JP4967273B2 - Conductive antireflection laminate and method for producing the same - Google Patents

Description

  The present invention relates to a conductive antireflection laminate, and more particularly, a conductive antireflection laminate useful as a filter used in front of an optical display device such as a CRT, a liquid crystal display device, a plasma display panel (PDP) or the like. It is about.

  Conventionally, an optical display device such as a CRT, a liquid crystal display device, or a plasma display panel (PDP) has a problem that it is difficult to recognize a display image due to reflection of external light on a display screen. In recent years, optical display devices have been increasingly used not only indoors but also outdoors, and the reflection of external light on the display screen has become a more serious problem.

  In order to reduce the reflection of external light, an antireflection laminate having a low reflectance over a wide range of wavelengths in the visible light region is provided on the front surface of the optical display device. Moreover, an antistatic function or an electromagnetic wave shielding function can be imparted by imparting conductivity to the antireflection laminate. For example, by providing a conductive laminate having an electromagnetic wave shielding property on the front surface of the image display unit of the PDP, it is possible to prevent adhesion of dust and shield unnecessary electromagnetic waves generated from the inside of the PDP.

  The conductive laminate is provided with conductivity by having a metal thin film layer. As the metal thin film layer, silver having high conductivity and low optical absorption is often used. Since silver is easily corroded by salt, alkali, etc., it is necessary to prevent water and solvent containing salt, alkali, etc. from penetrating to the metal thin film layer and deteriorating the metal thin film layer.

  On the surface of the conductive antireflection laminate, an antifouling layer having water repellency, oil repellency and low friction properties made of a fluorine-containing silicon compound or the like is provided. However, the antifouling layer is intended to prevent dirt from adhering to the surface of the conductive laminate, and cannot completely and completely prevent permeation of salt and alkali into the film.

  Further, silver contained in the conductive laminate is weak in adhesion to the transparent oxide conductor, and easily peels at the interface due to fine silver migration or external stress (see, for example, Patent Document 1). ), Migration of salt increases as alkali or the like permeates into the defect thus generated (see, for example, Non-Patent Document 1).

Prior art documents are shown below.
JP-A-9-85893 J. et al. Non-Crystalline Solids 178 (1994) 245-249

  The present invention has been made to solve the above-mentioned problems, and the problem is to suppress the penetration of water or a solvent containing salt, alkali or the like into the metal thin film layer and increase the migration of the metal thin film layer. An object of the present invention is to provide a conductive antireflection laminate that suppresses the above.

In the invention according to claim 1 of the present invention, at least the substrate (2) and the metal thin film layers (12) composed of the high refractive index transparent thin film layers (11, 13) and the alloy layer containing silver are alternately arranged. A conductive antireflection laminate (1) comprising a conductive thin film laminate layer (5), a low refractive index transparent thin film layer (6), and an antifouling layer (7), wherein the low refractive index The transparent thin film layer (6) is composed of two layers of a low density layer (14) having a low film stress and a high density layer (15) having a water vapor barrier property, and the low density layer (14) is low. It consists density SiO _2, the high-density layer (15) consists of high-density SiO _2, the high-density layer (15) is a conductive anti-reflection laminate, characterized in that located on the outermost layer side.

The invention according to claim 2 of the present invention is the conductive antireflective laminate according to claim 1 , wherein the high refractive index transparent thin film layer (11, 13) is a mixture of indium oxide, cerium oxide, tin oxide and titanium oxide. The conductive antireflection laminate is characterized in that the low refractive index transparent thin film layer (6) has a physical film thickness of 15 to 70 nm .

According to a third aspect of the present invention, a first high refractive index transparent thin film layer (11) is obtained by depositing a mixture of indium oxide, cerium oxide, tin oxide and titanium oxide on a substrate (2) by a sputtering method. Forming a metal thin film layer (12) on the first high-refractive-index transparent thin film layer (11) by depositing an alloy containing silver by a sputtering method, and the metal thin film layer ( 12) a step of depositing a mixture of indium oxide, cerium oxide, tin oxide and titanium oxide on the surface by sputtering to form a second high refractive index transparent thin film layer (13); and the second high refractive index transparent deposited on the thin film layer (13), forming a low-density layer (14) is deposited by vapor deposition of low-density SiO _2, wherein on the low-density layer (14), a high-density SiO ₂ by a sputtering method Forming a high-density layer (15), and depositing a fluorine-based material on the high-density layer (15) by a vacuum evaporation method to form an antifouling layer (7). This is a method for producing a conductive antireflection laminate .

