JP2006137933A - Near-infrared absorbing coating agent and near-infrared absorbing laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent suitable for forming a near-infrared absorbing filter excellent in heat resistance and light resistance, and having little color change of the near-infrared absorbing filter.
SOLUTION: A copolymer (A) having a cycloalkyl group-containing monomer (a1) as an essential constituent, and a diimonium compound (B) represented by the general formula (1) having a branched alkyl group A near-infrared absorbing coating agent characterized by comprising: Rings A and B other than 1,4- in formula (1) are unsubstituted or have 1 to 4 halogen atoms, lower alkyl groups, lower alkoxy groups, cyano groups and / or hydroxy groups as substituents. The near-infrared absorbing coating agent having a group.
[Selection figure] None

Description

  The present invention relates to a near-infrared absorbing coating agent, and more particularly, absorbs near-infrared rays generated from an image output device such as a plasma display device, and the near-infrared rays enter various electronic devices placed outside the plasma display device. It is related with the near-infrared absorptive coating agent suitable for formation of a near-infrared absorption laminated body which prevents doing and malfunctioning of a peripheral electronic device.

  In recent years, various types of displays have been developed and commercialized as large displays. A plasma display is one of them, and is particularly attracting attention as a large display for hanging on the wall from the viewpoint of enlargement, thickness reduction, and weight reduction of 40 inch size or more. This plasma display emits light rays other than the wavelength bands of the three primary colors (red, green, and blue) of the color image from the visible light region to the infrared wavelength region due to structural factors of each pixel portion constituting the light source or the discharge unit. . For example, the plasma display emits strong near infrared rays having wavelengths of 820 nm, 880 nm, 980 nm, and the like. These near-infrared rays match the operating wavelengths of peripheral electronic devices, for example, near-infrared communication devices such as TVs, video and cooler remote controllers, mobile communications, and personal computers. Therefore, there arises a problem that the plasma display causes malfunction of peripheral devices.

  Therefore, it has been proposed to use an optical filter that absorbs near infrared rays. As such a near-infrared absorption filter, a phosphate-containing glass filter containing divalent copper ions, a thin layer of metal (for example, silver) on the surface of glass or the like, vapor deposition method, sputtering method or ion plating method Examples thereof include filters formed by other methods, filters in which a dye that absorbs wavelengths in the near infrared region is added to the resin, and the like.

However, among the near-infrared absorption filters as described above, the phosphate-containing glass filter has a problem that it is complicated to manufacture and easily absorbs moisture.
In addition, when a thin metal layer is provided on the surface of glass or the like, although it is less than the near infrared region, light in the visible light region is also reflected. Therefore, if the metal layer is too thick, the transmittance is increased. There are problems such as lowering and high manufacturing costs.
Furthermore, since these methods use glass in common, there are problems that the obtained filter is heavy and easily broken, and that processing is difficult.

In contrast, a filter in which a dye that absorbs a wavelength in the near-infrared region is added to a resin is advantageous in that it is lighter and easier to manufacture than a filter using glass.
Known dyes that absorb near-infrared wavelengths include diimonium compounds as shown in Patent Documents 1 to 3, phthalocyanine compounds as shown in Patent Documents 4 to 5, and the like.

However, many dyes that absorb light in the near-infrared region have absorption in the visible light region at the same time, and near-infrared absorption filters to which these dyes are added often absorbs light outside the near-infrared region. Have. Absorption of light in the visible region is a big problem for an image display device such as a plasma display. Therefore, a pigment that absorbs light in the near infrared region is desired to have as little absorption in the visible light region as possible.
Of the dyes that absorb near-infrared absorption wavelengths, diimonium compounds are
(1) The light absorption rate in the visible light region is extremely small,
(2) absorb the ultraviolet region,
(3) The maximum absorption wavelength in the near infrared region is extremely large,
(4) Since the near infrared absorption region is also wide as 850 to 1200 nm,
Particularly preferred as a dye for a near-infrared absorption filter for plasma display.

However, many diimonium compounds are inferior in heat resistance and light resistance.
Therefore, for example, when a diimonium compound is kneaded and molded into various resins to obtain a near infrared absorption filter, that is, a near infrared absorption film, the diimonium compound is decomposed by heat during kneading and molding, and the obtained near infrared Absorption in the near infrared region of the absorption filter will decrease.

A coating agent in which a pigment that absorbs a wavelength in the near-infrared region is added to a resin, applied to a substrate such as a plastic film and dried, and a method for providing a near-infrared absorbing layer is also called a coating method, a casting method, etc. In the case of such a coating method, a filter can be produced at a relatively low temperature as compared with the kneading and molding methods described above.
However, in the plasma display, the surface of the phosphor substrate is about 50 ° C to 80 ° C. Therefore, the near-infrared absorption filter laminated on the front plate is also heated for a long time. As a result, after being laminated on the front plate of the plasma display, the dye in the near infrared absorption layer constituting the near infrared absorption filter is decomposed by heat, and the absorption in the near infrared region is lowered. Furthermore, there was a serious problem that the color of the filter itself was tinged with green.

Patent Documents 1 and 2 describe the use of a coating agent containing a polycarbonate resin or a polyarylate resin and a diimonium compound as a method for improving the heat resistance of a near-infrared absorption filter containing a diimonium compound (patents 1 and 2). Document 1: Japanese Patent Laid-Open No. 2000-206323, Patent Document 2: Japanese Patent Laid-Open No. 11-323121).
However, a coating agent containing a polycarbonate resin or polyarylate resin and a diimonium compound has a problem that light resistance is inferior.

  In addition, as a method for improving the light resistance of a near-infrared absorption filter containing a diimonium compound, the use of a coating agent containing a (meth) acrylic resin such as methyl methacrylate and a diimonium compound has been proposed. However, sufficient light resistance cannot be obtained, and heat resistance is further poor.

Furthermore, as a method for improving the heat resistance of a near-infrared absorption filter containing a diimonium compound, the use of a diimonium compound in which the end group of the diimonium compound is changed from a linear alkyl group to a branched alkyl group is disclosed in Patent Literature 3 (see Patent Document 3: Japanese Patent Laid-Open No. 2003-96040).
However, near-infrared absorption filters containing diimonium-based compounds whose end groups are branched alkyl groups are not sufficient, although heat resistance is improved compared to near-infrared absorption filters containing diimonium-based compounds whose end groups are linear alkyl groups. It was.

Patent Documents 4 to 5 describe a coating agent and a near-infrared absorbing coating film containing an acrylic resin obtained by copolymerizing a specific unsaturated monomer and a near-infrared absorbing pigment (Patent Document 4). : JP 2002-294721 A, Patent Document 5: JP 2004-182793 A)
However, the near-infrared absorbing dye is mainly related to a phthalocyanine dye, and there is no description about a diimonium dye.
JP 2000-206323 A JP 11-3231215 A JP 2003-96040 A JP 2002-294721 A JP 2004-182793 A

  The present invention is a near-infrared absorption filter that has high transmittance in the visible light region, absorbs near-infrared rays emitted from plasma display devices, and prevents malfunction of peripheral electronic devices, and has excellent heat resistance and light resistance. An object is to provide a coating agent suitable for forming a near-infrared absorption filter.

As a result of intensive studies in view of the above problems, the present inventors have found that a copolymer (A) containing a cycloalkyl group-containing monomer (a1) as an essential constituent, a diimonium compound (B) having a specific structure, and It was found that these drawbacks can be eliminated by combining the above, and the present invention was completed.
That is, the present invention contains a copolymer (A) having a cycloalkyl group-containing monomer (a1) as an essential constituent, and a diimonium compound (B) represented by the following general formula (1). It is a near-infrared absorptive coating agent characterized by these.

(In the formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them is a branched alkyl group, and the rings A and B may have a substituent. Well, X represents the anion necessary to neutralize the charge.)

  In the present invention, rings other than 1,4- in rings A and B are unsubstituted or have 1 to 4 halogen atoms, lower alkyl groups, lower alkoxy groups, cyano groups and / or hydroxy groups as substituents. It is the said near-infrared absorptive coating agent which has.

In the present invention, the branched alkyl group in R _{1 to} R ₈ is 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2 -The near-infrared absorbing coating agent which is a methylbutyl group, a 3-methylbutyl group, or a 2-ethylbutyl group.

Further, the present invention is a branched alkyl group in R ₁ to R ₈ is, - (CH ₂₎ a near-infrared absorbing coating agent characterized by having a structure represented by n _-R.
(However, n represents an integer of 1 or more, and R represents an alkyl group having a secondary or tertiary carbon.)

  In the present invention, the copolymer (A) is a monomer (a2) having a benzotriazole group and a polymerizable unsaturated group and / or a monomer (a3 having a piperidinyl group and a polymerizable unsaturated group). ) As a constituent component.

  Moreover, this invention is the said near-infrared absorptive coating agent characterized by further containing a phthalocyanine type compound (C) and / or a dithiol metal complex compound (D).

  Moreover, this invention is a said near-infrared absorptive coating agent characterized by further containing a cyanine type compound (G).

  Moreover, this invention is the said near-infrared absorptive coating agent characterized by the ultraviolet absorber and (E) and / or a hindered amine light stabilizer (F).

  Moreover, this invention is a near-infrared absorption laminated body by which the near-infrared absorption layer formed from the said near-infrared absorptive coating agent is laminated | stacked on a base material.

  In the present invention, at least one layer comprising an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, an anti-scratch layer, an antireflection layer, a color tone correcting layer, a heat radiation layer, and an impact resistant layer is formed on the substrate side and / or near infrared absorbing layer. It is the said near-infrared absorption laminated body laminated | stacked on the top.

  The near-infrared absorbing laminate using the near-infrared-absorbing coating agent of the present invention can sufficiently shield the near-infrared wavelength region, has high visible light permeability, and has excellent heat resistance and light resistance. Therefore, it has a stable near-infrared shielding effect over a long period of time, has little change in color, and is effective as a near-infrared absorption filter for plasma display panels.

Hereinafter, the present invention will be described in detail.
The copolymer (A) having the cycloalkyl group-containing monomer (a1) in the present invention as an essential constituent component constitutes a binder resin in the near-infrared absorbing coating agent, and is one type or two or more types. Can be used.

The cycloalkyl group-containing monomer (a1) in the present invention means a monomer having an aliphatic cyclic hydrocarbon structure (hereinafter referred to as alicyclic structure or simply alicyclic) group,
A monomer having one alicyclic structure such as a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, or a cyclododecyl group;
Examples thereof include a monomer having a plurality of alicyclic structures such as a bornyl group, an isobornyl group, a dicyclopentenyl group, a dicyclopentanyl group, and an adamantane group.

