KR20090050027A - Near-infrared absorbing film and optical filter for plasma display panel using the same - Google Patents

Abstract

[PROBLEMS] A dimonium salt compound having a relatively wide absorption wavelength band of near infrared rays, having good heat resistance and moisture resistance, and having a wide range of Tg of a binder resin that can be used, as well as a cured film layer according to a general manufacturing method, and having a relatively high Tg. To find a compound having good stability even in a coating resin layer using a low binder resin, and to develop a near-infrared absorbing film that maintains it, and to develop an optical filter for PDP using the same.

[Solution] A near-infrared absorbing film showing excellent stability using a dimonium salt compound represented by the following formula (1), and an optical filter for PDP using the same:

Where

R ₁ to R ₈ each independently represent an aliphatic hydrocarbon residue which may have a hydrogen atom or a substituent,

X ^- and Y ^- represent monovalent anions which are not identical to each other.

Near Infrared Absorption Film, Optical Filter

Description

Near-Infrared Absorbing Film And Optical Filter For Plasma Display Panel Using The Same}

The present invention is a near-infrared absorbing film using a dimonium salt compound that absorbs light of a wavelength in the near-infrared region broadly, and is excellent in heat resistance, moist heat resistance, and solvent solubility, and a plasma display panel using the same (hereinafter referred to as 'PDP'). It relates to an optical filter for.

The principle of the PDP is to apply a voltage to a rare gas neon, xenon, etc. enclosed in a cell between two sheets of glass, and the ultraviolet rays emitted by the rare gas in the plasma state to the light emitting unit installed on the wall of the cell to display visible light required for the image. In addition to the visible rays, harmful electromagnetic waves such as near-infrared rays, harmful electromagnetic waves to human body, and orange colored rays (hereinafter referred to as 'neon rays') around the wavelength of 595 nm, which reduce the color purity of red light due to neon gas, are also accompanied. Since it is emitted, beneficial visible light is transmitted, but harmful electromagnetic waves including near infrared rays need to be blocked, and an optical filter therefor is required (see Patent Document 1).

In particular, since near-infrared is used as a beam when remotely operating electrical devices, devices that emit near-infrared light may malfunction the electrical devices installed in the surroundings, and the device that emits such near-infrared rays, especially the front of the PDP. It is necessary to provide an optical filter having a function of blocking near infrared rays.

Near-infrared absorbing films used in optical filters are used to block near-infrared rays, which include a compound that absorbs near-infrared rays on the surface of a transparent support film, that is, a transparent base film or an anti-reflective film, and a film that blocks harmful electromagnetic waves (hereinafter, It is produced by forming a cured film layer of a polymer resin (hereinafter referred to as "binder resin") having a binder ability on the surface of a transparent functional film, such as "electromagnetic wave blocking film". There are several kinds of near-infrared absorbing compounds used herein, but usually, dimonium salt compounds having a relatively broad absorption wavelength band of near-infrared are used alone or in combination with one or more other near-infrared absorbing compounds as a base. However, many compounds having near-infrared absorptivity have insufficient heat stability and heat-and-moisture resistance, and the same can be said for dimonium salt compounds, and a dimonium salt compound having improved heat resistance and moisture resistance has been desired.

As a stabilization technique, the dimonium salt is contained in the method of making a dimonium salt compound into a cured film layer in the state below a fixed ratio, and binder resin which has a comparatively high glass transition temperature (henceforth "Tg"). Although the method of containing a compound and the like are disclosed, it is necessary to adjust the amount of the residual solvent, and it is preferable to obtain a cured film layer having good heat stability and heat-and-moisture stability in coating and drying treatment by a general method. (See Patent Document 2)

[Patent Document 1] Japanese Patent Application Publication No. 2000-98131

[Patent Document 2] Japanese Patent No. 3341741

[Patent Document 3] Japanese Patent Publication No. 43-25335

Problems to be Solved by the Invention

A dimonium salt compound having a relatively wide absorption wavelength band of near-infrared light, which has good heat stability and heat / moisture heat stability, and has a wide Tg width and a relatively low Tg of a binder resin that can be used, as well as a cured film layer according to a general manufacturing method. In the coating resin layer using resin, it is a problem to find the compound which is excellent in heat resistance and moisture-heat resistance, and to develop the near-infrared absorption film which hold | maintained this, and the optical filter for PDP using the same.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM The present inventors conducted research, and discovered that the near-infrared absorption film which has a layer containing the dimonium salt compound which has a specific structure, and the optical filter using the same can solve the said subject, and completed this invention. It came to the following.

 That is, the present invention,

(1) a near-infrared absorbing film comprising a dimonium salt compound represented by the following formula (1) as a near-infrared absorbing dye in a layer formed on a transparent support film,

Where

R ₁ to R ₈ each independently represent an aliphatic hydrocarbon residue which may have a hydrogen atom or a substituent,

X ^- and Y ^- represent monovalent anions which are not identical to each other.