  The conductive antireflection laminate according to the present invention includes at least a base material and a conductive thin film laminate layer in which a metal thin film layer made of an alloy layer containing silver and a high refractive index transparent thin film layer is provided alternately. A conductive antireflection laminate comprising a low refractive index transparent thin film layer and an antifouling layer, wherein the low refractive index transparent thin film layer has a water vapor barrier property, so that water or a solvent containing salt, alkali, etc. Permeation into the metal thin film layer is suppressed, and the metal layer is not easily deteriorated. Moreover, the function which the electroconductive functional layer containing a metal layer has is maintained for a long period of time.

  The conductive antireflection laminate (1) according to the present invention will be described below in detail with reference to FIGS.

  FIG. 1 is a side sectional view showing one embodiment of the layer configuration of the conductive antireflection laminate (1) according to the present invention, and FIG. 2 is the layer configuration of the conductive antireflection laminate (1) according to the present invention. It is a sectional side view which shows other Example of this, FIG. 3 is a spectral reflection curve figure of the electroconductive antireflection laminated body (1) based on this invention.

  As shown in FIG. 1, the conductive antireflection laminate (1) according to the present invention includes at least a base material (2) and a hard coat layer (3) provided on the base material (2), A primer layer (4) provided on the hard coat layer (3); a conductive thin-film laminate layer (5) (conductive functional layer) provided on the primer layer (4); A low refractive index transparent thin film layer (6) provided on the thin film laminate layer (5), an antifouling layer (7) provided on the low refractive index transparent thin film layer (6), and the substrate ( 2) and having an adhesive layer (8) provided on the other surface.

As said base material (2), the inorganic compound molding or organic compound molding which has transparency is mentioned. Transparency in the present invention means that light having a wavelength in the visible light region may be transmitted. The shape of the molded product is not particularly limited as long as the surface is smooth, and examples thereof include a plate shape and a roll shape. Further, the substrate (2) may be a transparent inorganic compound molded article or an organic compound molded article laminate.

  Examples of the inorganic compound having transparency include soda lime glass, borosilicate glass, quartz glass, Pyrex glass (registered trademark), alkali-free glass, lead glass, alumina, calcium fluoride, lanthanum fluoride, barium fluoride, Examples thereof include magnesium fluoride and magnesium oxide. Examples of the organic compound having transparency include polyester, polyamide, polyimide, polypropylene, polyethylpentene, polyvinyl chloride, polyvinyl acetal, polyurethane, polyethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyethersulfone, and polyolefin. , Plastics such as polyarylate, polyetheretherketone, polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose.

  The thickness of the base material (2) is appropriately selected according to the intended use, and the organic compound molded product is usually 25 to 300 μm. The organic compound molded product may contain known additives such as ultraviolet absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants and the like.

  Next, the hard coat layer (3) is a layer that protects each layer formed on the surface of the substrate (2) or the substrate (2) from mechanical injuries such as scratches by pencils, scratches by steel wool, and the like. It is. The material for forming the hard coat layer (3) may be any material having transparency, appropriate hardness, and mechanical strength, and examples thereof include resin materials such as acrylic resins, organic silicon resins, and polysiloxanes. .

  Examples of the acrylic resin include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (meth) acrylate, and triethylene glycol. Di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) acryloyloxypropionate, trimethylol Ethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2 Hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1,2-butadiene di (meth) Acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 3,8-bis (meth) Acryloyloxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1,4-bis (( (Meth) acryloyloxy Methyl) cyclohexane, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, epoxy-modified bisphenol A di (meth) acrylate and the like.

Examples of the organic silicon resin include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapentaethoxysilane, tetrapentaisoproxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyl Tributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, and the like.

  The hard coat layer (3) is formed by depositing these resin materials on the substrate (2) and curing them by heat curing, ultraviolet curing or ionizing radiation curing. The hard coat layer has a physical film thickness of 0.5 μm or more, preferably 3 to 20 μm, more preferably 3 to 6 μm.

  Transparent hard particles having an average particle diameter of 0.01 to 3 μm may be dispersed in the hard coat layer (3), and a treatment called antiglare may be performed. The fine particles in the hard coat layer (3) have fine irregularities on the surface, so that the light diffusibility is improved and the reflectance can be further reduced.

  The hard coat layer (3) is preferably subjected to a surface treatment. By performing the surface treatment, the adhesion with an adjacent layer can be improved. Examples of the surface treatment of the hard coat layer (3) include corona treatment, vapor deposition, electron beam treatment, radio frequency discharge plasma treatment, sputtering treatment, ion beam treatment, atmospheric pressure glow discharge treatment, Examples include an alkali treatment method and an acid treatment method.