  Examples of the cycloalkyl group-containing monomer (a1) include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tert-butylcyclohexyl methacrylate, dicyclopentenyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate , Cyclohexylbutyl (meth) acrylate, 4-methylcyclohexylmethyl (meth) acrylate, 4-ethylcyclohexylmethyl ( Acrylate), 4-propylcyclohexylmethyl (meth) acrylate, 4-butylcyclohexylmethyl (meth) acrylate, 4-methoxycyclohexylmethyl (meth) acrylate, 4-acetoxymethylcyclohexylmethyl (meth) acrylate, 3-methyl Cyclohexylmethyl (meth) acrylate, 3-ethylcyclohexylmethyl (meth) acrylate, 3-propylcyclohexylmethyl (meth) acrylate, 3-butylcyclohexylmethyl (meth) acrylate, 3-methoxycyclohexylmethyl (meth) acrylate, 3-acetoxy Methylcyclohexylmethyl (meth) acrylate, 3-hydroxymethylcyclohexylmethyl (meth) acrylate, 4-methylcyclohexylethyl (meta Acrylate, 4-ethylcyclohexylethyl (meth) acrylate, 4-propylcyclohexylethyl (meth) acrylate, 4-butylcyclohexylethyl (meth) acrylate, 4-methoxycyclohexylethyl (meth) acrylate, 4-acetoxymethylcyclohexylethyl (meth) ) Acrylate, 4-hydroxymethylcyclohexylethyl (meth) acrylate, 3-methylcyclohexylethyl (meth) acrylate, 3-ethylcyclohexylethyl (meth) acrylate, 3-propylcyclohexylethyl (meth) acrylate, 3-butylcyclohexylethyl ( (Meth) acrylate, 3-methoxycyclohexylethyl (meth) acrylate, 3-acetoxymethylcyclohexylethyl (meth) acrylate Relate, 3-hydroxymethylcyclohexylethyl (meth) acrylate, 4-methyltylcyclohexylpropyl (meth) acrylate, 4-ethylcyclohexylpropyl (meth) acrylate, 4-methoxycyclohexylpropyl (meth) acrylate, 4-acetoxymethylcyclohexylpropyl (Meth) acrylate, 4-hydroxymethylcyclohexylpropyl (meth) acrylate, 3-methyltylcyclohexylpropyl (meth) acrylate, 3-ethylcyclohexylpropyl (meth) acrylate, 3-methoxycyclohexylpropyl (meth) acrylate, 3-acetoxy Methylcyclohexylpropyl (meth) acrylate, 3-hydroxymethylcyclohexylpropyl (meth) acrylate, 4 Methyltylcyclohexylbutyl (meth) acrylate, 4-ethylcyclohexylbutyl (meth) acrylate, 4-methoxycyclohexylbutyl (meth) acrylate, 4-acetoxymethylcyclohexylbutyl (meth) acrylate, 4-hydroxymethylcyclohexylbutyl (meth) acrylate , 3-methyltylcyclohexylbutyl (meth) acrylate, 3-ethylcyclohexylbutyl (meth) acrylate, 3-methoxycyclohexylbutyl (meth) acrylate, 3-acetoxymethylcyclohexylbutyl (meth) acrylate, 3-hydroxymethylcyclohexylbutyl ( (Meth) acrylate, 2-methyl-1-cyclohexylmethyl (meth) acrylate, 2,3-dimethyl-1-cyclohexylme (Meth) acrylate, 2,6-dimethyl-1-cyclohexylmethyl (meth) acrylate, 2-phenyl-1-cyclohexylmethyl (meth) acrylate, 2-phenyl-3-methyl-1-cyclohexylmethyl (meth) acrylate 2-phenyl-4-methyl-1-cyclohexylmethyl (meth) acrylate, 2-phenyl-5-methyl-1-cyclohexylmethyl (meth) acrylate, 2-phenyl-6-methyl-1-cyclohexylmethyl (meth) An acrylate etc. are mentioned. Among these, those containing isomers may be each isomer alone and / or each isomer mixture. These cycloalkyl group-containing monomers (a1) may be used alone or in combination of two or more.

  The copolymer (A) containing the cycloalkyl group-containing monomer (a1) as an essential constituent component is for improving the heat resistance and light resistance of the near infrared absorbing layer formed from the near infrared absorbing coating agent. A monomer having a benzotriazole group and a polymerizable unsaturated group (a2) and / or a monomer having a piperidinyl group and a polymerizable unsaturated group (a3) as a cycloalkyl group-containing monomer (a1) And a copolymer of a monomer (a2) having a benzotriazole group and a polymerizable unsaturated group and a cycloalkyl group-containing monomer (a1). Is more preferable.

  As the monomer (a2) having the benzotriazole group and the polymerizable unsaturated group, monomers represented by the following general formula (2) and general formula (3) can be used. These monomers may be used alone or in combination of two or more.

(In the formula, R ₉ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ₁₀ represents an alkylene group, R ₁₁ represents a hydrogen atom or a methyl group. X1 represents a hydrogen atom, a halogen atom, or a carbon number of 1 to 6). Represents an alkoxy group, a cyano group or a nitro group.)

(In the formula, R ₁₂ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ₁₃ represents an alkylene group, R ₁₄ represents a hydrogen atom or a methyl group. X2 represents a hydrogen atom, a halogen atom, or a carbon number of 1 to 6). Represents an alkoxy group, a cyano group or a nitro group.)

Of R ₉ in the general formula (2) and R ₁₂ in the general formula (3), examples of the hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and isobutyl. Chain, tert-butyl, pentyl, hexyl, heptyl, octyl and other chain hydrocarbon groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and other alicyclic hydrocarbons Groups; aromatic hydrocarbon groups such as phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group and the like.

Among R ₁₀ in the general formula (2) and R ₁₃ in the general formula (3), examples of the alkylene group include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; a propylene group , Branched chain alkylene groups such as 2-methyltrimethylene group and 2-methyltetramethylene group. R ₁₀ is preferably an alkylene group having 1 to 6 carbon atoms, and R ₁₃ is preferably an alkylene group having 2 or 3 carbon atoms.

Of X ₁ in the general formula (2) and X ₂ in the general formula (3), examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Of X ₁ in the general formula (2) and X ₂ in the general formula (3), examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and peptoxy. Groups and the like.

  Examples of the monomer represented by the general formula (2) include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′. -(Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert -Butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, etc. Is mentioned.

  Examples of the monomer represented by the general formula (3) include 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-tert-butylphenyl] -4-tert-butyl- And 2H-benzotriazole.

  Of the monomers (a2) having such a benzotriazole group and a polymerizable unsaturated group, a commercially available RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) is preferable as the monomer represented by the general formula (2).

  Examples of the monomer (a3) having a piperidinyl group and a polymerizable unsaturated group that can be copolymerized with the cycloalkyl group-containing monomer (a1) include the following general formula (4) or general formula (5). The monomers shown can be used. These monomers may be used alone or in combination of two or more.

(In the formula, R ₁₅ represents a hydrogen atom or a cyano group, R ₁₆ and R ₁₇ are the same or different and represent a hydrogen atom or a methyl group, R ₁₈ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Y 1 represents oxygen. Represents an atom or an imino group.)

(In the formula, R ₁₉ represents a hydrogen atom or a cyano group. R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are the same or different and represent a hydrogen atom or an H methyl group. Y 2 represents an oxygen atom or an imino group. To express.)

Of R ₁₈ in the general formula (4), the hydrocarbon group having 1 to 8 carbon atoms is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, or a pentyl group. Chain hydrocarbon groups such as hexyl, heptyl and octyl; cycloaliphatic hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl, tolyl and xylyl And aromatic hydrocarbon groups such as a benzyl group and a phenethyl group.

  Examples of the monomer represented by the general formula (4) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6, 6-tetramethylpiperidine, 4- (meth) -acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine and the like.

  Examples of the monomer represented by the general formula (4) include 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl- Examples include cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine, and the like.

  Among the monomers (a3) having a piperidinyl group and a polymerizable unsaturated group, those represented by the general formula (4) include commercially available ADK STAB LA-82 and ADK STAB LA-83 (both manufactured by Asahi Denka Kogyo). FA-711MM and FA-712HM (both manufactured by Hitachi Chemical Co., Ltd.) are preferable.

In addition to the cycloalkyl group-containing monomer (a1), the monomer (a2) having a benzotriazole group and a polymerizable unsaturated group, and the monomer (a3) having a piperidinyl group and a polymerizable unsaturated group. Examples of other copolymerizable unsaturated monomer (a4) that can be used in obtaining the polymer (A) include carboxyl groups such as (meth) acrylic acid, itaconic acid, maleic anhydride, and the like. Unsaturated monomers;
Acidic phosphate ester unsaturated monomers such as 2- (meth) acryloyloxyethyl acid phosphate;
Unsaturated monomers having groups having active hydrogen, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate;
(Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate;
Unsaturated monomers having an epoxy group such as glycidyl (meth) acrylate, monomers having an alicyclic epoxy machine;

Unsaturated monomers having nitrogen atoms such as (meth) acrylamide, N, N′-dimethylaminoethyl (meth) acrylate, N, N′-diethylaminoethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide ;
Unsaturated monomer having two or more polymerizable double bonds such as ethylene glycol di (meth) acrylate, tritylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate body;
Unsaturated monomers having halogen atoms such as vinyl chloride;
Aromatic unsaturated monomers such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate;

  A monomer having both a vinyl ether group and a radical polymerizable group can also be used. For example, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, (meth) acrylic acid 2 -(Vinyloxyethoxy) isopropyl, vinyl ether of (meth) acrylic acid 2- (vinyloxyisopropoxy) propyl, and the like.

Moreover, the unsaturated monomer which has a fluorine atom can also be used. For example, the unsaturated monomer having a fluorine atom includes a radical polymerizable monomer having a polyfluoroalkyl group or a polyfluoroether group, and the perfluoroalkyl group includes a perfluoromethyl group, a perfluoroethyl group, Examples include perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, perfluorododecyl group, perfluorotetradecyl group and the like. As a monomer having such a fluorine atom, CH ₂ ═C (CH ₃ ) COOCH ₂ (CF ₂ ) ₄ CF ₃ , CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ CF _{3 , CH 2 = CHCOO (CF 2} ) 6 CF 3, CH 2 = CHCOOCH 2 CH 2 (CF 2) 7 CF 3, CH 2 = CHCOOCH 2 CH 2 (CF 2) 5 CF (CF 3) 2, CH 2 = _{C (CH 3) COOCH (OCOCH} 3) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CHCOOCH 2 CH (OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = _{CHCOOCH 2 CH 2 (CF 2)} 8 CF 3, CH 2 = C (CH 3) COOCH 2 CH 2 NHCO (CF 2) 8 CF 3, CH 2 = CHOC ONHCO (CF ₂ ) ₇ CF (CF ₂ Cl) CF ₃ , CH ₂ ═CHCOOOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ (CF ₂ ) ₇ CF ₃ , CH ₂ ═CHCOOCH ₂ CH ₂ CH ₂ CH _{2 (CF 2) 7 CF 3,} CH 2 = C (CH 3) COOCH 2 CH 2 N (C 2 H 5) SO 2 (CF 2) 7 CF 3, CH 2 = CHCOOCH 2 CH 2 NHCO (CF 2) 7 CF ₃ , CH ₂ = CHCOO (CH ₂ ) ₃ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₀ H, CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) _{10 CF 2 Cl, CH 2 =} CHCONHCH 2 CH 2 OCOCF (CF 3) OC 3 F 7, CH 2 = CHCONHCH 2 CH 2 OCOCF _{CF 3) (OC 3 F 6} ) 2 OC 3 F 7 , and the like.

  Other copolymerizable unsaturated monomers (a4) that can be used in addition to the monomers (a1) to (a3) may be used alone or in combination of two or more. .

The copolymer (A) having the cycloalkyl group-containing monomer (a1) as an essential constituent component is a cycloalkyl group-containing monomer used for copolymerization, assuming that all the monomer components are 100% by weight. (A1) is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 20 to 70% by weight.
The near-infrared absorbing layer formed from a coating agent containing a copolymer obtained when the cycloalkyl group-containing monomer (a1) used for copolymerization is less than 5% by weight has sufficient heat resistance and light resistance. May not improve. If it exceeds 90% by weight, the glass transition temperature becomes too low and the heat resistance is deteriorated, and problems such as blocking may occur.

When all the monomer components are 100% by weight, the monomer (a2) having a benzotriazole group and a polymerizable unsaturated group, a piperidinyl group, and a polymerizable unsaturated group used for copolymerization are used. The monomer (a3) is preferably 0.1 to 60% by weight, more preferably 0.5 to 40% by weight, and even more preferably 1 to 30% by weight. In the case where the monomers (a2) and (a3) are used in combination, it is preferable that both are within the above range.
When the amount is less than 0.5% by weight, the heat resistance and light resistance are not sufficiently improved. When the amount exceeds 60% by weight, the effect of improving the heat resistance and light resistance with respect to the amount used is reduced, and the cost is disadvantageous. There is a possibility that the solubility and stability of the near-infrared absorbing dye may be deteriorated.

