JPH1177909A - Transparent laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent laminate having excellent near infrared ray cut-off performance, electromagnetic wave shielding performance, flaw preventive performance, ray antireflection performance and transparency. SOLUTION: The transparent laminate comprises a near infrared ray cut-off layer having 10% or less of near infrared ray transmittance of 850 to 1100 nm of wavelength band, an electromagnetic wave shielding layer, a flaw preventive layer and a ray antireflection layer formed on a transparent resin base plate. In this case, the infrared ray cut-off layer contains at least one type of near infrared ray absorbent selected from a group consisting of imonium compound, diimonium compound and aluminum salt compound. And, visible light ray transmittance of 400 to 700 nm of wavelength band of the transparent laminate is 50% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a transparent laminate. More specifically, the present invention relates to a transparent laminate that can be suitably used as a filter for shielding near infrared rays.

[0002]

2. Description of the Related Art Regarding filters of an image display device,
Various proposals have been made. For example, JP-A-2-790
No. 83 discloses a hard coat layer having an antistatic function formed on at least one surface of a light-transmitting plastic sheet, an antireflection film formed on at least one surface of the light-transmitting plastic sheet, and an antistatic function. There is disclosed a translucent plastic filter which is grounded from the surface having a. In Japanese Patent Publication No. 7-19551, a hard coat layer is provided on both surfaces of a plastic transparent substrate, a conductive layer is provided on one surface of the hard coat layer, and an inorganic silica layer is further provided on the conductive layer. Further, an optical filter in which an antireflection layer is provided on a hard coat layer on the other side is disclosed.

However, these documents do not mention the near-infrared cut-off performance at all. For example, when these filters are used in a display device that emits near-infrared rays such as a plasma display panel, the near-infrared ray absorbing performance is not considered. Is not enough. On the other hand, various proposals have also been made regarding a near infrared absorbing transparent resin. For example,
JP-A-6-240146 describes a composition in which a phthalocyanine compound is blended with a transparent resin such as polycarbonate and (meth) acrylic resin.

[0004] JP-A-6-256541 discloses a molded film comprising a composition in which an anthraquinone compound is blended with a transparent resin such as a polycarbonate resin or a polyethylene terephthalate resin. Further, JP-A-7-179656 describes a composition in which lead sulfide and a thiourea derivative are blended with a transparent resin such as a polycarbonate resin or polystyrene. However, the compositions described therein do not satisfy the near-infrared absorbing ability, electromagnetic wave shielding ability, anti-scratching ability, and anti-reflection ability required for a filter for a plasma display panel.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a transparent laminate which is excellent in near-infrared ray cutting performance, and excellent in electromagnetic wave shielding performance, scratch prevention performance, antireflection performance and transparency. .

[0006]

The gist of the present invention is to provide a near-infrared cut layer having a near-infrared transmittance of 10% or less in a wavelength range of 850 to 1100 nm, an electromagnetic wave shielding layer, and a scratch prevention layer on a transparent resin substrate. And a transparent laminate on which a light reflection preventing layer is formed, wherein the near-infrared cut layer is at least one kind of near-infrared absorber selected from the group consisting of an immonium-based compound, a diimonium-based compound, and an aminium salt-based compound Containing, the wavelength region of the transparent laminate 400 ~
A transparent laminate having a visible light transmittance of 700 nm of 50% or more.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (1) Transparent Resin Substrate The transparent resin that is the material of the transparent resin substrate constituting the transparent laminate of the present invention is not particularly limited as long as it is substantially transparent and does not have large absorption and scattering. However, specific examples thereof include polyester resin, polycarbonate resin, poly (meth) acrylate resin, cyclic olefin resin, polystyrene, polyvinyl chloride, polyvinyl acetate and the like.

(A) Polyester Resin The polyester resin is produced by a polycondensation reaction between a dicarboxylic acid component and a glycol component. Examples of the dicarboxylic acid component include terephthalic acid, adipic acid, and maleic acid, and examples of the glycol component include ethylene glycol, propylene glycol, and 1,4-butanediol. Preferred polyester resins are polyethylene terephthalate, polybutylene terephthalate and the like.

(B) Polycarbonate Resin The above polycarbonate resin is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Examples of dihydric phenols include:
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4 -Hydroxy-
3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxy Phenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like. Preferred dihydric phenols include bis (4-
(Hydroxyphenyl) alkanes, particularly those containing bisphenol as a main component. Further, examples of the carbonate precursor include phosgene, diphenyl carbonate and the like.