  Next, the primer layer (4) is a layer that improves the adhesion between the hard coat layer (3) and the conductive thin film laminate layer (5). Examples of the material for the primer layer (4) include metals such as silicon, nickel, chromium, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium; alloys composed of two or more of these metals; These oxides, fluorides, sulfides, nitrides and the like can be mentioned. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as adhesion is improved.

  The primer layer (4) may have a thickness that does not impair the transparency of the substrate (2), and is preferably a physical film thickness of 0.1 to 10 nm. The primer layer (4) can be formed by a conventionally known method such as a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, a chemical vapor deposition (CVD) method, or a wet coating method.

  Next, the conductive thin film laminate layer (5) has a high refractive index transparent thin film layer (11) (transparent metal oxide layer) and a metal thin film layer (12) (metal layer) in this order from the substrate (2) side. And a high refractive index transparent thin film layer (13) (transparent metal oxide layer). The conductive thin film laminate layer (5) imparts electromagnetic wave shielding properties and antireflection properties.

  The high refractive index transparent thin film layers (11) and (13) are layers having a refractive index of light having a wavelength of 550 nm of 1.7 or more and an extinction coefficient of light having a wavelength of 550 nm of 0.5 or less.

  Materials for the high refractive index transparent thin film layers (11, 13) include indium, tin, titanium, silicon, zinc, zirconium, niobium, magnesium, bismuth, cerium, chromium, tantalum, aluminum, germanium, gallium, antimony, neodymium. And metals such as lanthanum, thorium and hafnium; these metal oxides, fluorides, sulfides and nitrides; and mixtures of oxides, fluorides, sulfides and nitrides. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as the chemical composition maintains transparency.

Examples of the oxide include a mixture of indium oxide and tin oxide (ITO), indium oxide, cerium oxide, a mixture of tin oxide and titanium oxide (ICO), a mixture of indium oxide and zinc oxide, zinc oxide and gallium. A mixture of zinc oxide and aluminum, a mixture of boron in zinc oxide, niobium oxide, a mixture of tin oxide and antimony oxide, a mixture of antimony and indium in tin oxide, zirconium in silicon And the like. Among these, ITO, ICO, and niobium oxide have a refractive index of 2.0 or more in the visible light region and an extinction coefficient close to zero, so that they have excellent transparency in the visible light region and absorb light by the material. It is preferable because it is small. In addition, ITO and ICO have high free electron density, that is, low specific resistance, so that high electromagnetic shielding properties are possible. Moreover, sputtering film formation by a direct current power supply is possible, and the film formation speed is improved, resulting in high productivity.

  The high refractive index transparent thin film layers (11, 13) are not necessarily made of the same material, and are appropriately selected according to the purpose. The high refractive index transparent thin film layers (11, 13) can be formed by a conventionally known method such as a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, or a wet coating method.

  The metal thin film layer (12) preferably has a refractive index of light having a wavelength of 550 nm of 1.0 or less and an extinction coefficient of 10.0 or less. Examples of the material for the metal thin film layer (12) include metals such as gold, silver, copper, platinum, aluminum, and palladium; and alloys containing two or more of these metals. Among these, silver, an alloy containing silver, and a mixture containing silver are preferable. Silver has a small refractive index of light with a wavelength of 550 nm as 0.055, while its extinction coefficient is as large as 3.32. Since the extinction coefficient with respect to the refractive index is large compared to other metals, the metal is high, that is, the conductivity is high.

  The silver thin film is easily corroded by oxygen, sulfur, halogen, alkali or the like, resulting in aggregation, migration, and the like. On the other hand, it is known that the chemical stability of silver improves when silver contains other metal elements. Examples of metal elements contained in silver include gold, copper, platinum, tin, aluminum, nickel, magnesium, titanium, bismuth, zirconium, neodymium, palladium, zinc, indium, germanium, iridium, osmium, ruthenium, rhenium, and rhodium. Etc. Two or more of these metal elements may be contained in silver. When these metal elements are contained in silver, the content thereof should be such that it contributes to corrosion resistance without deteriorating the optical performance of the metal thin film layer (12) or the conductive antireflection laminate (1). What is necessary is just about 0.1 atomic% to 20 atomic%.

  The metal thin film layer (12) preferably has a physical film thickness of 5 to 15 nm. The metal thin film layer (12) can be formed by a conventionally known method such as an evaporation method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, or a wet coating method. In the case of using the sputtering method, film formation is possible with a direct current power source, and a high film formation rate is obtained, so that productivity is excellent.

  Between the high refractive index transparent thin film layer (11) and / or the high refractive index transparent thin film layer (13) and the metal thin film layer (12), the metal thin film layer (12) is protected from corrosion, and the interlayer adhesion A protective layer (not shown) for improving the performance may be provided. Examples of the material for the protective layer include metals such as zinc, silicon, nickel, chromium, gold, platinum, aluminum, magnesium, antimony, titanium, palladium, bismuth, and tin; alloys containing two or more of these metals; These metal oxides, fluorides, sulfides, and nitrides may be mentioned.