(2) X ^- valent antimony hexafluoride, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide of formula (1), or pentafluorophenylbis (trifluoro) An anion selected from the anion of methanesulfonyl) methide, and Y ⁻ is antimony hexafluoride, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, or pentafluoro The near-infrared absorption film as described in said (1) which is an anion chosen from the anion of the phenylbis (trifluoromethanesulfonyl) methide,

(3) R ₁ to (1) The near-infrared absorbing film as described in said (2) whose at least one of R <_8> is a branched alkyl group,

(4) R ₁ to (1) The near-infrared absorption film as described in said (3) whose all R <_8> is a branched alkyl group,

(5) The near-infrared absorbing film as described in said (4) whose all of a branched alkyl group are C3-C6 alkyl which the terminal branched,

(6) The near-infrared absorbing film in any one of said (1)-(5) containing the compound which has an absorption maximum in wavelength 550-620 nm,

(7) the near-infrared absorbing film according to any one of the above (1) to (6), which includes any or both of a phthalocyanine-based compound and a dithiol metal complex-based compound as a near infrared absorbing dye,

(8) The near-infrared absorbing film in any one of said (1)-(7) whose transparent support film is a film which has an anti-reflective function or the electromagnetic wave shielding function,

(9) Optical filter for plasma display panel which has the near-infrared absorption film in any one of said (1)-(8), the film which has an electromagnetic wave blocking function, or the film which has an anti-reflective function,

It is about.

Effects of the Invention

The near-infrared absorptive dimonium salt compound used for this invention can be synthesize | combined at reasonable and low cost, and since solvent solubility is good, it is easy to handle and the near-infrared absorption film which has the layer containing the said dimonium salt compound is Good absorption of near-infrared rays in the wavelength range of 800 to 1100 nm, and also in the coating resin layer using a binder resin having a relatively low Tg, shows excellent heat stability and moisture-heat stability, deterioration of near-infrared absorptivity, layer discoloration and surface quality deterioration. The optical filter for PDP which combined this near-infrared absorbing film and another functional film shows the outstanding performance, and can fully respond to the said subject.

Best Mode for Carrying Out the Invention

The near-infrared absorbing film of this invention contains the dimonium salt compound represented by the said General formula (1) in the binder resin layer provided on a transparent support film, As a near-infrared absorption film, all physical properties are good, 800-1100. Good absorption of near infrared rays in the wavelength range of nm.

The dimonium salt compound used for this invention can be synthesize | combined, for example by oxidizing the aluminum salt compound represented by following General formula (2) synthesize | combined according to the method of patent document 3 in presence of a source of a Y anion. .

That is, the dimonium salt compound used by this invention is a water-soluble polar solvent, such as dimethylformamide (DMF), dimethyl imidazolidinone (DMI), and N-methylpyrrolidone (NMP) in an organic solvent, Preferably Among them, 1 equivalent of an oxidizing agent (for example, silver salt) corresponding to the Y anion is added at 0 to 100 ° C, preferably 5 to 70 ° C, followed by oxidation by adding an aluminum salt synthesized according to the method of Patent Document 3. You can get it. The same dimonium salt compound can be obtained also by adding the aluminum salt synthesize | combined by the said method to the mixture of oxidizing agents, such as silver nitrate, and the acid or salt corresponding to a Y anion.

R ₁ to the formula (2) R ₈ each independently represents an aliphatic hydrocarbon residue which may have a hydrogen atom or a substituent. An "aliphatic hydrocarbon residue" means a group excluding one hydrogen atom from saturated, unsaturated, straight, branched and cyclic aliphatic hydrocarbons. The carbon number is 1 to 36, preferably 1 to 20 carbon atoms, and particularly preferably 1 to 6 carbon atoms.

Specific examples of the saturated aliphatic hydrocarbon residue or the unsaturated aliphatic hydrocarbon residue having no substituent include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso- Pentyl, tert-pentyl, n-hexyl, octyl, decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, vinyl, allyl, propenyl, butenyl, hexenyl, hexadienyl, isopropenyl, isohexenyl , Cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, pentynyl, hexynyl, isohexynyl or cyclohexynyl and the like. Among them, preferred are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, tert-pentyl, vinyl, allyl C1 to C6 straight, branched and cyclic saturated aliphatic hydrocarbon residues such as propenyl, pentynyl or n-hexyl, or unsaturated aliphatic hydrocarbon residues of C1 to C6.

In the present invention, R ₁ to At least one of R ₈ is a straight or branched C ₁ to C 6 alkyl group, or R ₁ to It is preferable that at least one of R <_8> is a linear C1-C4 alkyl group, and R <_1> - At least one of R ₈ is a branched alkyl group, in particular from R ₁ to More preferably, R ₈ is an alkyl group all branched at the terminal. R ₁ to As the R ₈ is an alkyl group which is branched at both ends is, there are iso- propyl, and iso- butyl, iso- amyl, iso- hexyl, R ₁ to It is particularly preferable that all of R ₈ are iso-butyl.