(C) Poly (meth) acrylate-based resin As the poly (meth) acrylate-based resin,
Examples include a polyacrylate resin and a polymethacrylate resin. A typical polymethacrylate resin is a homopolymer of methyl methacrylate or a copolymer of a polymerizable unsaturated monomer mixture containing 50% or more of methyl methacrylate. Examples of the polymerizable unsaturated monomer copolymerizable with methyl methacrylate include methyl acrylate, ethyl (meth) acrylate (meaning ethyl acrylate or ethyl methacrylate; the same applies hereinafter), butyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid -N, N-diethylaminoethyl, glycidyl (meth) acrylate, tribromophenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate
Acrylate, tripropylene glycol di (meth) acrylate, trimethylol ethane di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like are included.

(D) Cyclic olefin resin As the cyclic olefin resin, cyclobutenes,
Homopolymer by vinylene polymerization of a cyclic olefin selected from monocyclic cycloolefins such as cyclopentenes and cyclohexenes and polycyclic cyclic olefins such as norbornenes and tricyclo-3-decenes, and vinylene polymerization of plural types of cyclic olefins Or copolymers of these cyclic olefins with ethylene.

Examples of the cyclic olefin include monocyclic cycloolefins such as cyclopentenes such as cyclobutene, cyclopentene and 4-methylcyclopentene; cyclohexenes such as cyclohexene, 3-methylcyclohexene and 3-vinylcyclohexene; norbornene; −
Norbornenes such as methyl norbornene, 5-ethylidene-2-norbornene, methylene norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, and tricyclo [4.3.0.1 ^2,5 ] -3- Decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3
- tricyclo-3-decene such as decene, dicyclopentadiene (tricyclo [4.3.0.1 ^{2, 5]} -3,7
-Decadiene or tricyclo [4.3.0.1 ^2,5 ]-
3,8-decadiene), dicyclopentadienes such as 7-methyldicyclopentadiene, and tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5,10-dimethyltetracyclo [4.4.
0.1 ^2,5 . ^Tetracyclo -3-dodecenes such as 1 ^7,10 ] -3-dodecene, pentacyclo [6.5.1.1
^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 10-methylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,
13 ] -4-pentadecene, pentacyclo [4.7.0.
^12.5 . 0 ^8,13 . Pentacyclopentadecenes such as [ ^1,9,12 ] -3-pentadecene, and pentacyclo [6.5.5.1.
^13-6 . 0 ^2,7 . 0 ^9,13] 4,10 penta octadecadienoic, pentacyclo [6.5.1.1 ^3,6. 0 ^2,7 . 0
^9,13] -4,11-penta cyclopentadiene octadecadienoic such as penta decadiene, hexacyclo [6.6.1.1
^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4 it can be mentioned polycyclic olefins such as hexamethylene cycloheptanone decene such as heptadecene.

The transparent resin may contain generally known additives such as antioxidants such as phenols and phosphorus, flame retardants such as halogen and phosphoric acid, heat aging inhibitors, ultraviolet absorbers, lubricants, An antistatic agent or the like can be blended. The transparent resin is formed into a film or a sheet (plate) by a method such as injection molding, T-die molding, calender molding, compression molding, or a method of dissolving in an organic solvent and casting. As a transparent resin substrate. At this time, the surface of the transparent resin substrate may be subjected to a known surface treatment, for example, a corona treatment, a plasma treatment, a flame treatment, a chemical treatment, a coating of a primer layer, or the like. The thickness of the transparent resin substrate varies depending on the purpose, but is preferably in the range of 10 μm to 5 mm.

(2) Near-infrared cut layer The near-infrared cut layer constituting the transparent laminate of the present invention has a near-infrared transmittance of 10% in a wavelength region of 850 to 1100 nm.
It must be: This near-infrared cut layer is formed by mixing a near-infrared absorber into a transparent resin, or by dispersing or dissolving in an organic solvent and adding a binder resin, or by applying a near-infrared absorber as a hard coat agent or an anchor coat. By applying the coating liquid added to the agent, the adhesive, etc. on the layers constituting the transparent laminate,
Can be formed.

