5 parts of methyl ethyl ketone were mixed to obtain a visible light absorbing composition B1.
(Comparative Example 1-3)
A visible light absorbing material B1 was obtained in the same manner as in Example 1-3 using the visible light absorbing composition B1. The visible light-near infrared absorption spectrum is shown in FIG. 5, and the fluorescence spectrum is shown in FIG. A heat resistance test of the visible light absorbing material B1 was performed and evaluated in the same manner as the visible light absorbing agent A1, and the results are shown in Table 1.
(Comparative Example 2-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.
(Comparative Example 2-2)
6.1 parts of the resin solution 1, 1.0 part of the visible light absorbing dye solution 2 and 2.5 parts of methyl ethyl ketone were mixed to obtain a visible light absorbing composition B2.

(Comparative Example 2-3)
A visible light absorbing material was obtained in the same manner as in Example 1-3 using the visible light absorbing composition B2. The visible light-near infrared absorption spectrum is shown in FIG. 7, and the fluorescence spectrum is shown in FIG. The heat resistance test of the visible light absorber B2 was performed and evaluated in the same manner as the visible light absorber A2, and the results are shown in Table 1.

In Table 1 and FIGS. 1 to 8, Comparative Example B1 did not show visible light absorption ability or light emission, but Example A1 showed high visible light absorption ability and light emission. Moreover, although both Example A2 and B2 showed visible light absorptivity and light emission, Example A2 had a smaller change in optical properties after the heat resistance test than Comparative Example B2.
(Example 3-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.
(Example 3-2)
CIR-1085 (manufactured by Nippon Carlit) as a diimonium dye was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 1 having a solid content of 3%. 6.1 parts of resin solution 1, 1.7 parts of diimonium dye solution 1, 1.0 part of visible light absorbing dye solution 2, 0.5 part of borate solution 1, and 0.8 part of methyl ethyl ketone are mixed. Thus, a visible light absorbing composition A3 was obtained.
(Example 3-3)
Using the visible light absorbing composition A3, a visible light absorbing material A3 was obtained in the same manner as in Example 1-3. The visible light-near infrared absorption spectrum is shown in FIG. The heat resistance test of the visible light absorbing material B2 is performed, and the visible light transmittance at a wavelength of 590 nm, the color difference value b *, the initial value and the degree of change of the near infrared transmittance (the difference between the value after the test and the value before the test) It is shown in Table 2.
(Example 4-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.
(Example 4-2)
Visible light absorbing dye solution 3 was obtained by adding 0.5 parts of Adeka Arcles GPZ-101 (manufactured by Adeka) and 99.5 parts of methyl ethyl ketone as a visible light absorbing dye. 6.1 parts of resin solution 1, 1.7 parts of diimonium dye solution 1, 1.0 part of visible light absorbing dye solution 3, 0.5 part of borate solution 1, and 0.8 part of methyl ethyl ketone are mixed. Visible light absorbing composition A4 was obtained.
(Example 4-3)
A visible light absorbing material A4 was obtained in the same manner as in Example 1-3 using the visible light absorbing composition A4. This visible light-near infrared absorption spectrum is shown in FIG. A heat resistance test of the visible light absorbing material A4 is performed, and the visible light transmittance at a wavelength of 590 nm, the color difference value b *, the initial value and the degree of change of the near infrared transmittance (the difference between the value after the test and the value before the test) are shown. It was shown in 2.
(Comparative Example 3-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.
(Comparative Example 3-2)
CIR-1085 (manufactured by Nippon Carlit) as a diimonium dye was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 1 having a solid content of 3%. 6.1 parts of the resin solution 1, 1.7 parts of the diimonium dye solution 1, 1.0 part of the visible light absorbing dye solution 2 and 1.1 parts of methyl ethyl ketone were mixed to obtain a visible light absorbing composition B3.
(Comparative Example 3-3)
A visible light absorbing material B3 was obtained in the same manner as in Example 1-3 using the visible light absorbing composition B3. The visible light-near infrared absorption spectrum is shown in FIG. A heat resistance test of the visible light absorbing material B3 was performed and evaluated in the same manner as the visible light absorbing agent A3. The results are shown in Table 2.
(Comparative Example 4-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.

(Comparative Example 4-2)
6.1 parts of the resin solution 1, 1.7 parts of the diimonium dye solution 1, 1.0 part of the visible light absorbing dye solution 3 and 0.8 part of methyl ethyl ketone were mixed to obtain a visible light absorbing composition B4.
(Comparative Example 4-3)
Using the visible light absorbing composition B4, a visible light absorbing material B4 was obtained in the same manner as in Example 1-3. This visible light-near infrared absorption spectrum is shown in FIG. A heat resistance test of the visible light absorbing material B4 was performed and evaluated in the same manner as the visible light absorbing agent A4. The results are shown in Table 2.
(Comparative Example 5-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.
(Comparative Example 5-2)
6.1 parts of the resin solution 1, 1.7 parts of the diimonium dye solution 1 and 2.0 parts of methyl ethyl ketone were mixed to obtain a near-infrared absorbing composition B5.
(Comparative Example 5-3)
A near-infrared absorbing material B5 was obtained in the same manner as in Example 1-3 using the near-infrared absorbing composition B5. This visible light-near infrared absorption spectrum is shown in FIG. The near-infrared absorbing material B5 was subjected to a heat resistance test and evaluated in the same manner as the visible light absorber A4. The results are shown in Table 2.