As an example of a substituent in the aliphatic hydrocarbon residue which may have a substituent, For example, a halogen atom (for example, F, Cl, BR), a hydroxyl group, an alkoxy group (for example, methoxy, ethoxy, isobutoxy etc.), an alkoxyalkoxy group (E.g., methoxyethoxy, etc.), aryl groups (e.g., phenyl, naphthyl, etc., these aryl groups may have substituents again), aryloxy groups (e.g., phenoxy, etc.), acyloxy groups (e.g., acetyl Oxy, butyryloxy, hexylyloxy, benzoyloxy and the like, these aryloxy groups may again have substituents, amino groups, alkyl-substituted amino groups (e.g. methylamino, dimethylamino, etc.), cyano groups, nitro groups, Carboxyl groups, carboxyamide groups, alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), acyl groups, amide groups (e.g., acetamide, etc.), sulfonamide groups (e.g., methanesulfonamides, etc.) and sulfonic acids have. Among these substituents, a halogen atom, cyano group, nitro group, hydroxy group, carboxyl group, carboxyamide group, alkoxycarbonyl group, acyl group, aryl group or alkoxy group is preferable.

Each of these groups may exist independently. For example, each combination of R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R _6, and R ₇ and R ₈ may be a combination of different groups. That is, the unsubstituted linear alkyl group and cyano substituted alkyl group are substituted by one amino group, the unsubstituted branched alkyl group and cyano substituted alkyl group are substituted, and the unsubstituted linear alkyl group and unsubstituted branched alkyl group are substituted. It is also good.

Specific examples of the aliphatic hydrocarbon residue having a substituent include cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 2-cyanopropyl, 4-cyanobutyl, 3-cyanobutyl, 2-cyanobutyl Cyano substituted (C1-C6) alkyl groups such as 5-cyanopentyl, 4-cyanopentyl, 3-cyanopentyl, 2-cyanopentyl, or 3,4-dicyanobutyl, methoxyethyl, ethoxyethyl , Alkoxy substituted (C1-C6) alkyl groups such as 3-methoxypropyl, 3-ethoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 5-ethoxypentyl or 5-methoxypentyl, trifluoro Methyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, heptafluoropropyl, perfluorobutyl, perfluorobutylethyl, perfluorohexyl, perfluorohexylethyl, purple Fluorine (C1-C8) alkyl groups, such as urooctyl and perfluorooctylethyl, etc. are also exist.

In said Formula (1), X <^-> and Y <^-> are monovalent anions, respectively, but X and Y are not the same. These anions include, for example, anions of inorganic and organic acids, and anions of organic metals.

As an anion of an organic acid and an anion of an organic metal, For example, anion of organic carboxylic acids, such as acetic acid, lactic acid, trifluoroacetic acid, propionic acid, benzoic acid, oxalic acid, succinic acid or stearic acid, methanesulfonic acid, toluenesulfonic acid, naphthalene monosulfonic acid, Anions of organic sulfonic acids such as naphthalenedisulfonic acid, chlorobenzenesulfonic acid, nitrobenzenesulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, ethanesulfonic acid or trifluoromethanesulfonic acid, tetraphenylboric acid, butyltriphenylboric acid, tetrakis (pentafluoro Anions of organic boric acid such as phenyl) boric acid, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, bis (fluorosulfonyl) imide acid, pentafluorophenylbis ( Negative ions of fluorine-containing organic acids such as trifluoromethanesulfonyl) methide, Phosphorus tetrakis (pentafluorophenyl) boric acid, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide or pentafluorophenylbis (trifluoromethanesulfonyl) methide Each anion corresponds to

As inorganic anions, for example, anions of halogens such as fluorine, chlorine, bromine and iodine, thiocyanic acid, hexafluoroantimonic acid, perchloric acid, periodic acid, nitric acid, tetrafluoroboric acid, hexafluorophosphoric acid and molybdic acid , Anions of tungstic acid, titanic acid, vanadic acid, phosphoric acid, boric acid, tetrafluorotantalic acid or tetrafluoroniobic acid, and the like are preferred anions of strong acid, perchloric acid, tetrafluoroboric acid and hexafluorophosphoric acid. And anions corresponding to hexafluoroantimonic acid.

Of these anions, it corresponds to antimony hexafluoride, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide or pentafluorophenylbis (trifluoromethanesulfonyl) methide Particularly preferred are each anion.

Next, the specific example of the dimonium salt compound used by this invention represented by the said General formula (1) is shown in Table 1. In the table, R ₁ to With respect to R ₈ , i- represents a branched chain like "iso-" and Cy- represents a state of a cyclic group like "cyclo-".