  As a polymerization method for producing the copolymer (A) having the cycloalkyl group-containing monomer (a1) as an essential constituent component, for example, using a polymerization initiator, solution polymerization, dispersion polymerization, suspension The polymerization can be performed by a conventionally known polymerization method such as polymerization or emulsion polymerization. The solvent for performing the solution polymerization is not particularly limited. For example, an aromatic solvent such as toluene and xylene; methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol Alcohol solvents such as propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; chloroform, dichloromethane, trichloromethane, methylene chloride, etc. Chlorinated solvents of: ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, 1,3-dioxolane; N-methylpyrrolidone, dimethylformamide, dimethyls Sulfoxide, can be used alone or in combination of two or more such dimethylacetamide.

  The polymerization initiator is not particularly limited. For example, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2-amidinopropane) · dihydrochloride 2,2′-azobis ( 4-cyanopentanoic acid), 2,2′-azobisisobutyronitrile, azo initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile); persulfates such as potassium persulfate, Hydrogen peroxide, peracetic acid, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, di-tert-butyl peroxide, 1,1-bis (tert-butylperoxy) -3, 3, 5 -Normal radical initiators, such as peroxide-type initiators, such as trimethylcyclohexane and tert-butyl hydroperoxide. At this time, sodium hydrogen sulfite, L-ascorbic acid, Rongalite, sodium metabisulfite, or the like can be used as a reducing agent to obtain a redox initiator. These may be used alone or in combination of two or more. The amount used may be set appropriately from the desired molecular properties of the polymer, such as the molecular weight of the polymer. For example, when the total monomer component is 100% by weight, it is 0.01-50% by weight. It is preferably 0.05 to 20% by weight.

  Moreover, a polymerization accelerator can also be used as needed. Examples of such a polymerization accelerator include various transition metal ions, specifically, ferric sulfate, cupric sulfate, ferric chloride, cupric chloride and the like.

  In addition, when the unsaturated monomer is polymerized, a chain transfer agent or a regulator can be used for the purpose of adjusting the molecular weight as necessary. Examples of such chain transfer agents and regulators include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; ketones such as acetone, methyl ethyl ketone, mail isobutyl ketone, cyclohexanone, and acetophenone; acetaldehyde, n-butyraldehyde, Examples include aldehydes such as furfural and benzaldehyde; mercaptans such as dodecyl mercaptan, lauryl mercaptan, thioglycolic acid, octyl thioglycolate, thioglycerol, and 2-mercaptoethanol.

  As the usage-amount of the said chain transfer agent or a regulator, when all the monomer components are 100 weight%, it is preferable to set it as 0.01 to 10 weight%, and 0.02 to 5 weight% is more preferable.

  The polymerization conditions in the polymerization method may be appropriately set depending on the polymerization method, and are not particularly limited. For example, the polymerization temperature is preferably room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set suitably as reaction time so that a polymerization reaction may be completed according to the composition of a monomer component, the kind of polymerization initiator, etc.

  The copolymer (A) having the cycloalkyl group-containing monomer (a1) as an essential constituent component preferably has a weight average molecular weight of 1,000 or more and 1,000,000 or less. More preferably, it is 10,000 or more and 600,000 or less. In addition, a weight average molecular weight is a measured value by polystyrene conversion GPC.

  The diimonium compound (B) used in the present invention has a structure represented by the following general formula (1).

In the general formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them is a branched alkyl group.
For example, 1-methylethyl group (iso-propyl group), 1,1-dimethylethyl group (tert-butyl group), 1-methylpropyl group (sec-butyl group), 1,1-dimethylpropyl group, 2- Methylpropyl group (iso-butyl group), 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group (iso-amyl group), 1,1 An alkyl group having 1 to 20 carbon atoms such as a dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group and 2-ethylbutyl group, preferably 1 to 1 carbon atom; 10 alkyl groups are mentioned.
Among these, for example, 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group and 2-ethylbutyl group Etc. are preferred as the branched alkyl group.

Further, branched-chain alkyl group in _R 1 to R ₈ of general formula (1) is, - _{(CH 2)} preferably have a structure represented by n -R. In this case, n represents an integer of 1 or more, preferably 1 to 17, and more preferably 1 to 7. R represents an alkyl group having secondary or tertiary carbon. Then, - _{(CH 2)} carbon atoms of the entire structure of the n -R is preferably 4 to 20.

Of the R _{1 to} R ₈ in the general formula (1), the remaining functional group other than the branched alkyl group is preferably a linear alkyl group having 1 to 8 carbon atoms that may have a functional group. Selected.
Specific examples of these linear alkyl groups include an ethyl group, an n-propyl group, and an n-butyl group.
Examples of substituents that can be bonded to these groups include: cyano group; hydroxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, n-propoxy group, n-butoxy group and the like An alkoxy alkoxy group having 2 to 8 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group; C3-C5 alkoxyalkoxyalkoxy group such as methoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, etc .; allyloxy group; phenoxy group, trioxy group, xylyloxy group, naphthyloxy group, etc. ~ 12 aryloxy groups C2-C7 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyl C2-C7 alkylcarbonyloxy groups such as oxy group and n-butylcarbonyloxy group; C2 such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group and n-butoxycarbonyloxy group -7 alkoxycarbonyloxy and the like.

Rings A and B in general formula (1) may or may not have 1 to 4 substituents in addition to the 1,4-position.
Examples of the substituent that can be bonded include a halogen atom, a hydroxy group, a lower alkoxy group, a cyano group, and a lower alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the lower alkoxy group include C1-C5 alkoxy groups such as methoxy group and ethoxy group. Examples of the lower alkyl group include C1-C5 alkyl groups such as methyl group and ethyl group. Preferably, A and B do not have a substituent or are substituted with a halogen atom (especially a chlorine atom or a bromine atom), a methyl group or a cyano group. In addition, when B has a substituent, all of the four B rings are the same, and further, the position of the substituent is m-position with respect to the nitrogen atom bonded to the phenylenediamine skeleton. preferable. Further, rings A and B preferably have no substituent other than the 1,4-position in terms of synthesis.

  X in the general formula (1) is an anion necessary for neutralizing the charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent. These anions are selected from, for example, organic acid anions or inorganic anions. Specifically, examples of the organic acid anion include organic carboxylate ions such as acetate ion, lactate ion, trifluoroacetate ion, propionate ion, benzoate ion, oxalate ion, succinate ion and stearate ion; Acid ion, toluenesulfonate ion, naphthalene monosulfonate ion, naphthalene disulfonate ion, chlorobenzenesulfonate ion, nitrobenzenesulfonate ion, dodecylbenzenesulfonate ion, benzenesulfonate ion, ethanesulfonate ion, trifluoromethanesulfonate ion And organic borate ions such as tetraphenylborate ion and butyltriphenylborate ion, preferably trifluoromethanesulfonate ion, Alkylsulfonate ion and alkylaryl sulfonate ion such as toluenesulfonic acid ion.

  Examples of inorganic anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion; thiocyanate ion, hexafluoroantimonate ion, perchlorate ion, periodate ion, nitrate ion and tetrafluoroborate ion. Hexafluorophosphate ion, molybdate ion, tungstate ion, titanate ion, vanadate ion, phosphate ion, borate ion, etc., and preferable ones include perchlorate ion, iodine ion, tetrafluoro Examples thereof include borate ion, hexafluorophosphate ion and hexafluoroantimonate ion.

  Among these anions, preferred are, for example, perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion and toluenesulfonate ion. Can be mentioned.

Next, specific examples of the diimonium compound (B) represented by the general formula (1) used in the present invention are shown in Table 1. In Table 1, i- represents an iso-, s- represents a sec-, t- represents a branched state such as tert-, and TsO represents a toluene sulfonate ion. In addition, regarding A and B, when there is no substitution at positions other than the 1,4-positions, “4H” is indicated. When R _{1 to} R ₈ are all iso-butyl groups, that is, (R ₁ , R ₂ ), (R ₃ , R ₄ ), (R ₅ , R ₆ ) and (R ₇ , R ₈ ) When all four combinations of substituents are iso-butyl groups, they are abbreviated as “4 (i-C ₄ H ₉ , i-C ₄ H ₉ )”, and similarly all iso-amyl groups (—C If it is _{2 H 4 CH (CH 3)} 2) are abbreviated as _{"4 (i-C 5 H 11} , i-C 5 H 11) ." Further, among R _{1 to} R ₈ , for example, when one is an n-butyl group and the rest is an iso-butyl group, that is, n-butyl is contained in one of the four combinations of substituents, and the remaining When all three sets are iso-butyl groups, they are abbreviated as “3 (i-C ₄ H ₉ , i-C ₄ H ₉ ) (i-C ₄ H ₉ , n-C ₄ H ₉ )”. In addition, Compound No. In 23 and 24, all four B rings are the same, and the position of the substituent is the m-position with respect to the nitrogen atom bonded to the phenylenediamine skeleton.

The diimonium compound (B) represented by the general formula (1) used in the present invention can be obtained by the following method disclosed in, for example, Japanese Patent Publication No. 43-25335. That is, an amino compound represented by the following general formula (6) obtained by reducing a product obtained by Ullmann reaction of p-phenylenediamine and 1-chloro-4-nitrobenzene is preferably used in an organic solvent. Corresponds to the desired R _{1 to} R ₈ in a water-soluble polar solvent such as dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone at 30 to 160 ° C., preferably 50 to 140 ° C. A halogenated compound to be reacted (for example, BrCH ₂ CH (CH ₃ ) ₂ when R ₁ is i-C ₄ H ₉ ), and all the substituents (R _{1 to} R ₈ ) are the same ( Hereinafter, it is referred to as a total substitution product). In the case of synthesizing compounds other than all substitution products, for example, No. When synthesizing the compound of 25, previously prescribed moles reagent (formula (amine compound per mole 7 moles of _{6)) (BrCH 2 CH (} CH 3) 2) and reacted _R 1 ~ After introducing an iso-butyl group into 7 of R _8, the number of moles necessary to introduce the remaining substituent (n-butyl group) (1 mole per mole of amine compound of general formula (6)) The reagent (BrC ₄ H ₉ ) is reacted.

(Wherein rings A and B are as defined above.)

  Thereafter, the compound synthesized above is heated in an organic solvent, preferably in a water-soluble polar solvent such as dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, and 0 to 100 ° C., preferably 5 Addition with an oxidizing agent (for example, silver salt) corresponding to X in the general formula (1) at ˜70 ° C. to carry out an oxidation reaction. If the equivalent of the oxidizing agent is 2 equivalents, the diimonium compound represented by the general formula (1) of the present invention can be obtained. In addition, the compound synthesized above is oxidized with an oxidizing agent such as silver nitrate, silver perchlorate, cupric chloride, etc., and then an acid or salt of a desired anion is added to the reaction solution to perform salt exchange. The diimonium compound represented by the general formula (1) of the present invention can also be obtained.

The content of the diimonium compound (B) contained in the coating agent of the present invention is such that the near-infrared absorbing laminate formed by laminating the near-infrared absorbing layer formed by the near-infrared absorbing coating agent of the present invention is absorbed in the near infrared. When used as a filter, it is determined by the thickness of the near infrared absorption filter and the required absorption capacity.
If the absorption capacity is constant, if the near-infrared absorbing layer to be formed is thin, it is necessary to add a large amount of a diimonium compound in the coating agent. Is thick, the amount of the diimonium compound added to the coating agent may be small. That is, the amount of the diimonium compound in the coating agent and the thickness of the formed near-infrared absorbing layer can be determined according to the required near-infrared absorbing ability.