In the present invention, an immonium compound, a diimonium compound or an aminium salt compound is used as a near infrared absorbing agent. The immonium-based compound,
Examples of the diimonium-based compound include compounds represented by the following formulas (1) to (4).

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

The aminium salt compound includes, for example, a compound represented by the following formula (5). Specific examples of X in the formula include antimonate hexafluoride, perchlorate, boron fluoride, arsenate hexafluoride, periodate, trifluoroacetate, and chloride. Can be

[0021]

Embedded image

In the present invention, as a near-infrared absorbing agent,
An immonium-based compound, a diimonium-based compound or an aminium salt-based compound is used, but another near-infrared absorbing agent may be used in combination. Examples of such near-infrared absorbers include nitroso compounds and metal complexes thereof, which are organic substances, cyanine compounds, squarylium compounds, thiol nickel complex salt compounds, phthalocyanine compounds, naphthalocyanine compounds, triarylmethane compounds, Naphthoquinone-based compounds, anthraquinone-based compounds, or amino compounds, or inorganic carbon black, antimony oxide, or tin oxide doped with indium oxide, oxides of metals belonging to Group 4, 5, or 6 of the periodic table, or Examples thereof include carbides and borides. In this case, the above compounds can be appropriately combined and used so that the near-infrared transmittance in a wavelength region of 850 to 1100 nm is 10% or less. In particular, a combination of a diimonium-based compound and a phthalocyanine-based compound is preferable from the viewpoint of transparency and near-infrared absorption performance.

Examples of the phthalocyanine-based compound include compounds having a skeleton represented by the following general formula (6). R _{1 to} R ₁₆ in the formula are the same or different atoms or functional groups, and are a hydrogen atom, a fluorine atom, an alkoxy group,
Examples include a phenoxy group, a thioalkyl group, a thiophenyl group, an aminoalkyl group, and an aminophenyl group. Preferably, they are a fluorine atom and an aminophenyl group. Further, M in the formula is copper, zinc, cobalt, nickel,
Examples include iron, vanadyl, titanyl, chloroindium, chloroaluminum, dichlorotin, cobalt carbonyl, iron carbonyl, and the like.

[0024]

Embedded image

The transparent resin used for forming the near-infrared cut layer by blending the above-mentioned near-infrared absorbing agent with the transparent resin may be a resin which is substantially transparent and does not have large absorption and scattering. It does not matter, but there is no particular limitation,
Specifically, the above-mentioned polycarbonate resin, poly (meth) acrylate resin, cyclic olefin resin, polyester resin, polystyrene, polyvinyl chloride, polyvinyl acetate and the like can be mentioned. In the transparent resin, known additives, for example, phenol-based, phosphorus-based antioxidants, halogen agents, phosphoric acid-based flame retardants, heat aging inhibitors, ultraviolet absorbers, lubricants, antistatic agents and the like. Can be blended.

The transparent resin is mixed with the above-mentioned near-infrared ray absorbing agent, and is formed into a film by a method such as injection molding, T-die molding, calendar molding, compression molding, or the like, or by dissolving in an organic solvent and casting. Into a near-infrared cut layer. As its thickness,
10 μm to 1 mm is preferred. The compounding amount of the near-infrared absorber is usually 0.005 parts by weight based on 100 parts by weight of the resin.
To 8 parts by weight, preferably 0.01 to 5 parts by weight. If the amount of the near infrared absorbing agent is too small, the transmittance of visible light is improved, but the near infrared absorbing ability is reduced. On the other hand, if the blending amount is too large, the near-infrared absorbing ability becomes good, but the visible light transmittance decreases.

The near-infrared cut layer is formed by coating or dispersing or dissolving in an organic solvent and adding a binder resin, or by adding a near-infrared absorbing agent to a hard coat agent, an anchor coat agent, an adhesive or the like. It can also be formed by applying a liquid on any of the transparent resin substrate, the electromagnetic wave shielding layer, the anti-scratch layer, and the anti-reflection layer according to the lamination order. As the organic solvent,
Halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent,
Alternatively, a mixed solvent thereof is used. As the binder, an ester resin, an acrylic resin, a melamine resin, a urethane resin, a polycarbonate resin, a polyolefin resin, a polyvinyl resin, or the like can be used.