X ^- and Y ^- represent an anion that is a counter ion, the bis (trifluoromethanesulfonyl) imide ion is TFSI, the bis (fluorosulfonyl) imide ion is FSI, tris (trifluoromethanesulfonyl) The methion ion is abbreviated as TFSM, the pentafluorophenylbis (trifluoromethanesulfonyl) methion ion as Z, and the tetrakis (pentafluorophenyl) boric acid ion as W.

 Table 1 Specific Examples of Dimonium Salt Compounds

Although the dimonium salt compound represented by General formula (1) used by this invention may be used independently, even if it uses together with one or more other near-infrared absorption compounds in consideration of the absorption wavelength range, absorption ratio, or price of desired near-infrared rays, good. Examples of other near-infrared absorbing compounds include dimonium salt compounds, nitroso compounds and metal salts thereof, cyanine compounds, squawa-lithium compounds, thiol nickel complex salt compounds, and phthalocyanine compounds other than the dimonium salt compound represented by the formula (1). A compound, a naphthalocyanine type compound, a triallyl methane type compound, a naphthoquinone type compound, an anthraquinone type compound, etc. are mentioned.

Hereinafter, the method of manufacturing a near-infrared absorbing film by forming the layer containing the dimonium salt compound represented by General formula (1) on a transparent support film is demonstrated. In addition, when using other near-infrared absorption compound together, the method of mixing and coating in the same coating liquid as the dimonium salt compound represented by General formula (1) is reasonable, but as a separate layer by a well-known method to the same transparent support film, Can be coated.

Although the kind and thickness are not specifically limited if the transparent support film used for this invention is high transparency, there is no damage, etc., and can endure use as an optical film, 10-500 micrometers of thickness are preferable because workability is favorable. It can be said that the range. Specifically, there are polymer resin films such as polyester (hereinafter referred to as 'PET'), polycarbonate, triacetate, norbornene, acryl, cellulose, polyolefin or urethane, and absorb ultraviolet rays from the outside. In order to stabilize the function of the inner member, a transparent support film containing an ultraviolet absorber may be used. The surface of the film may be coated with a corona discharge treatment, a plasma treatment, a glow discharge treatment, a roughening treatment, a chemical treatment and an anchor coat agent and a primer in order to improve the adhesion with the coating film. Further, the transparent support film is more preferably a film having a single or a plurality of functions such as antireflection, anti-glare, antireflection, antistatic, antifouling, neon light absorbing, electromagnetic wave blocking, or color tone adjustment. It is logical and becomes the optical filter of the outstanding form.

Next, although the example of the transparent support film which maintains the above-mentioned functionality is demonstrated below, it is not limited to these.

The anti-reflective film is hard between the transparent support film and the low refractive index layer which coated the low refractive index agent with binder resin and other additives on the surface of the transparent support film such as PET and suppressed light reflection from the outside. It is a film which provided the coating layer and the high refractive index layer, and was adjusted so that the reflection light by each layer may be removed, and the visibility was improved, and the anti-glare anti-reflective film is the high refractive index layer of an anti-reflection film In the film which contained fine particles in the and other layers and diffusely reflected the light from the outside to improve visibility, the arc top series (manufactured by Asahi Glass Co., Ltd.), KAYACOAT ARS series (manufactured by Nippon Kayaku), KAYACOAT AGRS series (product made in Nippon Kayaku), rear look As a series (made by Nippon Yushi) etc., the anti-reflective film of a non-adhesion process can be used as a transparent support film, These can be purchased commercially.

Next, the method to hold the dimonium salt compound represented by General formula (1) as a cured film layer using a binder resin on a transparent support film is demonstrated. The dimonium salt compound represented by the general formula (1) includes a binder resin, a neon light absorbing dye, a color adjusting dye, a leveling agent, an antistatic agent, an antioxidant, a dispersant, a flame retardant, a lubricant, a plasticizer, as necessary. The method of dissolving and / or dispersing in a solvent with a ultraviolet absorber, other additives, etc. to make a coating liquid, coating with a coating machine, and then drying is used. In the case of using a binder resin such as thermosetting or active energy ray curability, a curing step is required after drying, but since the heat of curing and the active energy ray may cause deterioration of the dye and increase the process, special circumstances may arise. It is desired to use a thermoplastic binder resin unless otherwise.

When a dimonium salt compound is contained in a binder resin layer, the dimonium salt compound (for example, brand name; IRG-022 made by Nippon Kayaku) and many diimos which use only the antimony hexafluoride ion most commonly used as an anion In the nium salt compound, as described in Patent Literature 2, the use of a binder resin having a Tg of less than 85 ° C and a relatively low binder is poor, but in the dimonium salt compound represented by the general formula (1), the Tg is less than 85 ° C. Even if it is drying by extremely normal drying conditions which do not manage the residual solvent amount in a binder resin layer as disclosed in patent document 2, it can use without a problem.