For example, the addition amount of the diimonium compound (B) is preferably 1 to 1000 mg, more preferably 5 to 500 mg per unit area 1 m ² of the near-infrared absorbing layer formed by the coating agent of the present invention.
More specifically, the coating agent of the present invention contains diimonium compounds in an amount of 0.1 to 100 parts by weight of the copolymer (A) containing the cycloalkyl group-containing monomer (a1) as an essential constituent. It is preferable to mix 10 parts by weight, and more preferably 0.5 to 5 parts by weight.
When the blending amount of the diimonium compound (B) is less than the above range, it is preferable to make the film thickness of the near infrared absorbing layer considerably thick in order to obtain a desired near infrared absorbing ability. On the other hand, when the blending amount of the diimonium compound exceeds the above range, the visible light transmittance may be lowered. Therefore, it is preferable to make the near-infrared absorption layer considerably thin.

  Incidentally, the diimonium compound (B) represented by the general formula (1) has a near-infrared absorbing ability in the range of 850 to 1200 nm, particularly has a strong near-infrared absorption around 1000 nm, and is used for a remote control or the like. In addition to the light of the wavelength, the light of the wavelength of the computer communication that is expected to be used in the future is also blocked, and the effect of preventing this malfunction can be expected.

The coating agent of the present invention preferably further contains a phthalocyanine compound (C) and a later-described dityl metal complex (D).
The phthalocyanine compound (C) used in the present invention is phthalocyanine, a phthalocyanine complex, or a phthalocyanine and phthalocyanine complex, and has one or more of OR, SR, NHR, or NRR ′ on the benzene ring of the phthalocyanine skeleton. Is. R and R ′ are the same or different and each represents a phenyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In addition, it is preferable that one of the substituents is phthalocyanine substituted with NHR.

  The phthalocyanine compound (C) used in the present invention is preferably a compound represented by the following general formula (7). The compound represented by the general formula (7) has excellent solvent solubility and excellent compatibility with the copolymer (A). Furthermore, when using the near-infrared absorption laminated body in which the near-infrared absorption layer formed with the near-infrared absorption coating agent using the phthalocyanine type compound represented by General formula (7) is laminated | stacked as a near-infrared absorption filter. In particular, a near-infrared absorption filter having high visible light transmittance, high near-infrared absorption efficiency, and excellent heat resistance and light resistance can be obtained.

(In the formula, α is the same or different and represents SR ¹ , OR ² , NHR ³ or a halogen atom, and NHR ³ is essential. R ¹ , R ² and R ³ are the same or different and are substituents. Represents a phenyl group, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, β is the same or different and represents SR ¹ , OR ² or a halogen atom, and SR ¹ Or, OR ² is essential, and M represents a metal-free, metal, metal oxide, or metal halide.)

  In the general formula (7), examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group A linear or branched alkyl group such as 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group; cyclohexyl group And the like, and the like. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The phenyl group, the alkyl group having 1 to 20 carbon atoms, or the aralkyl group having 7 to 20 carbon atoms in R ¹ , R ² , and R ³ may have one or more substituents. Examples of such substituents include halogen atoms, acyl groups, alkyl groups, alkoxy groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkylcarbonylamino groups, arylamino groups, arylcarbonylamino group carbonyls. Group, alkoxycarbonyl group and the like.

  In M in the general formula (7), a metal-free means an atom other than a metal, for example, two hydrogen atoms. Specifically, a structure in which a hydrogen atom is bonded to two opposing nitrogen atoms that may have a substituent and exist in the central portion of the phthalocyanine structure. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin chloride, and silicon chloride. M is preferably a metal, metal oxide or metal halide, and specific examples include nickel, cobalt, copper, zinc, iron, vanadyl, dichlorotin and the like. More preferred are zinc, copper, cobalt, vanadyl and dichlorotin.

As a preferred form of the phthalocyanine compound (C) represented by the general formula (7), 4 to 8 of 8 βs are the same or different and are SR ₁ or OR ₂ . More preferably, all eight βs are the same or different and are SR ₁ or OR ₂ . Examples of such phthalocyanine compounds include ZnPc (PhS) ₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ (PhNH) ₄ F ₄ , ZnPc (PhS) ₈ (PhNH) ₅ F ₃ , ZnPc (PhS). ) ₈ (PhCH ₂ NH) ₄ F ₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₅ F ₃ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₇ F, CuPc (PhS) ₈ (PhNH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH) ₆ F _{2, VOPc (PhO) 8 (} PhCH 2 NH) 8, VOPc (PhS) 8 (PhCH 2 NH) 8, VOP _{(2,5-Cl 2 PhO) 8} {2,6- (CH 3) 2 PhO} 4 {Ph (CH 3) CHNH} 3 F, VOPc (2,5-Cl 2 PhO) 8 {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , VOPc (4-CNPhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₄ , ZnPc (2,4-Cl ₂ PhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Phthalocyanine represented by an abbreviation of Ph (CH ₃ ) CHNH} ₃ F Compounds and the like.

Among these compounds, 4 of 8 αs are the same or different and represent OR ₂ or a halogen atom. For example, ZnPc (PhS) ₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ ( PhNH) ₄ F ₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₄ F ₄ , VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (2,5-Cl ₂ PhO) ₈ {2, 6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , VOPc (4-CNPhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₄ , ZnPc (2,4-Cl ₂ PhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F is preferably a phthalocyanine compound represented by an abbreviation.

In the abbreviations of the above compounds, Pc represents a phthalocyanine nucleus, and after Pc, represents eight substituents substituted at the β-position, and then represents eight substituents substituted at the α-position. Moreover, said Ph represents a phenyl group. More specifically, the above abbreviations represent central metal: Pc: 8 substituents at β-position: 8 substituents at α-position. For example, in VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, the central metal is 2 in the VO: phthalocyanine nucleus: β position. , 5-Cl ₂ PhO is substituted: represents a phthalocyanine compound in which α is substituted with 4,6- (CH ₃ ) ₂ PhO, ₃ Ph (CH ₃ ) CHNH, and 1 F.

  The method for producing the phthalocyanine compound represented by the general formula (7) is not particularly limited, and a conventionally known method can be appropriately used. For example, the phthalonitrile compound is produced by a cyclization reaction with one selected from metal salts, metal oxides, metal carbonyls, metal halides, and organic acid metals, followed by reaction with an amino compound.

Commercially available products of the phthalocyanine compound (C) represented by the general formula (7) include, for example, “EX color IR10A”, “EX color IR12”, “EX color IR14”, and “EX color HA. -1 "," EX Color HA-14 "(both made by Nippon Shokubai Co., Ltd.) and the like. From the viewpoint of solvent solubility of the phthalocyanine compound and compatibility with the copolymer (A), a near infrared absorption filter From the viewpoint of visible light transmittance and near-infrared absorption efficiency when used as “EX color IR10A”, “EX color IR12”, and “EX color IR14”.

The content of the phthalocyanine compound (C) contained in the near-infrared absorbing coating agent of the present invention is that the near-infrared absorbing laminate formed by laminating the near-infrared absorbing layer formed by the near-infrared absorbing coating agent of the present invention. When used as a near-infrared absorption filter, it is determined by the thickness of the near-infrared absorption filter and the required absorption capacity.
If the absorption capacity is constant, when the near infrared absorption layer formed is thin, it is necessary to add a large amount of a phthalocyanine compound in the coating agent. Is thick, the amount of the phthalocyanine compound added to the coating agent may be small. That is, the amount of the phthalocyanine compound in the coating agent and the thickness of the formed near-infrared absorbing layer can be determined according to the required near-infrared absorbing ability.

For example, the addition amount of the phthalocyanine compound (C) is preferably 1 to 1000 mg, more preferably 5 to 500 mg per unit area 1 m ² of the near infrared absorbing layer formed by the near infrared absorbing coating agent of the present invention. .
More specifically, the near-infrared absorbing coating agent of the present invention contains 0 phthalocyanine compound per 100 parts by weight of the copolymer (A) containing the cycloalkyl group-containing monomer (a1) as an essential constituent. 0.1 to 10 parts by weight is preferable, and 0.2 to 5 parts by weight is more preferable.
When the blending amount of the phthalocyanine compound is less than the above range, it is preferable that the film thickness of the near infrared absorbing layer is considerably increased in order to obtain a desired near infrared absorbing ability. On the other hand, if the blending amount of the phthalocyanine compound exceeds the above range, the visible light transmittance may be lowered. Therefore, it is preferable to make the near-infrared absorption layer considerably thin.

These phthalocyanine-based complex compounds (C) represented by the general formula (7) are characterized by having an absorption maximum in the near infrared region of 800 to 900 nm and a small absorption in the visible light region. Therefore, by combining with a diimonium-based compound, the near-infrared region of 800 to 1000 nm is efficiently absorbed and shielded by the synergistic effect of both, so that unnecessary near-infrared rays emitted from the plasma display can be absorbed.
In addition, it is known that the heat resistance of diimonium compounds generally decreases significantly when mixed with other dyes, but the heat resistance of diimonium compounds decreases when mixed with phthalocyanine compounds. In this respect, the combined use of both is preferable.

  The dithiol metal complex compound (D) used in the present invention is not particularly limited as long as it is generally called a dithiol metal complex compound. Specifically, the metal complex compound represented by the general formula (8) is used. It is.

(In the general formula (8), R _{24 to} R ₂₇ are the same or different from each other, hydrogen atom, halogen, cyano group, acyl group, carbamoyl group, alkylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, substituted or unrepresented. It represents a substituted alkyl group or a substituted or unsubstituted aryl group, and two adjacent substituents may be linked via a linking group, and M is nickel, platinum, palladium, or copper. These dithiol metal complex compounds (C) represented by the general formula (8) may be used alone or in combination of two or more.

In the dithiol metal complex compound (D) represented by the general formula (8), the substituents represented by R _{24 to} R ₂₇ are specifically described below.

  Examples of the halogen include fluorine, chlorine, bromine and iodine.

  Examples of the acyl group include acetyl group, ethylcarbonyl group, propylcarbonyl group, butylcarbonyl group, pentylcarbonyl group, hexylcarbonyl group, benzoyl group, pt-butylbenzoyl group and the like.

  Examples of alkylaminocarbonyl group include methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexyl. Aminocarbonyl group, n-heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl Group, di-sec-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptylaminocarbonyl group, di-octylaminocarbonyl group and the like. That.

  Examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl Group, n-pentyloxycarbonyl group, iso-pentyloxycarbonyl group, neo-pentyloxycarbonyl group, 1,2-dimethyl-propyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, 1,3- Dimethyl-butyloxycarbonyl group, 1-iso-propylpropyloxycarbonyl group, 1,2-dimethylbutyloxycarbonyl group, n-heptyloxycarbonyl group, 1,4-dimethylpentoxyl Nyl group, 2-methyl-1-iso-propylpropyloxycarbonyl group, 1-ethyl-3-methylbutyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3-methyl-iso-propyl Linear or branched having 2 to 20 carbon atoms such as butyloxycarbonyl group, 2-methyl-1-iso-propyloxycarbonyl group, 1-t-butyl-2-methylpropyloxycarbonyl group, n-nonyloxycarbonyl group And alkyloxycarbonyl groups.

  Examples of the aryloxycarbonyl group include a phenyloxycarbonyl group, a naphthyloxycarbonyl group, a trioxycarbonyl group, a xylyloxycarbonyl group, a chlorophenyloxycarbonyl group, and the like.

  Among the substituted or unsubstituted alkyl groups, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a sec-butyl group. , T-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, cyclopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1- iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n- Octyl group, 2-ethylhexyl group, 3-methyl 1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-t-butyl-2-methyl Propyl group, n- nonyl, 3,5,5 linear 1 to 20 carbon atoms such as trimethyl hexyl group, and a hydrocarbon group branched or cyclic.