As the hard coating agent, those containing acrylates such as polyurethane acrylate and epoxy acrylate or polyfunctional acrylates, a photopolymerization initiator and an organic solvent as main components can be used.
The above-mentioned near-infrared absorbing agent is usually used in an amount of 1 to 40 parts by weight, preferably 2-1 to 100 parts by weight of the hard coating agent.
5 parts by weight are added, and this is applied by a coating method such as a dipping method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, and an air knife coating method. After that, the solvent is dried,
The coating liquid is cured by irradiating active energy rays using a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, or the like to form a near-infrared cut layer. The thickness of the near-infrared cut layer at this time is usually 1 to 50 μm, preferably 3 to 20 μm.
μm.

As the above-mentioned anchor coating agent, known anchor coating agents such as isocyanate type, polyurethane type, polyester type, polyethyleneimine type, polybutadiene type and alkyl titanate type can be used. Preferably, it is an isocyanate compound, a polyurethane, a urethane prepolymer, or a mixture and a reaction product thereof, or a mixture of a polyester polyol or a polyether polyol with an isocyanate. Usually, 1 to 50 parts by weight of the above-mentioned near-infrared absorbing agent is added to 100 parts by weight of these anchor coating agents, and this is dipped, flow coated, sprayed, bar coated, gravure coated, roll coated. Then, coating is performed by a coating method such as a blade coating method or an air knife coating method, and then the solvent is dried to form a near-infrared cut layer. The coating amount of the coating liquid at this time, usually, 0.01-5 g / m ² (dry solids), and preferably from 0.1 to 3 g / m ² (dry solids).

(3) Electromagnetic Wave Shielding Layer The electromagnetic wave shielding layer constituting the transparent laminate of the present invention may be any material as long as it can transmit visible light with a metal or a metal oxide. . Preferably, tin oxide, indium oxide-doped tin oxide (hereinafter, referred to as “ITO”), antimony-doped tin oxide (hereinafter, referred to as “ATO”), and silver are used. The metal or metal oxide forming the electromagnetic wave shielding layer is formed by vacuum evaporation, ion plating, sputtering, C
It can be formed on a substrate by a method such as a VD method or a plasma chemical vapor deposition method. Alternatively, it can be formed by coating a metal paste on a substrate.
The thickness of the electromagnetic wave shielding layer varies depending on required physical properties, applications, and the like, but is preferably in the range of 20 to 300 nm from the viewpoint of transparency.

(4) Anti-Scratch Layer The anti-scratch layer constituting the transparent laminate of the present invention comprises an acrylate such as polyurethane acrylate or epoxy acrylate or a polyfunctional acrylate, a photopolymerization initiator,
And a coating agent containing an organic solvent as a main component. Epoxy acrylate is obtained by esterifying an epoxy group of an epoxy resin with acrylic acid and converting a functional group into an acryloyl group. An acrylic acid adduct to a bisphenol A type epoxy resin, an acrylic acid adduct to a novolak type epoxy resin, etc. is there.

Urethane acrylate is obtained by acrylically modifying a urethane prepolymer obtained by reacting a polyol and a diisocyanate with an acrylate having a hydroxyl group. Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexanediol, neopentyl glycol, hexanetriol, trimethylolpropane, polytetramethylene glycol, and a condensation polymer of adipic acid and ethylene glycol. No. Examples of the diisocyanate include tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like. Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like.

The polyfunctional acrylate has three or more acryloyl groups in the molecule, and specifically includes trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, Tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl-modified Dipentaerythritol triacrylate,
Examples thereof include alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and a mixture of two or more of these.

Examples of photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal,
Hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, benzophenone,
2,4,6-trimethylbenzoindiphenylphosphine oxide, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone,
Examples thereof include 2,4-diethylthioxanthone, and two or more of these photopolymerization initiators may be used in combination.

Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, propyl acetate and butyl acetate, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, and n-propyl alcohol. Alcohols such as butyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether And ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, and 2-butoxyethyl acetate.
Also, two or more of these can be used in combination.