As binder resin, if it is easy to coat, adhesiveness with the transparent support film of a binder resin layer is good, visible ray permeability is good, and there is no problem in surface quality, etc., it will not specifically limit but it is polyester resin and acrylic resin from a viewpoint of ease of handling. And a thermoplastic resin such as polyamide resin, polyurethane resin, polyolefin resin or polycarbonate resin. As the thermoplastic resin, for example, Acridict series (manufactured by Dainippon Ingiga Chemical Co., Ltd.), Harth Hybrid series (manufactured by Nihon Shokubai), etc. can be used, and these can be purchased commercially. After coating and winding onto a roll, it is necessary to select a material that has a glass transition temperature and other properties that do not cause problems such as blocking during storage and does not adversely affect stability.

It is preferable that the near-infrared absorbing film of this invention is designed so that the transmittance | permeability of the near-infrared wavelength of wavelength 800-1100 nm may be 20% or less, and the dimonium salt compound represented by General formula (1) may use the quantity according to it, and a binder What is necessary is just to contain in binder resin so that it may become about 0.1 to 10 weight% with respect to resin. As needed, you may use together 1 or more types of other near-infrared absorbing compounds, and these may be contained in binder resin so that it may become about 0.01 to 5 weight% with respect to binder resin.

Examples of the solvent for the coating solution include alcohols such as methanol, ethanol, isopropanol, diacetone alcohol, ethyl cellosolve or methyl cellosolve, ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone, Amides such as N, N-dimethylformamide and N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane and ethylene glycol monomethyl ether, methyl acetate and acetic acid Esters such as ethyl and butyl acetate, aliphatic hydrocarbons such as chloroform, methylene chloride, dichloroethylene or trichloroethylene, aromatics such as benzene, toluene, xylene, monochlorbenzene or dichlorbenzene, or n-hexane, n Aliphatic hydrocarbons such as heptane, fluoro solvents such as tetrafluoropropyl alcohol, pentafluoropropyl alcohol, and the like; The solubility of a composition is good, there is no problem of coating, drying, etc., It is necessary to consider a safety enough, and to select a solvent.

Coating of the coating liquid is finished by well-known coating methods, such as the flow coating method, the spray method, the bar coat method, the gravure coating method, the roll coating method, the blade coating method, the air knife coating method, the lip coating method, or the die coating method. The coating layer is fixed by coating the film so that the film thickness is usually 0.1 to 30 m, preferably 1 to 10 m, and then drying.

In the method of blocking electromagnetic waves, a mesh form in which a micro fine wire such as copper is held on a transparent support film in a checkered geometric shape, and a thin film in which an ultrathin metal film is kept in a transparent support film in a range having light transmittance There is a form, and since the thin film form generally does not reflect and transmit near infrared rays, it does not particularly require a near infrared absorbing film. In the present invention, an electromagnetic wave blocking film in the form of a mesh can be used as the transparent support film.

In the PDP, since neon light having a wavelength of 550 to 620 nm derived from neon gas or the like generated at the time of applying voltage decreases the color purity of red light, the neon light absorbing compound needs to be cut to some extent in the front of the display. Neon light absorbing filter in which the transparent support film is kept is usually used, but there is a method of obtaining a coating layer capable of simultaneously absorbing near infrared light and neon light by containing a compound having neon light absorbing ability in a coating layer having near infrared absorbing ability. . In addition, examples of the neon light absorbing compound include compounds such as tetraazaporphyrin-based, cyanine-based, squarylium-based, azomethine-based, xanthene-based, oxonol-based or azo-based compounds, but stability in the case of containing them in the adhesive layer. It is necessary to be careful about the back. For example, the tetraaza porphyrin compound is relatively stable, but other compounds can be used as long as stabilization can be achieved.

The pressure-sensitive adhesive which can be used in the present invention is not particularly limited as long as it forms a transparent layer on the surface of the transparent support film and does not impair the function as an optical filter. However, acrylic, polyester, polyamide, polyurethane, and polyolefin-based resins are not particularly limited. , An acrylic resin pressure sensitive adhesive is preferable in that there are adhesives such as polycarbonate-based, rubber-based or silicone-based resins, and excellent in transparency, adhesiveness, heat resistance, and the like. The acrylic resin pressure sensitive adhesive is obtained by copolymerizing an acrylic acid alkyl ester having no functional group as a main component and other monomer components other than the acrylic acid alkyl ester and the acrylic acid alkyl ester having a functional group. The copolymerization ratio of the monomer component other than the acrylic acid alkyl ester and the acrylic acid alkyl ester having the functional group is 0.1 to 20 parts by weight, more preferably 1 to 10 weight per 100 parts by weight of the acrylic acid alkyl ester component having no functional group. It is wealth.