The substituted alkyl group is a group in which at least one hydrogen of the above-described unsubstituted alkyl group is substituted with various functional groups.
For example,
An alkoxyalkyl group in which an hydrogen of an unsubstituted alkyl group is substituted with an alkoxy group,
An alkoxyalkoxyalkyl group in which hydrogen of an unsubstituted alkyl group is substituted with an alkoxyalkoxy group,
An alkoxyalkoxyalkoxyalkyl group in which hydrogen of an unsubstituted alkyl group is substituted with an alkoxyalkoxyalkoxy group,
A halogenated alkyl group in which the hydrogen of an unsubstituted alkyl group is replaced by a longogen,
An aminoalkyl group in which an hydrogen of an unsubstituted alkyl group is substituted with an amino group,
An alkylaminoalkyl group or a dialkylaminoalkyl group in which an hydrogen of an unsubstituted alkyl group is substituted with an alkylamino group,
Other examples include an alkoxycarbonylalkyl group, an alkylaminocarbonylalkyl group, and an alkoxysulfonylalkyl group.

Alkoxyalkyl groups include methoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, methoxyethoxymethyl, ethoxyethoxyethyl, dimethoxymethyl Group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group and the like,
Examples of the halogenated alkyl group include chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group and the like.

Among the substituted or unsubstituted aryl groups, examples of the unsubstituted one include a phenyl group, a naphthyl group, a biphenyl group, and the like. The substituted aryl group includes various kinds of at least one hydrogen of the above-described unsubstituted aryl group. The functional group is substituted.
For example, as a substituted phenyl group,
Halogenated phenyl groups such as chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, fluorophenyl group, pentafluorophenyl group, phenyl iodide group,

  Tolyl group, xylyl group, mesityl group, ethylphenyl group, dimethylethylphenyl group, iso-propylphenyl group, t-butylphenyl group, t-butylmethylphenyl group, octylphenyl group, nonylphenyl group, trifluoromethylphenyl group Alkyl derivative-substituted phenyl groups such as

  Methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, 3,5,5-trimethylhexyloxyphenyl group Methylethoxyphenyl group, dimethoxyphenyl group, 1-methoxy-5-ethoxyphenyl group, 1-methoxy-2-ethoxyphenyl group, 1-methoxy-3-ethoxyphenyl group, 1-methoxy-4-ethoxyphenyl group, 1-ethoxy-2-methoxyphenyl group, 2-methoxy-3-ethoxyphenyl group, 2-methoxy-4-ethoxyphenyl group, 2-methoxy-5-ethoxyphenyl group, 1-ethoxy-4-methoxyphenyl group, 2-methoxy-3-e Xiphenyl group, diethoxyphenyl group, ethoxyethoxyphenyl group, di (ethoxyethoxy) phenyl group, ethoxyethoxyethoxyphenyl group, di (ethoxyethoxyethoxy) phenyl group, 3-methoxy-4- (2-methoxyethoxy) phenyl group 3-methoxy-4- (2-ethoxyethoxy) siphenyl group, 3-ethoxy-4 (2-methoxyethoxy) siphenyl group, 3-ethoxy-4- (2-ethoxyethoxy) siphenyl group, 3-propoxy-4- ( 2-methoxyethoxy) phenyl group, 3-propoxy-4- (2-ethoxyethoxy) siphenyl group, 3-iso-propoxy-4- (2-methoxyethoxy) siphenyl group, 3-iso-propoxy-4- (2- Ethoxyethoxy) siphenyl group, 2- (2-hydroxy) -3-meth Shifeniru group, 3-methoxy-4- (2-hydroxyethoxy) phenyl group, chloro-methoxyphenyl group, an alkoxy substituted phenyl group such as chloro ethoxyphenyl group,

  Alkylthio group-substituted phenyl groups such as methylthiophenyl group, ethylthiophenyl group, t-butylthiophenyl group, di-tert-butylthiophenyl group, 2-methyl-1-methylthiophenyl group,

  N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-dipropylaminophenyl group, N, N-dibutylaminophenyl group, N, N-diamylaminophenyl group, N, N- Dihexylaminophenyl group, N-methyl-N-ethylaminophenyl group, N-butyl-N-ethylaminophenyl group, N-hexyl-N-ethylaminophenyl group, 4- (N, N-dimethylamino) -ethyl Alkylamino such as phenyl group, 4- (N, N-diethylamino) -ethylphenyl group, 3- (N, N-dimethylamino) -ethylphenyl group, 2- (N, N-dimethylamino) -ethylphenyl group A phenyl group etc. are mentioned.

As the substituted naphthyl group,
Halogenated naphthyl groups such as chloronaphthyl group, dichloronaphthyl group, trichloronaphthyl group, bromonaphthyl group, fluoronaphthyl group, pentafluoronaphthyl group, iodonaphthyl group,

  An alkyl derivative substituted naphthyl group of ethyl naphthyl group, dimethyl ethyl naphthyl group, iso-propyl naphthyl group, t-butyl naphthyl group, t-butylmethyl naphthyl group, octyl naphthyl group, nonyl naphthyl group, trifluoromethyl naphthyl group,

  Methoxynaphthyl group, ethoxynaphthyl group, propoxynaphthyl group, hexyloxynaphthyl group, cyclohexyloxynaphthyl group, octyloxynaphthyl group, 2-ethylhexyloxynaphthyl group, 3,5,5-trimethylhexyloxynaphthyl group, methylethoxynaphthyl group Group, dimethoxynaphthyl group, chloromethoxynaphthyl group, ethoxyethoxynaphthyl group, alkoxy group-substituted naphthyl group such as ethoxyethoxyethoxynaphthyl group,

  Alkylthio group-substituted naphthyl groups such as methylthionaphthyl group, ethylthionaphthyl group, t-butylthionaphthyl group, methylethylthionaphthyl group, butylmethylthionaphthyl group,

  N, N-dimethylaminonaphthyl group, N, N-diethylaminonaphthyl group, N, N-dipropylaminonaphthyl group, N, N-dibutylaminonaphthyl group, N, N-diamylaminonaphthyl group, N, N- Dihexylaminonaphthyl group, N-methyl-N-ethylaminonaphthyl group, N-butyl-N-ethylaminonaphthyl group, N-hexyl-N-ethylaminonaphthyl group, 4- (N, N-dimethylamino) -ethyl Alkylamino such as naphthyl group, 4- (N, N-diethylamino) -ethylnaphthyl group, 3- (N, N-dimethylamino) -ethylnaphthyl group, 2- (N, N-dimethylamino) -ethylnaphthyl group A naphthyl group is mentioned.

  In addition to these, the substituted or unsubstituted aryl group includes a substituted or unsubstituted p-nitrophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolidyl group, a substituted or unsubstituted piperidyl group, a substituted Alternatively, an unsubstituted morpholine group, a substituted or unsubstituted tetrahydropyridyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted furyl group, and the like can also be mentioned.

Particularly preferred among the substituents represented by R _{24 to} R ₂₇ of the thiol metal complex compound (D) represented by the general formula (8) are the same or different alkyl groups, phenyl groups, naphthyl groups, and tolyl groups. , Xylyl group, mesityl group, ethylphenyl group, dimethylphenyl group, iso-propylphenyl group, t-butylphenyl group, t-butylmethylphenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, N, N- Dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-dibutylaminophenyl group, ethylnaphthyl group, dimethylethylnaphthyl group, iso-propylnaphthyl group, t-butylnaphthyl group, t-butylmethylnaphthyl group, Methoxy naphthyl group, ethoxy naphthyl group, propoxy naphthyl group, Tylthionaphthyl, ethylthionaphthyl, t-butylthionaphthyl, methylethylthionaphthyl, butylmethylthionaphthyl, N, N-dimethylaminonaphthyl, N, N-diethylaminonaphthyl, N, N-di A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms such as a propylaminonaphthyl group and N, N-dibutylaminonaphthyl group, a phenyl group or a naphthyl group,
Particularly preferred M is nickel.

These dithiol metal complex compounds (D) represented by the general formula (8) are characterized by having an absorption maximum in the near-infrared region of 800 to 900 nm and small absorption in the visible light region. Therefore, by combining with a diimonium-based compound, the near-infrared region of 800 to 1000 nm is efficiently absorbed and shielded by the synergistic effect of both, so that unnecessary near-infrared rays emitted from the plasma display can be absorbed.
In addition, it is known that the heat resistance of diimonium compounds generally decreases significantly when mixed with other dyes, but the heat resistance of diimonium compounds decreases when mixed with dithiol metal complex compounds. In this respect, the combination of both is preferable.

The content of the dithiol metal complex compound (D) contained in the near-infrared absorbing coating agent of the present invention is such that the near-infrared absorbing laminate formed by laminating the near-infrared absorbing layer formed by the near-infrared absorbing coating agent of the present invention. Is used as a near infrared absorption filter, it is determined by the thickness of the near infrared absorption filter and the required absorption capacity.
If the absorption capacity is constant, when the near-infrared absorbing layer formed is thin, it is necessary to add a large amount of dithiol metal complex compound to the coating agent. When the thickness is large, the addition amount of the dithiol metal complex compound in the coating agent may be small. That is, the amount of the dithiol metal complex compound in the coating agent and the film thickness of the formed near infrared absorption layer can be determined according to the required near infrared absorption ability.

For example, the addition amount of the dithiol metal complex compound (D) is preferably 1 to 1000 mg, more preferably 5 to 500 mg, per 1 m ² of the near infrared absorbing layer formed by the near infrared absorbing coating agent of the present invention. is there.
More specifically, the near-infrared absorbing coating agent of the present invention contains a dithiol metal complex compound with respect to 100 parts by weight of the copolymer (A) having the cycloalkyl group-containing monomer (a1) as an essential constituent. It is preferable to mix 0.05 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight.
When the blending amount of the dithiol metal complex compound is less than the above range, it is preferable to make the film thickness of the near infrared absorbing layer considerably thick in order to obtain a desired near infrared absorbing ability. On the other hand, when the blending amount of the dithiol metal complex compound exceeds the above range, the visible light transmittance may be lowered. Therefore, it is preferable to make the film thickness of the near infrared absorption layer considerably thin.

  Further, a diimonium compound (B) represented by the general formula (1), a phthalocyanine compound (C) represented by the general formula (7), and a dithiol metal complex compound (D) represented by the general formula (8) Is preferably 10: 1: 1 to 1: 1: 1 (weight ratio) in this order because the wavelength in the near infrared region is efficiently absorbed.

  The cyanine compound (G) used in the present invention is preferably, for example, the following general formula (13).

Formula (13)

(In formula (13), R ^{31 to} R ³⁵ each independently represents an alkyl group which may have a substituent, and specific examples thereof are the same as those described above.
n represents an integer of 0 or more, and is usually 1 to 3. Z ¹ and Z ² are each independently an S atom, an O atom, NR ³⁶ , or CR ³⁷ R ³⁸ . R ^{36 to} R ³⁸ each independently represents an optionally substituted alkyl group or an optionally substituted phenyl group. Specific examples thereof are the same as those described above.
L ¹ and L ² independently form a 5- to 7-membered ring, and are preferably aromatic rings such as a benzene ring and a pyridine ring.
Specific examples of the compound (G) include, for example, Nippon Kayaku CY-17, CY-40, CYP-4646, Sumitomo Seika SD50, Hayashibara Biochemical Laboratories NK-5706, Yamamoto Kasei YKR. Cyanine compounds such as -2900, YKR-2081, TZ-113 and TZ-115 manufactured by Asahi Denka Kogyo can be suitably used. The above is an example, and the present invention is not limited to these.
The content of the cyanine compound (G) contained in the near-infrared absorbing coating agent of the present invention is 100 parts by weight of the copolymer (A) having the cycloalkyl group-containing monomer (a1) as an essential constituent. On the other hand, it is preferable to use 0.1 to 3.0 parts by weight.