In addition to the above components, a colloidal metal oxide or a silica sol using an organic solvent as a dispersion medium can be added to improve abrasion resistance. The anti-scratch layer is formed by applying the coating solution of the above coating agent by a dipping method, a flow coating method, a spray method, a bar coating method, a gravure coating method, a roll coating method, a blade coating method, or an air knife coating method. After the application, the solvent is dried, and the applied coating agent is cross-linked and cured by irradiating with an active energy ray. As the active energy ray, a xenon lamp,
Ultraviolet light emitted from a light source such as 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 usually 20 to 200
An electron beam extracted from a 0 keV electron beam accelerator, α
Rays, β rays, γ rays and the like can be used. The thus formed scratch prevention layer has a thickness of usually 1 to 50 μm, preferably 3 to 20 μm.

(5) Anti-reflection layer The anti-reflection layer constituting the transparent laminate of the present invention has a relatively low refractive index, such as silicon oxide, zirconium oxide, titanium oxide, magnesium fluoride, calcium fluoride, and oxide. It is formed using aluminum or the like, or an antireflection coating agent (for example, manufactured by Asahi Glass Co., Ltd .; trade name “Cytop”). These layers are provided as a single layer or a combination of two or more types to form a multilayer to form an antireflection layer. As a method of forming the antireflection layer, a method of baking after applying a metal alkoxide, a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, a plasma chemical vapor deposition method,
Alternatively, a roll coating method, a dipping method and the like can be mentioned. This antireflection layer is preferably provided on the outermost surface of the transparent laminate. The thickness of the antireflection layer is usually 5
The range is from 0 to 100 nm.

(6) Transparent laminate The transparent laminate of the present invention may be a film or a sheet (plate).
The near-infrared cut layer, the electromagnetic wave shielding layer, the anti-scratch layer, and the anti-light-reflection layer are laminated on a transparent resin substrate having a visible light transmittance of 50% in a wavelength region of 400 to 700 nm. It is necessary to be above. The order of lamination is not particularly limited, but the antireflection layer is preferably provided on the outermost surface. Further, this transparent laminate can be used alone, but for example, the thickness is 1
In the case where the resin does not have a self-supporting property of 0 μm to 1 mm, the thickness of polyester resin, polycarbonate resin, poly (meth) acrylate resin, alicyclic olefin resin, polystyrene, polyvinyl chloride, polyvinyl acetate, etc.
It can also be used as a laminate by attaching it to a transparent resin plate of about 5 mm with an adhesive or the like.

[0039]

EXAMPLES Specific embodiments of the present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.
In the following examples, the near-infrared transmittance was measured using a spectrophotometer (manufactured by BIO-RAD: FTS-60A).
The visible light transmittance was measured using a spectrophotometer (MPS-2000, manufactured by Shimadzu Corporation).

Example 1 Dipentaerythritol hexamethyldimethacrylate (manufactured by Mitsubishi Rayon Co., Ltd .: trade name “Acrypet VH5”) was molded on a 10 mm × 2 mmt sheet-like molded product as a transparent resin substrate. Coating of a mixture of acrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd .; trade name "Kayad DPHA") in a 40% methyl ethyl ketone solution (100 parts by weight) and benzyl dimethyl ketal (0.2 parts by weight) mixed with a hard coat agent coating Apply the solution, heat and dry at 80 ° C for 5 minutes, output 7.5k
Using a high-pressure mercury lamp having an output density of 120 w / cm and using a high-pressure mercury lamp at a position 10 cm below the light source, the film was irradiated with ultraviolet rays at a conveyor speed of 2 m / min and cured by ultraviolet rays to form a scratch-resistant layer. Further, 1 part by weight of a near-infrared absorbing agent (manufactured by Nippon Shokubai Co., Ltd .: trade name "EEX Color 803K"(phthalocyanine); and Nippon Kayaku Co., Ltd .: trade name "IRG"
-022 "(4 parts by weight of diimonium)) with an anchor coating agent (trade name" T-120 "manufactured by Nippon Soda Co., Ltd.).
A coating solution obtained by adding (isocyanate-based)) to 100 parts by weight of a solution obtained by diluting 2% by weight (solid content) with ethyl acetate is coated on the above-mentioned scratch-resistant layer, and cured at 40 ° C. for 1 day. And a near infrared cut layer. The coating amount of the coating liquid was 0.6 g / m ² (dry solid content).