Examples of the acrylic acid alkyl ester having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and (meth) acrylic acid Alkyl alkyl ester or methacryl having 1 to 12 carbon atoms of an alkyl group, such as heptyl, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylate, undecyl (meth) acrylate or dodecyl (meth) acrylate Although acid alkyl ester exists, these may use two or more types together as needed.

As monomers other than the acrylic acid type alkyl ester or acrylic acid type alkyl ester which have a functional group, what functions as a crosslinking point with a crosslinking agent mentioned later, etc. are used, Although it does not specifically limit about the kind, 2-hydroxyl ethyl (meth) acrylate , Amino group-containing (meth) acrylic acid monomers such as hydroxy group-containing (meth) acrylic acid ester monomers such as hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl acrylate, N-tert-butylaminoethyl acrylate, Or acrylic acid, maleic acid, etc. are mentioned, These may use two or more types together as needed.

It is preferable to use an adhesive in the composition which can bridge | crosslink the said acrylic acid type resin etc. by mix | blending a crosslinking agent. As a crosslinking agent, it is used suitably according to the kind of said monomer, For example, aliphatic diisocyanate, such as hexamethylene diisocyanate and the trimethylolpropane adduct of hexamethylene diisocyanate, tolylene diisocyanate, or the trimethylolpropane adduct of tolylene diisocyanate, etc. Polyisocyanate compounds such as aromatic diisocyanates, melamine compounds such as trimethylolmelamine, diamine compounds such as hexamethylenediamine or triethyldiamine, epoxy resin compounds such as bisphenol A and epichlorohydrin reaction products, urea resin compounds, aluminum chloride And metal salts such as ferric chloride or aluminum sulfate are used, and the compounding amount thereof is usually 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the acrylic resin.

The coating of the pressure-sensitive adhesive is an antioxidant when the resin, which is a main component of the pressure-sensitive adhesive, is discolored by contact with a polymerization initiator, a crosslinking agent, a UV absorber, a color tone adjusting dye, and other necessary additives, for example, a metal used for the electromagnetic wave blocking mesh. And dissolving or dispersing it in a solvent such as methyl ethyl ketone (MEK) together with a rust preventive agent to form a pressure-sensitive adhesive liquid, so that the layer thickness after drying is 5 to 100 m, preferably 10 to 50 m Coating. The coating method is not particularly limited, and after coating with a bar coater, a reverse coater, a comma coater, a gravure coater, or the like, drying and adhering the adhesive layer and a pressure-sensitive adhesive liquid on a release film, a bar coater, a reverse coater, a comma After apply | coating with a coater or a gravure coater etc., and drying, the method of transferring an adhesion layer on a transparent support film, etc. are mentioned.

The acrylic resin pressure sensitive adhesive is preferable because it is excellent in adhesive force and cohesive force and has no unsaturated bond in the polymer, and thus has high stability against light and oxygen, and also has a high degree of freedom in selecting the type and molecular weight of the monomer. In order to maintain the adhesiveness to a transparent support film, as for the thing with high molecular weight (polymerization degree), ie, the weight average molecular weight (Mw) of a main polymer, about 600,000-2 million are preferable, More preferably, about 800,000-1,800,000 to be.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. In addition, in an Example, a part means a weight part.

Melting | fusing point of the compound synthesize | combined in the Example was measured using the following apparatus and conditions.

 Measuring instrument: DSC 220 (manufactured by Seiko Instruments Inc.)

 Measurement condition: temperature increase rate 10 ℃ / min

Synthesis Example 1

According to the method of patent document 3, 6 parts of N, N, N ', N'- tetrakis {p-di (iso-butyl) aminophenyl} -p-phenylenediamine are added to 30 parts of DMF, and it heats at 60 degreeC Thereafter, 2.52 parts of a silver salt of bis (trifluoromethanesulfonyl) imide dissolved in 35 parts of DMF was added and stirred for 30 minutes. After the insoluble fraction was separated by filtration, water was added to the reaction solution, and the precipitated crystals were obtained by filtration, followed by washing with water and drying, followed by N, N, N ', N'-tetrakis {p-di (iso-butyl). 6 parts of bis (trifluoromethanesulfonyl) imide salts of aminophenyl} -p-phenylene aluminum were obtained. Maximum absorption wavelength: 420 nm, 946 nm (acetone).

In 30 parts of DMF, 0.29 parts of nitric acid and 0.91 part of cesium tris (trifluoromethanesulfonyl) methide were added and stirred. 2 parts of bis (trifluoromethanesulfonyl) imide salts of N, N, N ', N'-tetrakis {p-di (iso-butyl) aminophenyl} -p-phenylenealuminum were added and the mixture was stirred at 25 ° C. Stir for 30 minutes. After the insoluble fraction was separated by filtration, water was added to the reaction solution, and the precipitated crystals were obtained by filtration, washed successively with methanol and water, and dried to obtain 1.8 parts of compound No. 2 in Table 1. Melting point: 203-209 degreeC.