  In addition, other near infrared absorbing compounds may be added to the near infrared absorbing coating agent of the present invention as long as the stability of the diimonium compound, the phthalocyanine compound, the dithiol metal complex compound, or the cyanine compound is not lowered. it can. Such near-infrared absorbing compounds include cyanine (polymethine), azulenium, squarylium, croconium, oxazine, azine, trisazotriphenylamine, naphthalocyanine, naphthoquinone, anthraquinone, triphenyl ( Aryl) In addition to near-infrared absorbing dyes such as methane, indoaniline, and aminium, copper salts such as metallic copper or copper sulfide, metal mixtures based on zinc oxide, tungsten compounds, YbPO4, ITO (tin-doped oxidation) Fine particles such as oxides, carbides and borides of metals belonging to Group 4, 5 or 6 of the periodic table, including fine particles such as indium) and ATO (tin-doped antimony oxide) can also be added. These average particle diameters are 1 micrometer or less, Preferably it is 0.2 micrometer or less, More preferably, they are 0.1 micrometer, These can also be added independently and can also use 2 or more types together.

  In the coating agent of the present invention, it is also possible to adjust the color tone using a color tone correcting dye. Such a color tone-correcting dye is stable for a long time, is soluble in the copolymer (A) containing the solvent and the cycloalkyl group-containing monomer (a1) described below as essential constituents, and absorbs visible light. Those having a narrow region and high transmittance at other wavelengths are preferable. Examples of color correction dyes include, but are not limited to, cyanine (polymethine), quinone, azo, indigo, polyene, spiro, porphyrin, phthalocyanine, and naphthalocyanine dyes. is not.

The coating agent of the present invention may further contain an ultraviolet absorber (E) and / or a hindered amine light stabilizer (F).
As the ultraviolet absorber (E) and the hindered amine light stabilizer (F) used in the present invention, conventionally known ultraviolet absorbers and hindered amine light stabilizers can be used.
For example, examples of the ultraviolet absorber (E) include salicylic acid-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.

  Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate. Commercially available products of these salicylic acid ultraviolet absorbers are SAP (manufactured by Iwaki Pharmaceutical Co., Ltd.), Zalol (manufactured by Dow Chem.), Zalor P (manufactured by Yatsushiro Pharmaceutical Co., Ltd.), TBS (manufactured by Dow Chem. Co.), and Biosorb-90 (Manufactured by Kyodo Yakuhin Co., Ltd.), SEESORB-201, SEESORB-202 (all manufactured by Sipro Kasei Co., Ltd.), butyrzarol (manufactured by Iwaki Pharmaceutical Co., Ltd.), OPS (manufactured by Eastman Chemical Company), and the like.

  Examples of the benzophenone-based UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′- Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) Examples include methane.

  Commercially available products of these benzophenone ultraviolet absorbers are ASL-23, ASL-40 (all manufactured by Shonan Chemical Co., Ltd.), SEESORB-100, SESORB-101, SESORB-101S, SESORB-102, SESORB-103, SESORB- 105, SEESORB-106, SEESORB-107 (all manufactured by Sipro Kasei Co., Ltd.), disilizer O, disilizer E (all manufactured by Sankyo Kasei Co., Ltd.), Sumisorb-130 (manufactured by Sumitomo Chemical Co., Ltd.), DHBA, DOPB (all yeast Man Chemical Co.), Biosorb-100, Biosorb-105, Biosorb-110, Biosorb-111, Biosorb-130 (all manufactured by Kyodo Yakuhin Co., Ltd.), Uvinul-400, Uvinul-M-4 , Uvinul-D-49, Uvinul-MS-40, UVA-633L, UVA-635L, UVA-935LH, UVA-383MA (all manufactured by BASF), Cyasorb UV-9, Cyasorb UV-24 (all Cytec) Manufactured), Ortholex 360 (manufactured by Merck Japan), Adeka Stub 1413, Adeka Stub LA-51 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Hostavin-ARO8 (manufactured by Clariant), Tomissorb-800 (manufactured by API Corporation), etc. Can be mentioned.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-5'-amyl Phenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy) 3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2 (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, 2,2'-methylenebis [4- (1,1 , 3,3-tetramethylbutyl) -6-{(2H-benzotriazol-2-yl) phenol}], 2 (2'-hydroxy-3 ', 5'-di-t-aminophenyl) benzotriazole, etc. Is mentioned.

  Examples of commercially available products of these benzotriazole ultraviolet absorbers include JF-77, JF-78, JF-79, JF-80, JF-86 (all manufactured by Johoku Chemical Co., Ltd.), Tinuvin-P, and Tinuvin-PS. , Tinuvin-320, Tinuvin-326, Tinuvin-327, Tinuvin-328, Tinuvin-384-2 (all manufactured by Ciba Specialty Chemicals), SEESORB-701, SEESORB-702, SEESORB-703, SEESORB-704 , SEESORB-705, SEESORB-706, SEESORB-709 (all manufactured by Sipro Kasei Co., Ltd.), Sumisorb-200, Sumisorb-250, Sumisorb-300, Sumisorb-340, Su isosorb-350 (all manufactured by Sumitomo Chemical Co., Ltd.), Biosorb-510, Biosorb-520, Biosorb-550, Biosorb-580, Biosorb-582, Biosorb-583, Biosorb-590, Biosorb-591 (all Kyodo Yakuhin) ), Adeka Stub LA-29, Adeka Stub LA-31, Adeka Stub LA-32, Adeka Stub LA-36 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Tomissorb-100, Tomissorb-600, Tomissorb-700 (all manufactured by API Corporation) ) And the like.

  Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate and ethyl-2-cyano-3,3′-diphenyl acrylate. Commercial products of these cyanoacrylate ultraviolet absorbers include Uniol 3035 (manufactured by BASF), Biosorb-910, Biosorb-920, (all manufactured by Kyodo Pharmaceutical Co., Ltd.), SEESORB-501, and SEESORB-502 (all of which are Sipro Kasei Co., Ltd.) Manufactured) and the like.

  Commercially available products of the above benzoate-based ultraviolet absorbers include Tinuvin-120 (manufactured by Ciba Specialty Chemicals), Sumisorb-400 (manufactured by Sumitomo Chemical), SEESORB-712 (manufactured by Cypro Kasei Co., Ltd.), Viosorb-80 ( (Manufactured by Kyodo Pharmaceutical Co., Ltd.).

  Moreover, a metal complex type ultraviolet absorber can also be used. For example, [2,2′-thiobis (4-tert-octylphenolate)]-2 ethylhexylamine nickel (II) and the like are listed, and commercially available products include SEESORB-612NH (manufactured by Cypro Kasei Co., Ltd.) and the like. .

  Further, malonic acid ester UV absorbers and oxalic anilide UV absorbers can also be used. For example, as commercially available products of malonic acid ester UV absorbers, Hostavin PR-25 (manufactured by Clariant) and the like, and as commercially available products of oxalic acid anilide UV absorbers, Sanduvor VSU (manufactured by Clariant) and the like can be mentioned.

  Examples of the hindered amine light stabilizer (F) include a hindered amine light stabilizer having no hindered phenol skeleton and a hindered amine light absorber having a hindered phenol skeleton.

  Commercially available hindered amine light stabilizers having no hindered phenol skeleton include Sanol LS-770 (manufactured by Sankyo Co., Ltd.), ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-63P, ADK STAB LA-67, ADK STAB LA-68LD, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-82, ADK STAB LA-87 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Sumisorb-577 (manufactured by Sumitomo Chemical Co., Ltd.), Viosorb-03, Viosorb- 04 (all manufactured by Kyodo Yakuhin Co., Ltd.), Chimassorb 944LD (manufactured by Ciba Specialty Chemicals), Tinuvin-622LD (manufactured by Ciba Specialty Chemicals), Goodrite UV-3034 (Good) As a commercially available product of the hindered amine light stabilizer having the hindered phenol skeleton, Tinuvin-144 (manufactured by Ciba Specialty Chemicals) and the like can be mentioned.

  The total amount of the ultraviolet absorber (E) and / or the hindered amine light stabilizer (F) used in the present invention is preferably 0.1 to 60 parts by weight when the copolymer (A) is 100 parts by weight. When the amount is less than 0.1 parts by weight, the heat resistance and light resistance are not sufficiently improved. When the amount exceeds 60 parts by weight, the effect of improving heat resistance and light resistance with respect to the amount used is reduced, and the cost is disadvantageous. There is a possibility that the solubility and stability of the near-infrared absorbing dye may be deteriorated.

  The coating agent of the present invention can further contain a plasticizer, a crosslinking agent, an antioxidant, a polymerization retarder and the like.

  In order to produce the near-infrared absorbing coating agent of the present invention, the diimonium compound (B), and the phthalocyanine compound (C) and / or the dithiol metal complex compound (D), which are used as necessary, Alternatively, the cyanine compound (G) may be simply added to the copolymer (A) having a cycloalkyl group-containing monomer as an essential constituent, and there is no particular limitation on the means thereof. A) A copolymer solution is obtained using a solvent that dissolves (a solution polymerized resin is already a solution), a diimonium compound (B), and a phthalocyanine compound (C) used as necessary, It is preferable to add a dithiol metal complex compound (D) or a cyanine compound (G) to the copolymer solution and dissolve it. Furthermore, it manufactures by adding a ultraviolet absorber (E) and / or a hindered amine light stabilizer (F) as needed.

  As the solvent contained in the near-infrared absorbing coating agent of the present invention, a copolymer containing a cycloalkyl group-containing monomer as an essential constituent is dissolved, and a diimonium compound, a phthalocyanine compound, and a dithiol metal complex compound Can be used. For example, aromatic solvents such as toluene and xylene; alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, propylene glycol monomethyl ether; ethyl acetate, Ester solvents such as butyl acetate and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; chlorine solvents such as chloroform, dichloromethane, trichloromethane, and methylene chloride; tetrahydrofuran, diethyl ether, 1,4- Ether solvents such as dioxane and 1,3-dioxolane; one or two of N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, dimethylacetamide and the like Or more can be used.

By laminating a near-infrared absorbing layer formed from the above-mentioned near-infrared absorbing coating agent on a substrate, the near-infrared absorbing laminate of the present invention can be obtained.
Specifically, the near-infrared-absorbing coating agent is applied to at least one surface of a flat substrate by various methods, dried, and the solvent in the coating agent is removed to form a near-infrared-absorbing layer. It can form on a base material and the near-infrared absorption laminated body of this invention can be obtained.

  Examples of methods for applying the coating agent of the present invention to a substrate include bar coating, blade coating, spin coating, reverse coating, diting, spray coating, roll coating, gravure coating, lip coating, air knife coating, and dipping method. It can apply | coat and heat-dry so that it may become tack-free, and can obtain a near-infrared absorption laminated body.

Examples of the substrate used in the present invention include a plastic film and glass. Of course, a plastic film is preferable in terms of cost and ease of handling as well as high transparency. Specifically, films formed from polyester, acrylic, triacetyl cellulose, polyethylene, polypropylene, polyolefin, polycycloolefin, polyvinyl chloride, polycarbonate, phenol, urethane resin, etc. Polyester films are preferred from the standpoints of physical properties, optical properties, chemical resistance, environmental impact, and the like. More specifically, a polyethylene terephthalate film (hereinafter also referred to as PET film) is preferable.
As the base material, a so-called easy-adhesion type film in which a polyester film is further provided with a resin layer such as an acrylic resin, a copolyester resin, a polyurethane resin, a styrene-maleic acid graft polyester resin, and an acrylic graft polyester resin. Can also be used.