Table 1 shows the near-infrared transmittance of the near-infrared cut layer. On top of that, the I
TO was coated to form a 200 nm electromagnetic wave shielding layer. The sputtering was performed using an indium-tin alloy (tin 10% by weight) as a target and a magnetron sputtering apparatus while introducing argon gas and oxygen gas. Next, silicon dioxide was deposited thereon using a vacuum deposition apparatus to form an antireflection layer. This film thickness was 200 nm. Table 2 shows the visible light transmittance of the obtained transparent laminate, and FIG. 1 schematically shows the laminate structure of the laminate. This transparent laminate showed excellent near-infrared cut performance, electromagnetic wave shielding performance, anti-scratch performance, and transparency, and could be suitably used as a filter for a plasma display panel.

Example 2 As a transparent resin substrate, a polycarbonate resin (manufactured by Mitsubishi Engineering-Plastics Corporation: trade name "Iupilon S-3000") was molded into a 10 mm square x 2 mm t
Silver was deposited on the sheet-like molded product by a resistance heating type vacuum deposition method to form an electromagnetic wave shielding layer. Thickness 50nm
Met. In addition, near-infrared absorbers (Nippon Kayaku Co., Ltd.)
Manufactured by: trade name "IRG-022" (diimonium-based) 4 parts by weight, manufactured by Japan Photographic Dye Laboratories: trade name "NKX-11"
4 "(nickel complex) and 1 part by weight of" NK-3027 "(benzopyrium-based) manufactured by Japan Photosensitive Dye Laboratories, Inc. as anchor coating agents (Nippon Soda Co., Ltd.)
Manufactured by: A solution 100 in which "T-120" (isocyanate type) is diluted to 2% by weight (solid content) with ethyl acetate.
The coating liquid added to the parts by weight was applied on the electromagnetic wave shielding layer to form a near infrared cut layer. The coating amount of the coating liquid is
0.6 g / m ² (dry solid content).

Table 1 shows the near-infrared transmittance of the near-infrared cut layer. Further, 100 parts by weight of a 40% methyl ethyl ketone solution of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd .: trade name “Kayad DPHA”) was added with 0.2 parts of benzyl dimethyl ketanol.
Apply a hard coat agent coating solution mixed with
After heating and drying at 5 ° C for 5 minutes, the output is 7.5 kW and the output density is 12
Using a high-pressure mercury lamp of 0 w / cm, ultraviolet rays were irradiated at a position of 10 cm below the light source at a conveyor speed of 2 m / min and cured by ultraviolet rays to form a scratch prevention layer. Next, silicon dioxide was deposited thereon using a vacuum deposition apparatus to form an antireflection layer. The film thickness was 200 nm. Table 2 shows the visible light transmittance of the obtained transparent laminate, and FIG. 2 schematically shows the laminate structure of the laminate. This transparent laminate showed excellent near-infrared cut performance, electromagnetic wave shielding performance, anti-scratch performance, and transparency, and could be suitably used as a filter for a plasma display panel.

Example 3 A 100 parts by weight of a polyester resin (manufactured by Mitsubishi Chemical Corporation: trade name "Novapex GM330") was mixed with a near-infrared absorbing agent (manufactured by Nippon Shokubai Co., Ltd .: trade name "EX Color 803").
A film (thickness: 100 μm) was added using a composition containing 1 part by weight of “K” (phthalocyanine) and 4 parts by weight of “IRG-002” (aminium salt type) manufactured by Nippon Kayaku Co., Ltd. Manufactured. Both surfaces of this film were subjected to a surface treatment by corona treatment. Table 1 shows the near-infrared transmittance of the near-infrared cut layer. On one side of the obtained film, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd .: trade name "Kayad DPH")
A)) is coated with a coating solution of a hard coat agent obtained by mixing 0.2 parts by weight of benzyldimethyl ketal with 100 parts by weight of a 40% methyl ethyl ketone solution, and after heating and drying at 80 ° C. for 5 minutes, an output of 7.5 kW and an output density of 7.5% Using a high-pressure mercury lamp of 120 w / cm, ultraviolet rays were irradiated at a position of 10 cm under the light source at a conveyor speed of 2 m / min and cured by ultraviolet rays to form a scratch prevention layer.

Further, ITO was coated on the damage preventing layer by a sputtering method to form an electromagnetic wave shielding layer having a thickness of 200 nm. Sputtering conditions target indium-tin alloy (tin 10% by weight),
This was performed using a magnetron sputtering apparatus while introducing argon gas and oxygen gas. Next, silicon dioxide was deposited thereon using a vacuum deposition apparatus to form an antireflection layer. This film thickness was 118 nm. Further, on the other surface of the polyester resin composition film, polymethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd .: trade name “Acrypet VH5”) was molded into a 10 mm square × 2.
The sheet-shaped molded product of mmt was bonded using an adhesive.