In the same manner as in the above synthesis example, other compounds listed in Table 1 can be synthesized by oxidizing a corresponding aluminum salt with an oxidizing agent in the presence of a corresponding anion or anion source.

Example 1

<Production of Near Infrared Absorption Film>

The coating liquid which mixed and melt | dissolved each raw material shown in Table 2 on the opposite surface of the anti-reflective film (brand name, KAYACOAT ARS-D501, Nippon Kayaku Co., Ltd.) so that it may become uniform is coated with a microgravure coater for 10 m / min. It coated by speed, it dried at 130 degreeC, and the near-infrared absorbing film which has an antireflection property of 5 micrometers in thickness of a cured film layer was obtained. Tg of acrylic resin PAN-125 used at this time was 75 degrees C or less.

TABLE 2

material usage Dimonium Salt Compounds of Synthesis Example 1   0.17 parts Near-infrared absorber (brand name CY-40MC (S); product made by Nippon Kayaku)   0.012 parts Near-infrared absorber (brand name IR-12; product made by Nippon Shokubai)   0.035 parts Acrylic resin (brand name PAN-125; product made by Sokengagaku)  16.0 parts Methyl ethyl ketone   6.0 parts

Product name CY-40MC (S); Cyanine compound, trade name IR-12; Phthalocyanine-based compound.

The coating solution obtained by mixing and dissolving each raw material shown in Table 3 below is uniformly coated on a peeling PET film (trade name, MRF-75, manufactured by Mitsubishi Chemical Co., Ltd.) at a coating speed of 0.8 m / min with a comma coater. Then, it dried at 110 degreeC, the adhesive layer of 18 micrometers in thickness was formed, and it bonded with this and the near-infrared absorbing film which has the said anti-reflective property, and obtained the near-infrared absorbing film which absorbs neon light and has an anti-reflective property.

 Table 3

material usage Neon light absorber (brand name TAP-2; product of Yamada Gakuku Kogyo)   0.096 parts Ultraviolet light absorber (brand name Tinubin109; product made by Shiba GIGI)   1.2 parts Acrylic resin (brand name PTR-104; Nippon Kayaku) 120.0 parts Curing agent (brand name M12ATY; product made by Nippon Kayaku)   0.324 parts Hardener (brand name L45EY; product made by Nippon Kayaku)   0.444 parts Additive (brand name C-50; product of Sokengaku)   0.142 parts Methyl ethyl ketone  84.0 parts

(Trade name) TAP-2; Tetraazaporphyrin compound, trade name TINUBIN 109; Benzotriazole compound, trade name M12 ATY; Metal chelate compounds, trade name L45EY; Isocyanate compounds, trade name C-50; Silane coupling agent.

<Manufacture of optical filter for PDP>

Peel off the protective film of the electromagnetic wave shielding film (trade name, ES-1534U (HCD-42-02) A, manufactured by Hitachi Chemical Co., Ltd.) having an adhesive layer, and attach the near-infrared absorbing film through the adhesive layer on the optical film for PDP. A filter was obtained. This filter may be directly bonded to the front surface of the PDP module, may be bonded to a transparent plate such as a glass plate, and may be installed in front of the module, thereby sufficiently exhibiting the performance required as a PDP filter.

Example 2

<Production of Near Infrared Absorption Film>

A near-infrared absorptive film which has anti-reflective properties and absorbs neon light was obtained in the same manner as in Example 1 except that acrylic resin IR-G205 (manufactured by Nihon Shokubai) was used instead of PAN-125 of Example 1. Tg of acrylic resin IR-G205 used at this time was 85 degreeC or more.

<Manufacture of optical filter for PDP>

Peel off the protective film of the electromagnetic wave shielding film (trade name, ES-1534U (HCD-42-02) A, manufactured by Hitachi Chemical Co., Ltd.) having an adhesive layer, and attach the near-infrared absorbing film through the adhesive layer on the optical film for PDP. A filter was obtained. The filter may be directly bonded to the front surface of the PDP module through the adhesive layer of the electromagnetic wave shielding film, or may be bonded to a transparent plate such as a glass plate to be installed in front of the module, thereby sufficiently exhibiting the required performance as a PDP filter.

Comparative Example 1

<Production of Near Infrared Absorption Film>

Near-infrared absorption which has anti-reflective properties and absorbs neon light in the same manner as in Example 1 except that the dimonium salt compound IRG-022 (manufactured by Nippon Kayaku) is used instead of the dimonium salt compound of Synthesis Example 1 of Example 1. A film was obtained.