In the present invention, at least one layer having various functions such as an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, an anti-scratch layer, an antireflection layer, a color tone correction layer, a heat dissipation layer, and an impact resistance layer is further laminated on the plastic film. Can be used as a substrate.
Alternatively, a film in which an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, an anti-scratch layer, an antireflection layer, a color tone correction layer, or the like is provided between the above-described plastic film and the plastic film can also be used as a substrate. For example, such a multilayer plastic film can be obtained by bonding a plurality of plastic films using pressure-sensitive adhesives and adhesives having various functions.

  When the coating agent of the present invention is applied to a functional base material previously provided with an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, an anti-scratch layer, an antireflection layer, a color tone correction layer, a heat radiation layer, and an impact resistant layer on a plastic film. , And can be provided between or on the layers. Moreover, when the electromagnetic wave absorption layer has a mesh shape as described later, the electromagnetic wave absorption layer may be provided by being applied to the opening of the mesh.

The ultraviolet absorbing layer is preferably one that can efficiently absorb ultraviolet rays having a wavelength of 400 nm or less, and can absorb 80% or more of a wavelength of 350 nm. The ultraviolet absorbing layer is not particularly limited, but it is preferable to add an ultraviolet absorber to the resin and form a film on the plastic film by a coating method, a calendar method, a casting method or the like.
The resin is not particularly limited as long as it is bonded to a plastic film with a transparent polymer resin, such as copolymer polyester, polymethyl methacrylate, polycarbonate, polystyrene, amorphous polyolefin, cycloolefin, polyurethane, polyarylate, and triacetyl cellulose. In addition, amorphous engineer plastic resins such as polysulfone, polyetherimide, polyamideimide, polyimide, polyphenylene ether, polyethersulfone can also be used.
As the ultraviolet absorber, either an inorganic type or an organic type can be used, but an organic ultraviolet absorber is practical. As an organic ultraviolet absorber, it has a maximum absorption between 300 to 400 nm, and absorbs light in that region efficiently. A benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, a salicylic acid ester ultraviolet ray Examples thereof include an absorbent, an acrylate ultraviolet absorber, an oxalic acid anilide ultraviolet absorber, and a hindered amine ultraviolet absorber. These may be used alone, but are more preferably used in combination of several kinds. Moreover, stabilization can be improved by blending the said ultraviolet absorber and a hindered amine light stabilizer, or antioxidant. Moreover, it can also substitute for an ultraviolet absorber layer by using a plastic film containing an ultraviolet absorber (kneading etc.) as a base material.

  The electromagnetic wave absorbing layer blocks electromagnetic waves emitted from the plasma display, and the production method thereof is not particularly limited. For example, the electromagnetic wave absorption layer is a transparent conductive film, and a plastic film obtained by vapor-depositing a thin film of metal, metal oxide, metal salt or the like is preferably used. The lower the surface resistance of the conductive film, the higher the electromagnetic wave absorption ability, but conversely the visible light transmittance decreases as the vapor deposition layer becomes thicker. Moreover, what printed the electroconductive coating material in mesh shape by screen printing etc., or what laminated | stacked the electroconductive metal on the plastic film and formed this in the mesh shape by etching etc. can be used.

  The scratch-preventing layer is for preventing the surface of the plasma display from being scratched, and a resin such as an ultraviolet curable type, an electron beam curable type, or a thermosetting type can be used, but the production method thereof is not particularly limited. . For example, it can be formed with various (meth) acrylates, a photopolymerization initiator, and, if necessary, a coating agent containing an organic solvent as a main component. As various (meth) acrylates, (meth) acrylates such as polyurethane (meth) acrylate and epoxy (meth) acrylate, or other polyfunctional (meth) acrylates can be preferably used.

  Epoxy (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to a (meth) acryloyl group, and a (meth) acrylic acid adduct to a bisphenol A type epoxy resin, There are (meth) acrylic acid adducts to novolac type epoxy resins.

The urethane (meth) acrylate can be obtained, for example, by reacting an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under an excess of isocyanate groups with (meth) acrylates having a hydroxyl group. . Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.
Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.
Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.
Examples of (meth) acrylates having an isocyanate group include 2-methacryloyloxyethyl isocyanate and methacryloyl isocyanate.

  Other polyfunctional (meth) acrylates have two or more (meth) acryloyl groups in the molecule, and preferably have three or more acryloyl groups in the molecule. Specifically, trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, tris (acryloyloxyethyl) isocyanurate, caprolactone modified tris (acryloyloxyethyl) isocyanurate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl modified dipentaerythritol triacrylate, alkyl modified dipentaerythritol pentaacrylate, caprolactone modified dipentaerythritol hexaacrylate, Beauty mixtures of two or more of these and the like.

  As photopolymerization initiators, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, gendyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone 2,4,6-trimethylbenzoindiphenylphosphine oxide, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. The above can also be used together as appropriate.

  Examples of the organic solvent used in the coating agent for forming a scratch-resistant layer include aromatic hydrocarbons such as toluene and xylene, ethyl acetate, acetic acid-n-propyl, acetic acid-iso-propyl, acetic acid-n-butyl, acetic acid-iso Esters such as butyl, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone cyclohexanone, 2-methoxyethanol, Ethers such as 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether, 2-methoxyethyl acetate Over DOO, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, ether esters such as propylene glycol methyl ether acetate and the like, can also be used as a mixture of two or more thereof.

  In addition to the above components, a colloidal metal oxide or silica sol using an organic solvent as a dispersion medium may be added to improve wear resistance. Scratch prevention layer can be applied to the above coating agent coating solutions such as bar coating, blade coating, spin coating, reverse coating, diting, spray coating, roll coating, gravure coating, lip coating, air knife coating, dipping method, etc. After coating by the method, it is formed by drying the solvent and further crosslinking and curing the coated coating agent by irradiating with active energy rays. Examples of the active energy ray include ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp, or an electron extracted from an electron beam accelerator usually 20 to 2000 KeV. Lines, α rays, β rays, γ rays and the like can be used. The scratch-preventing layer thus formed has a thickness of usually 1 to 50 μm, preferably 3 to 20 μm.

  The antireflection layer prevents surface reflection, increases visible light transmittance, and at the same time prevents glare, and any processing method can be selected for the formation method, and there is no particular limitation. A method for reducing luminous reflectance by irregularly reflecting external light, for example, forming an antireflection film that causes irregular reflection of light by coating and coating fine particles of silicon dioxide, acrylic, melamine, etc. on one side of a plastic film A method, or a method in which a cured film is formed on one side of a plastic film and an antireflection layer is formed thereon by vapor deposition of a magnesium fluoride layer, or a low refractive index layer of a thin film on one or both sides of a plastic film, or refractive A method is generally used in which multilayer thin films having different rates are formed and the reflectivity is reduced by interference between the surface reflected light of the thin film and the refracted reflected light at the interface.

  In particular, in a display device using a fluorescent material such as a plasma display, a CRT, a fluorescent display tube, or a field emission display, the applied fluorescent material is irradiated with an electron beam or ultraviolet light to emit the fluorescent material, and the fluorescent screen is Display is performed by transmitted or reflected light. Since phosphors are generally white and have high reflectance, external light is often reflected on the phosphor screen. For this reason, the problem of a decrease in display contrast due to reflection of external light is particularly serious in a display device using a phosphor. It is technically difficult to prevent reflection on the phosphor screen. Therefore, in a display device using a phosphor, a neutral gray filter is installed in front of the display in order to absorb reflected light as another countermeasure. The neutral gray filter is also called an ND filter, and its transmittance is generally 40 to 80%.

  Further, in order to correct the color balance of the display color, a color adjustment filter is installed on the front surface of the display. As described above, in the plasma display device, color tone correction filters such as a color adjustment filter and a neutral gray filter are often provided on the front surface of the display for the purpose of improving display contrast and improving display quality. In particular, a color correction filter mainly for color adjustment is important. This color tone correction filter is formed by laminating a color tone correction layer on a plastic film.

  As such a color correction layer, it is preferable to add a color correction dye into the resin and form a film on a plastic film by a coating method, a calendar method, a casting method or the like. The resin is not particularly limited as long as it is bonded to a plastic film with a transparent polymer resin, and the resins described in the ultraviolet absorption layer can be used. Examples of color correction dyes include, but are not limited to, cyanine (polymethine), quinone, azo, indigo, polyene, spiro, porphyrin, phthalocyanine, and naphthalocyanine dyes. is not.

The near-infrared absorbing laminate of the present invention is selected from the group consisting of an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, an anti-scratch layer, an antireflection layer, a color tone correction layer, a heat dissipation layer and an impact resistant layer after providing a near infrared absorbing layer. At least one layer can be further laminated.
That is, the layer having various functions described above can be further laminated on the near-infrared absorbing layer, and the above-mentioned various functional layers can be provided on the substrate, that is, on the surface opposite to the near-infrared absorbing layer. When various functional layers are provided on the surface opposite to the near infrared absorbing layer, various functional layers can be provided on the plastic film, or when the near infrared absorbing layer is provided, various functional layers are already provided. When used as a base material, various functional layers can be further formed on the laminated functional layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these specific examples. In the examples, “parts” means “parts by weight”.
[Synthesis Example 1]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube was charged with 120 parts of methyl ethyl ketone, 60 parts of methyl methacrylate, and 40 parts of cyclohexyl methacrylate, and the temperature was raised to the reflux temperature under a nitrogen stream. To this, a mixture of 0.05 part of tert-butyl-peroxy-2-ethylhexanote and 30 parts of methyl ethyl ketone was continuously added dropwise over 1 hour, and then reacted at reflux temperature for 2 hours. Furthermore, 0.05 part of tert-butyl-peroxy-2-ethylhexanote was added three times every 2 hours, and the reaction was continued. After 14 hours from the end of the dropping, 83 parts of toluene was added to complete the reaction, and a copolymer (1) solution having a nonvolatile content of 30%, a viscosity of 1,300 mPa · s (25 ° C.), and a weight average molecular weight of 315,000 was obtained. .

[Synthesis Examples 2 to 4]
Except that the polymerizable monomers used in Synthesis Example 1 were as shown in Table 2, the same operations as in Synthesis Example 1 were performed to obtain Copolymer (2) to (4) solutions. Table 2 shows the nonvolatile content, viscosity, and weight average molecular weight of the obtained copolymers (2) to (4).

The abbreviations in Table 2 are as follows.
CHMA is cyclohexyl methacrylate,
MMA is methyl methacrylate,
2EHMA is 2-ethylhexyl methacrylate,
RUVA93 (trade name) is 2- (2'-hydroxy-5-methacryloylethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.), which is a monomer having a benzotriazole group and a polymerizable unsaturated group. is there.

The nonvolatile content, viscosity, and weight average molecular weight were measured as follows.
(Nonvolatile content) About 1 g of a sample was weighed and dried at 150 ° C. for 20 minutes.
(Viscosity) Measured at 25 ° C. with a BM type rotational viscometer (manufactured by Tokyo Seiki Co., Ltd.). The rotor and rotation speed were selected according to the viscosity.
(Weight average molecular weight) Shodex GPC KF-802L, KF-803L and KF-805L (all manufactured by Showa Denko KK) as columns in Shodex GPC SYSTEM21 type gel perem chromatography (manufactured by Showa Denko KK) Were measured in series (polystyrene conversion).

[Example 1]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (1) solution obtained in Synthesis Example 1 to obtain a solution having a nonvolatile content of 20% by weight.
To this, a diimonium compound (1) represented by the following formula (9), wherein the branched alkyl group is a 2-methylpropyl (iso-butyl) group and the anion of X is hexafluoroantimonic acid (the former 0.6 part of No. 1 compound in Table 1 and 0.17 part of dithiol metal complex compound [trade name MIR-101 (manufactured by Midori Chemical Co., Ltd.)] represented by the following formula (10) are added and dissolved. Thus, a near-infrared absorbing coating agent was prepared.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. Thus, a near-infrared absorbing laminate (1) having a coating thickness of 12 μm was obtained, and heat resistance and light resistance were evaluated as follows. The results are shown in Table 3.