  In Table 2 and FIGS. 9 to 13, Comparative Examples B3 and B4 showed visible light absorption ability and near infrared absorption ability, but compared with Comparative Example B5, the change in b * and near infrared transmittance after the heat test was large. It was confirmed that the near-infrared absorbing dye was deteriorated by the addition of the visible light absorbing dye. However, it was confirmed that Examples A3 and A4 had a smaller change in color difference and near-infrared transmittance after the heat test than Comparative Examples B3 and B4, and had an effect of suppressing deterioration of the near-infrared absorbing dye.

  Since the borate for visible light absorbing material and luminescent material of the present invention enhances the visible light absorbing ability and luminescence intensity of the dye, it can be used as an optical filter for thin displays, an optical information recording material, and a luminescent material. wear. Further, the visible light absorbing material of the present invention containing a near infrared absorbing dye is useful as an optical filter for PDP.

It is a graph which shows the visible-near infrared absorption spectrum of visible light absorber A1 obtained in Example 1. FIG. 2 is a graph showing a fluorescence spectrum of a visible light absorbing material A1 obtained in Example 1. FIG. It is a graph which shows the visible-near-infrared absorption spectrum of visible light absorber A2 obtained in Example 2. FIG. 4 is a graph showing a fluorescence spectrum of a visible light absorbing material A2 obtained in Example 2. It is a graph which shows the visible-near-infrared absorption spectrum of visible light absorber B1 obtained by the comparative example 1. 6 is a graph showing a fluorescence spectrum of a visible light absorbing material B1 obtained in Comparative Example 1. It is a graph which shows the visible-near-infrared absorption spectrum of visible light absorber B2 obtained by the comparative example 2. It is a graph which shows the fluorescence spectrum of visible light absorber B2 obtained by the comparative example 2. It is a graph which shows the visible-near infrared absorption spectrum of visible light absorber A3 obtained in Example 3. FIG. It is a graph which shows the visible-near-infrared absorption spectrum of visible light absorber A4 obtained in Example 4. FIG. It is a graph which shows the visible-near-infrared absorption spectrum of visible light absorber B3 obtained by the comparative example 3. It is a graph which shows the visible-near-infrared absorption spectrum of visible light absorber B4 obtained by the comparative example 4. It is a graph which shows the visible-near-infrared absorption spectrum of near-infrared absorber B5 obtained by the comparative example 5.

Claims (18)

A borate for visible light absorption or emission material having an anion represented by the following formula (1).

In the formula, R ¹ represents an aryl group having an electron attractive group, R ² represents an organic group, a halogen group or a hydroxyl group, m is an integer of 1 to 4. In the formula (1), an electron withdrawing _{group, -C p F 2p + 1 (} p is a natural _number), - NO 2, -CN, -F, at least one substituent selected from the group consisting of -Cl and -Br The borate for visible light absorption or luminescent material according to claim 1, wherein The borate for visible light absorbing materials according to claim 1 or 2, wherein in the formula (1), the aryl group having an electron-withdrawing group represented by R ¹ is a phenyl group having an electron-withdrawing group. The visible light absorption or luminescent material boron according to any one of claims 1 to 3, wherein in the formula (1), the aryl group having an electron-withdrawing group represented by R ¹ is a pentafluorophenyl group. Acid salt.   The borate for visible light absorption or light-emitting materials according to any one of claims 1 to 4, wherein the anion represented by the formula (1) is a tetrakis (pentafluorophenyl) borate anion. A visible light absorbing composition comprising the borate according to claim 1 and a visible light absorbing dye.   The visible light absorbing composition according to claim 6, wherein the visible light absorbing dye is a cyanine dye.   The visible light absorption composition of Claim 6 and 7 containing a near-infrared absorption pigment | dye.   The visible light absorbing composition according to claim 8, wherein the near infrared absorbing dye is a diimonium dye.   The visible light absorption composition of any one of Claims 6-9 containing (meth) acrylic-type resin.   The visible light absorption material containing the visible light absorption composition of any one of Claims 6-10. The visible light absorption material which laminated | stacked the visible light absorption composition of any one of Claims 6-10 on the transparent base material.   The visible light absorbing material according to claim 11, wherein the transparent substrate is glass, PET film, easy-adhesive PET film, TAC film, antireflection film, or electromagnetic wave shielding film.   An optical filter for thin display, comprising the visible light absorbing material according to any one of claims 11 to 13.   An optical information recording material comprising the visible light absorbing material according to claim 11.   The visible light absorbing composition according to any one of claims 6 to 10, the visible light absorbing material according to any one of claims 11 to 13, or the optical filter according to claim 14. , Thin display. The luminescent composition containing the borate of any one of Claims 1-5, and a luminescent pigment | dye. A luminescent material comprising the luminescent composition according to claim 17.

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