<Test method>

The heat resistance test which keeps the test piece of the film of each Example and the film of each comparative example for 500 hours in the 80 degreeC thermostat, and the heat-and-moisture resistance test which hold | maintain for 500 hours in the 60 degreeC-90 degreeC constant temperature and humidity chamber were performed.

The measurement was performed using a spectrophotometer (trade name, UV-3150, manufactured by Shimadzu Seisakusho), and the luminous transmittance (Y /%), chromaticity coordinates (x, y), and transmittance at wavelength 950 nm of near infrared ray before and after the test. Was measured.

The luminous transmittance (Y /%) and chromaticity coordinates (x, y) were calculated according to the display method of the color by the XYZ table color system of JIS Z 8701.

 The results of the durability test are shown in Table 4 (dry heat test) and Table 5 (humid heat test).

 Table 4 Change in Durability Test (Dry Heat Test)

Retention time Example 1 Example 2 Comparative Example 1  Visual transmission Y (%) 0 hours 63.60 64.00 62.94 500 hours 63.86 63.64 63.94 car 0.26 0.36 1.00  Chromaticity coordinates x 0 hours 0.302 0.301 0.303 500 hours 0.304 0.301 0.309 car 0.002 0.000 0.006  Chromaticity coordinate y 0 hours 0.326 0.324 0.329 500 hours 0.330 0.325 0.341 car 0.004 0.001 0.012  950 nm transmittance (%) 0 hours 3.79 3.03 1.97 500 hours 4.52 3.33 3.94 car 0.73 0.30 1.97

 [Table 5] Change in durability test (wet heat test)

Retention time Example 1 Example 2 Comparative Example 1  Visual transmission Y (%) 0 hours 63.76 64.93 63.37 500 hours 64.29 64.91 64.05 car 0.53 0.02 0.68  Chromaticity coordinates x 0 hours 0.301 0.301 0.302 500 hours 0.304 0.302 0.308 car 0.003 0.001 0.006  Chromaticity coordinate y 0 hours 0.326 0.324 0.328 500 hours 0.330 0.325 0.339 car 0.004 0.001 0.011  950 nm transmittance (%) 0 hours 3.52 3.92 2.22 500 hours 4.73 4.14 3.61 car 1.21 0.22 1.39

<Consideration of results>

From the above result, in the film using the dimonium salt compound represented by General formula (1) of Example 1 and 2, the favorable result was obtained in the durability test. Considering the Tg of the binder resin, it can be seen that it can be applied to the binder resin of 75 ℃ or less and low Tg, it was confirmed that it can be adapted to a wide range of binder resin.

Since the dimonium salt compound which has near-infrared absorptivity used for this invention can be synthesize | combined at reasonable and low cost, and since solvent solubility is good, it is easy to handle and the near-infrared absorption film which has the layer containing the said dimonium salt compound is 800 Near-infrared rays in the wavelength range of ˜1100 nm are well absorbed, and the coating resin layer using a binder resin having a relatively low Tg exhibits excellent heat stability and moisture-heat stability, and also decreases near-infrared absorptivity, layer discoloration, and surface degradation. Since it does not exist, this near-infrared absorption film and another functional film can be compounded and the outstanding optical filter for PDP can be provided.

Claims (9)

A near-infrared absorbing film containing a dimonium salt compound represented by the following general formula (1) as a near-infrared absorbing dye in a layer formed on a transparent support film:

Where R ₁ to R ₈ each independently represent an aliphatic hydrocarbon residue which may have a hydrogen atom or a substituent, X ^- and Y ^- represent monovalent anions which are not identical to each other. A compound according to claim 1, wherein X ^- in formula (1) is antihexanoic acid, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, or pentafluorophenylbis ( An anion selected from the anion of trifluoromethanesulfonyl) methide, wherein Y ⁻ is antimony hexafluoride, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methide, or A near infrared absorbing film which is an anion selected from anions of pentafluorophenylbis (trifluoromethanesulfonyl) methide. The compound according to claim 2, wherein R ₁ to The near-infrared absorbing film whose at least one of R <_8> is a branched alkyl group. 4. A compound according to claim 3, wherein R ₁ to A near-infrared absorbing film in which all of R ₈ are branched alkyl groups. The near-infrared absorbing film of Claim 4 whose all branched alkyl groups are C3-C6 alkyl groups which the terminal branched. The near-infrared absorbing film of any one of Claims 1-5 containing the compound which has an absorption maximum in wavelength 550-620 nm. The near-infrared absorbing film of any one of Claims 1-6 which contains either or both of a phthalocyanine type compound and a dithiol metal complex system compound as a near-infrared absorbing dye. The near-infrared absorbing film in any one of Claims 1-7 whose transparent support film is a film which has an anti-reflective function or the electromagnetic wave shielding function. An optical filter for plasma display panel having a near-infrared absorbing film according to any one of claims 1 to 8 and a film having an electromagnetic wave blocking function or a film having an anti-reflective function.