The visible light transmittance of the obtained transparent laminate is shown in Table 2, and the laminated structure of this laminate is schematically shown in FIG. This transparent laminate shows excellent near-infrared cut performance, electromagnetic wave shielding performance, scratch prevention performance, and transparency,
It could be suitably used as a filter for a plasma display panel.

Example 4 Polyester film (Diafoil Hoechst Co., Ltd.)
(Trade name: “T100E”, thickness: 100 μm) was coated with silver by a resistance heating type vacuum evaporation method to form a 30 nm electromagnetic wave shielding layer. A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd .: trade name “Kayad DPHA”) was placed on the electromagnetic wave shielding layer.
A hard coat agent coating solution in which 0.2 parts by weight of benzyldimethyl ketal was mixed with 100 parts by weight of a 0% methyl ethyl ketone solution, heated and dried at 80 ° C. for 5 minutes, and the output was 7.
Using a high-pressure mercury lamp with a power density of 5 kw and a power density of 120 w / cm,
Ultraviolet rays were irradiated at a position of 10 cm under the light source under the condition of a conveyor speed of 2 m / min and cured by ultraviolet rays to form an anti-scratch layer. Furthermore, a near-infrared absorber (Nippon Shokubai Co., Ltd.)
Manufactured by Nippon Kayaku Co., Ltd .: 1 part by weight of trade name "EX Color 803K" (phthalocyanine) and trade name "I"
RG-022 "(4 parts by weight of diimonium)), an anchor coating agent (trade name" T-12 "manufactured by Nippon Soda Co., Ltd.).
0 "(isocyanate-based) in ethyl acetate at 2% by weight.
A coating liquid added to 100 parts by weight of the solution diluted to (solid content) was coated on the scratch-resistant layer and cured at 40 ° C. for 1 day to obtain a near-infrared cut layer. The coating amount of the coating liquid was 0.6 g / m ² (dry solid content). Further, silicon dioxide was deposited on the near-infrared cut layer using a vacuum deposition apparatus to form an antireflection layer. This film thickness is 1
18 nm.

Further, on the other surface of the polyester film, a polycarbonate resin (manufactured by Mitsubishi Engineering-Plastics Corporation: trade name "Iupilon S-3")
000 ") were bonded together using an adhesive. Table 2 shows the visible light transmittance of the obtained transparent laminate, and FIG. 4 schematically shows the laminate structure of the laminate. This transparent laminate showed excellent near-infrared cut performance, electromagnetic wave shielding performance, anti-scratch performance, and transparency, and could be suitably used as a filter for a plasma display panel.

Example 5 Polyester film (Diafoil Hoechst Co., Ltd.)
(Trade name: “T100E”, thickness: 100 μm) was coated with silver by a resistance heating type vacuum evaporation method to form a 30 nm electromagnetic wave shielding layer. On top of that, a hard coat agent obtained by mixing 0.2 parts of benzyldimethyl ketal with 100 parts of a 40% methyl ethyl ketone solution of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., Calayad DPHA). After applying and drying by heating at 80 ° C. for 5 minutes, a high-pressure mercury lamp having an output of 7.5 kW and an output density of 120 w / cm is irradiated with ultraviolet rays at a position of 10 cm under a light source at a conveyor speed of 2 m / min and cured by ultraviolet rays. And an anti-scratch layer. Next, silicon dioxide was deposited thereon using a vacuum deposition apparatus to form an antireflection layer. This film thickness is 11
It was 8 nm. PMMA binder (manufactured by Mitsubishi Rayon Co., Ltd .: trade name "Dianal BR-80") 10
0 parts by weight of a near-infrared absorbing agent (manufactured by Nippon Kayaku Co., Ltd .: trade name "IRG-022"(diimonium-based); 8 parts by weight; and Nippon Shokubai Co., Ltd .: trade name "EEX Color EX"
803K (2 parts by weight of phthalocyanine)) was diluted to 10% by weight (solid content) with methyl ethyl ketone to prepare a coating solution. This coating solution was applied to the surface opposite to the surface provided with the electromagnetic wave shielding layer, the scratch prevention layer, and the antireflection layer, and dried to obtain a near-infrared cut layer having a thickness of 2 μm. The thus-obtained transparent laminate was bonded to a near-infrared cut layer side and a 10 mm square x 2 mmt sheet-like molded product molded with polycarbonate resin "Iupilon S-3000". Table 1 shows the near-infrared transmittance and Table 2 shows the visible light transmittance of the obtained transparent laminate, and FIG. 5 schematically shows the laminate structure of the laminate. This laminate showed excellent near-infrared cut performance, electromagnetic wave shielding performance, anti-scratch performance, and transparency, and could be suitably used as a filter for a plasma display panel.