[Heat resistance evaluation]
About the obtained near-infrared absorption laminated body (1), the transmittance | permeability (%) in each wavelength of 850 nm and 950 nm was measured with the spectrophotometer (The JASCO Corporation make, V-570 type | mold) (before a test). Then, the transmittance (%) after standing in a thermostatic chamber at 80 ° C. for 500 hours was measured in the same manner as described above (the transmittance after the test). The criteria for evaluating the transmittance change before and after the test are as follows.
Difference in transmittance before and after test is less than ± 3: Good Difference in transmittance before and after test is ± 3 or more and 5 or less: Slightly good,
The difference in transmittance before and after the test exceeded ± 5: Poor Also, the near-infrared absorbing laminate (1) before and after the heat resistance test was measured with a color difference meter (CR-300, manufactured by Minolta Co., Ltd.). Color (Y, x, y) was performed.
The color change of the laminate before and after the test was evaluated according to the following criteria.
A: Difference in y value before and after test (Δy) is less than ± 0.005 ○: Difference in y value before and after test (Δy) is ± 0.005 or more and 0.010 or less Δ: Difference in y value before and after test (Δy) exceeds ± 0.010, 0.015 or less x: Difference in y value before and after the test (Δy) exceeds ± 0.015

[Light resistance evaluation]
About the obtained near-infrared absorption laminated body (1), the transmittance | permeability (%) in each wavelength of 850 nm and 950 nm was measured with the spectrophotometer (The JASCO Corporation make, V-570 type | mold) (before a test). (Transmittance) and then transmittance after light resistance test (light irradiation only, 60 ° C., 60% RH, continuous irradiation for 24 hours) using a strong energy xenon weather meter (SC700-WN, manufactured by Suga Test Instruments Co., Ltd.) %) Was measured as described above (transmittance after test). The criteria for evaluating the change in transmittance before and after the test are the same as in the heat resistance evaluation.
Further, for the near-infrared absorbing laminate (1) before and after the light resistance test, color measurement (Y, x, y) was performed with a color difference meter (manufactured by Minolta Co., Ltd., CR-300). The standard for evaluating the color change before and after the test is the same as in the heat resistance evaluation.

[Example 2]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (1) solution obtained in Synthesis Example 1 to obtain a solution having a nonvolatile content of 20% by weight.
To this, a diimonium compound (2) represented by the following formula (11), in which the branched alkyl group is a 2-methylpropyl (iso-butyl) group and the anion of X is hexafluorophosphate 0.6 part of the compound No. 2 in Table 1) and the phthalocyanine compound (C1) [structure abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ 0.3 parts of {Ph (CH ₃ ) CHNH} ₃ F] was added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. The near-infrared absorbing laminate (2) having a coating thickness of 13 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

[Example 3]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (2) solution obtained in Synthesis Example 2 to obtain a solution having a nonvolatile content of 20% by weight.
To this, a diimonium compound (5) represented by the following formula (12) in which the branched alkyl group is a 3-methylbutyl group and the anion of X is hexafluoroantimonic acid (No. 5 in Table 1 above) Compound) and phthalocyanine compound (C2) [structure abbreviation: VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (Ph (CH ₂ NH ₄ ) 0.3 parts of ₄ ) was added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. And a near-infrared absorbing laminate (3) having a coating thickness of 13 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

[Example 4]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (2) solution obtained in Synthesis Example 2 to obtain a resin solution having a nonvolatile content of 20% by weight.
To this, a diimonium compound (6) represented by the following formula (13) in which the branched alkyl group is a 3-methylbutyl group and the anion of X is hexafluorophosphoric acid (No. 6 in Table 1 above) Compound) and phthalocyanine compound (C3) [structure abbreviation: CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (Ph (CH ₂ NH ₄ ) 0.3 parts of ₄ ) was added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. And a near-infrared absorbing laminate (4) having a coating thickness of 11 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

[Example 5]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (3) solution obtained in Synthesis Example 3 to obtain a resin solution having a nonvolatile content of 20% by weight.
Similarly to that used in Example 1, diimonium represented by the formula (9), wherein the branched alkyl group is 2-methylpropyliso-butyl) and the anion of X is antimony hexafluoride 0.6 part of the compound (1) and 0.3 part of a phthalocyanine compound [trade name EX Color IR-10A (manufactured by Nippon Shokubai Co., Ltd.)] were added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent is applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. A near-infrared absorbing laminate (5) having a coating thickness of 11 μm was obtained and evaluated for heat resistance and light resistance. The results are shown in Table 3.

[Example 6]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (1) solution obtained in Synthesis Example 1 to obtain a solution having a nonvolatile content of 20% by weight.
To this, 0.16 part of the ultraviolet absorber Tinuvin-384-2, represented by the same formula (9) as used in Example 1, the branched alkyl group is 2-methylpropyliso-butyl) 0.6 part of a diimonium compound (1) in which the anion of X is antimony hexafluoride, and a phthalocyanine compound [trade name EX Color IR-10A (manufactured by Nippon Shokubai Co., Ltd.)] 0.3 Part was added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. And a near-infrared absorbing laminate (6) having a coating thickness of 12 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

[Example 7]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (1) solution obtained in Synthesis Example 1 to obtain a resin solution having a nonvolatile content of 20% by weight.
To this, 0.6 parts of diimonium compound [trade name IRG-068 (manufactured by Nippon Kayaku Co., Ltd.)] and 0.17 parts of cyanine compound [trade name CY-17 (manufactured by Nippon Kayaku Co., Ltd.)] Furthermore, it melt | dissolved and the near-infrared absorption coating agent was prepared.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. The near-infrared absorbing laminate (7) having a coating thickness of 13 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

[Comparative Example 1]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (1) solution obtained in Synthesis Example 1 to obtain a solution having a nonvolatile content of 20% by weight.
To this, 0.6 part of a linear alkyl group diimonium compound [trade name CIR-1081 (manufactured by Nippon Carlit Co., Ltd.)] represented by the following formula (14), and a phthalocyanine compound [trade name EX color IR -14 (manufactured by Nippon Shokubai Co., Ltd.)] was added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent is applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. A near-infrared absorbing laminate (8) having a coating thickness of 12 μm was obtained and evaluated for heat resistance and light resistance. The results are shown in Table 3.

[Comparative Example 2]
50 parts of methyl ethyl ketone was added to 100 parts (solid content: about 30 parts) of the copolymer (4) solution obtained in Synthesis Example 4 to obtain a solution having a nonvolatile content of 20% by weight.
Similarly to that used in Example 1, the branched alkyl group represented by the formula (9) is a 2-methylpropyl (iso-butyl) group and the anion of X is hexafluoroantimonic acid. 0.6 parts of the diimonium compound (1) and a dithiol metal complex compound represented by the formula (12) as used in Example 1 [trade name: MIR-101 (manufactured by Midori Chemical Co., Ltd.)] 0.17 parts was added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. And a near-infrared absorbing laminate (9) having a coating thickness of 11 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

[Comparative Example 3]
In 100 parts of 1,3-dioxolane, 17.6 parts of a polyarylate resin [trade name U-100 (manufactured by Unitika Ltd.)] was dissolved to obtain a resin solution having a nonvolatile content of 15% by weight.
Similarly to that used in Example 1, the branched alkyl group represented by the formula (9) is a 2-methylpropyl (iso-butyl) group and the anion of X is hexafluoroantimonic acid. 0.35 parts of the diimonium compound (1) and a dithiol metal complex compound represented by the formula (12) as used in Example 1 [trade name: MIR-101 (manufactured by Midori Chemical Co., Ltd.)] 0.1 part was added and melt | dissolved, and the near-infrared absorption coating agent was prepared.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. And a near-infrared absorbing laminate (10) having a coating thickness of 13 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

[Comparative Example 4]
25 parts of a polyester resin [trade name Byron 200 (manufactured by Toyobo Co., Ltd.)] was dissolved in a mixed solvent of 50 parts of toluene and 50 parts of methyl ethyl ketone to obtain a resin solution having a nonvolatile content of 20% by weight.
Similarly to that used in Example 1, the branched alkyl group represented by the formula (9) is a 2-methylpropyl (iso-butyl) group and the anion of X is hexafluoroantimonic acid. 0.5 parts of the diimonium compound (1) and a dithiol metal complex compound represented by the formula (12) as used in Example 1 [trade name: MIR-101 (manufactured by Midori Chemical Co., Ltd.)] 0.14 parts was added and dissolved to prepare a near-infrared absorbing coating agent.
This coating agent was applied to the easy-adhesion surface of an ultraviolet-absorbing PET film [trade name HBF8W (manufactured by Teijin DuPont Films Ltd.)] having an easy-adhesion layer with a thickness of 100 μm using a bar coater and dried at 100 ° C. for 1 minute. The near-infrared absorbing laminate (11) having a coating film thickness of 12 μm was obtained, and the heat resistance and light resistance were evaluated. The results are shown in Table 3.

As shown in Table 3, the near-infrared absorbing laminates obtained in Examples 1 to 7 showed not only a small difference in transmittance before and after the test, but also a small color change in both the heat resistance test and the light resistance test. It can be seen that it has excellent heat resistance as well as excellent light resistance.
In contrast, the near-infrared absorbing laminates obtained in Comparative Examples 1 to 4 have a large difference in transmittance or color change before and after the test in either the heat resistance test or the light resistance test, and the heat resistance and light resistance. There is no one that satisfies both.

  The near-infrared-absorbing laminate comprising the near-infrared-absorbing coating agent of the present invention has a high visible light transmittance, good near-infrared shielding, and excellent heat resistance and light resistance, and thus is useful as an optical filter. is there.

Claims (10)

A near infrared ray comprising a copolymer (A) having a cycloalkyl group-containing monomer (a1) as an essential constituent, and a diimonium compound (B) represented by the following general formula (1) Absorbent coating agent.

(In the formula (1), R _{1 to} R ₈ may be the same or different, and at least one of them is a branched alkyl group, and the rings A and B may have a substituent. Well, X represents the anion necessary to neutralize the charge.) Rings A and B other than 1,4- are unsubstituted or have 1 to 4 halogen atoms, lower alkyl groups, lower alkoxy groups, cyano groups and / or hydroxy groups as substituents. 1. A near-infrared absorbing coating agent according to 1. The branched alkyl group in R _{1 to} R ₈ is 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3 The near-infrared absorbing coating agent according to claim 1, which is a methylbutyl group or a 2-ethylbutyl group. 4. The near-infrared absorbing coating agent according to claim 1, wherein the branched alkyl group in R _{1 to} R ₈ has a structure represented by — (CH ₂ ) _n —R.
(However, n represents an integer of 1 or more, and R represents an alkyl group having a secondary or tertiary carbon.) The copolymer (A) comprises a monomer (a2) having a benzotriazole group and a polymerizable unsaturated group and / or a monomer (a3) having a piperidinyl group and a polymerizable unsaturated group as constituent components. The near-infrared absorptive coating agent in any one of Claims 1-4 characterized by the above-mentioned. The near-infrared absorbing coating agent according to any one of claims 1 to 5, further comprising a phthalocyanine compound (C) and / or a dithiol metal complex compound (D). The near-infrared absorbing coating agent according to claim 1, further comprising a cyanine compound (G). The near-infrared absorbing coating agent according to any one of claims 1 to 7, further comprising an ultraviolet absorber and (E) and / or a hindered amine light stabilizer (F). The near-infrared absorption laminated body by which the near-infrared absorption layer formed from the near-infrared absorptive coating agent in any one of Claims 1-8 is laminated | stacked on a base material. At least one layer composed of an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, an anti-scratch layer, an antireflection layer, a color tone correction layer, a heat dissipation layer, and an impact resistant layer is laminated on the substrate side and / or on the near infrared absorbing layer. The near-infrared absorption laminated body of Claim 9.