Comparative Example 1 100 parts by weight of a polyester resin (manufactured by Mitsubishi Chemical Corporation: trade name "Novapex GM330") was mixed with a near-infrared absorbing agent (manufactured by Nippon Shokubai Co., Ltd .: trade name "EX Color 803"
A film (100 μm in thickness) was prepared by using a composition containing 1 part by weight of “K” (phthalocyanine) and 2 parts by weight of “NK-124” (cyanine) manufactured by Japan Photosensitive Dye Laboratories. Was manufactured. Both surfaces of this film were subjected to a surface treatment by corona treatment. Table 1 shows the near-infrared transmittance of the near-infrared cut layer. On one side of the obtained film, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd .: trade name "Kayad DPH")
A)) is coated with a coating solution of a hard coat agent obtained by mixing 0.2 parts by weight of benzyldimethyl ketal with 100 parts by weight of a 40% methyl ethyl ketone solution, and after heating and drying at 80 ° C. for 5 minutes, an output of 7.5 kW and an output density of 7.5% Using a high-pressure mercury lamp of 120 w / cm, ultraviolet rays were irradiated at a position of 10 cm under the light source at a conveyor speed of 2 m / min and cured by ultraviolet rays to form a scratch prevention layer.

Further, ITO was coated on the scratch preventing layer by a sputtering method to form an electromagnetic wave shielding layer having a thickness of 200 nm. Sputtering conditions target indium-tin alloy (tin 10% by weight),
This was performed using a magnetron sputtering apparatus while introducing argon gas and oxygen gas. Next, silicon dioxide was deposited thereon using a vacuum deposition apparatus to form an antireflection layer. This film thickness was 118 nm. Further, on the other surface of the polyester resin composition film, polymethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd .: trade name “Acrypet VH5”) was molded into a 10 mm square × 2.
The sheet-shaped molded product of mmt was bonded using an adhesive. Table 2 shows the visible light transmittance of the obtained transparent laminate,
FIG. 3 schematically shows a laminated structure of the laminate.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

The transparent laminate of the present invention has good near-infrared cut performance, electromagnetic wave shielding performance, anti-scratch performance, anti-light reflection performance and transparency, so that it can be used for filters for displays such as plasma display panels. Can be suitably used.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a laminated structure of a transparent laminate obtained in Example 1.

FIG. 2 is a schematic diagram showing a laminated structure of a transparent laminate obtained in Example 2.

FIG. 3 is a schematic diagram showing a laminated structure of a transparent laminate obtained in Example 3 and Comparative Example 1.

FIG. 4 is a schematic diagram showing a laminated structure of a transparent laminate obtained in Example 4.

FIG. 5 is a schematic view showing a laminated structure of a transparent laminate obtained in Example 5.

Claims (3)

[Claims] 1. A wavelength range of 850 to 1 on a transparent resin substrate.
A transparent laminate having a near-infrared cut layer having a 100 nm near-infrared transmittance of 10% or less, an electromagnetic wave shielding layer, an anti-scratch layer, and an anti-light reflection layer, wherein the near-infrared cut layer is formed of an immonium-based material. The compound contains at least one kind of near-infrared absorbing agent selected from the group consisting of a compound, a diimonium-based compound, and an aminium salt-based compound, and the transparent laminate has a visible light transmittance of 5 to 400 nm in a wavelength region of 400 to 700 nm.
A transparent laminate characterized by being at least 0%. 2. The transparent laminate according to claim 1, wherein the near-infrared cut layer includes a near-infrared absorbent comprising a diimonium-based compound and a phthalocyanine-based compound. 3. A filter for a plasma display panel comprising the transparent laminate according to claim 1 or 2.