  The thickness of this protective layer should just be a grade which does not impair the transparency of an electroconductive antireflection laminated body (1), and is about 0.1-10 nm in a physical film thickness. The formed protective layer may have a uniform thickness on the entire surface, or may have an island shape. The island shape is a form in which a portion where the material of the protective layer is attached and a portion where the material is not attached coexist. When providing a protective layer on both surfaces of this metal thin film layer (12), these protective layers do not need to be the same material, the same film-forming method, and the same film thickness.

In addition, the said conductive thin film laminated body layer (5) is a conductive thin film laminated body layer (5) of the three-layer structure of the example of illustration.
If the high refractive index transparent thin film layer and the metal thin film layer are provided alternately, and the uppermost layer and the lowermost layer are the high refractive index transparent thin film layer, the three high refractive index transparent thin film layers and It may have a five-layer structure in which two metal thin film layers are alternately provided, or may have seven or more layers. By increasing the high-refractive-index transparent thin film layer, the conductive antireflection laminate (1) has a wide wavelength range in the visible light region where the reflectance is low. However, by providing the low refractive index transparent thin film layer (6), which will be described later, the conductive antireflection laminate (1) has a sufficiently wide wavelength range of visible light where the reflectance is low, so that the conductive antireflection layer is provided. From the viewpoint of thinning the laminate (1), a three-layer structure is preferable.

  Next, the said low refractive index transparent thin film layer (6) is a layer whose refractive index of the light of wavelength 550nm is less than 1.7, and whose extinction coefficient of the light of wavelength 550nm is 0.5 or less. By providing the low refractive index transparent thin film layer (6) in contact with the high refractive index transparent thin film layer (13) of the conductive thin film laminate layer (5), the conductive antireflection laminate (1) is reflected. The wavelength range of visible light where the rate is low is sufficiently widened.

  The low-refractive-index transparent thin film layer (6) includes a low-density layer (14) that relieves stress in the film and suppresses film cracking and defect generation, and a metal thin film layer included in the conductive thin film laminate layer (5). In order to protect (12) from corrosion caused by water or a solvent containing acid, halogen, alkali, etc., it is composed of a high-density layer (15) having a high water vapor barrier property. The water vapor barrier property of the low refractive index transparent thin film layer (6) is preferably 0.01 cc / m 2 / day or less.

  Examples of the material of the low density layer (14) and the high density layer (15) include silicon oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, cerium fluoride, hafnium fluoride, and lanthanum fluoride. Sodium fluoride, aluminum fluoride, lead fluoride, strontium fluoride, ytterbium fluoride, and the like.

  The low-density layer (14) and the high-density layer (15) are not necessarily made of the same material, and are appropriately selected according to the purpose. The low-density layer (14) and the high-density layer (15) can be formed by a conventionally known method such as a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, or a wet coating method. The thickness of the low refractive index transparent thin film layer (6) is preferably 15 to 70 nm in terms of physical film thickness.

  The low refractive index transparent thin film layer (6) is not limited to the two-layer structure of the low density layer (14) and the high density layer (15), and is continuously inclined from the low density to the high density. At least one layer between the low-density layer (14) and the high-density layer (15). A structure in which the above intermediate density layer (not shown) is sandwiched may be employed.

  Incidentally, the low refractive index transparent thin film layer (6) is not limited to the surface of the conductive thin film laminate layer (5) in contact with the high refractive index transparent thin film layer (13), as shown in FIG. You may provide in both the surface which contact | connects a high refractive index transparent thin film layer (11), and the surface which contact | connects a high refractive index transparent thin film layer (13).

  Next, the antifouling layer (7) is a layer that facilitates wiping off water droplets, fingerprints and the like on the surface of the conductive antireflection laminate (1) and prevents external damage such as scratches due to impact on the surface. is there. As the material of the antifouling layer (7), any material having water repellency, oil repellency and low friction properties may be used. For example, silicon oxide, fluorine-containing silane compound, fluoroalkylsilazane, fluoroalkylsilane, fluorine-containing Examples thereof include silicon compounds and perfluoropolyether group-containing silane coupling agents.

The antifouling layer (7) can be formed by a wet process such as a microgravure method, a screen coating method, or a dip coating method in addition to a vacuum dry process such as an evaporation method, a sputtering method, a CVD method, or a plasma polymerization method. The physical film thickness of the antifouling layer (7) is about 5 to 10 nm. It is possible to control the reflection color of the conductive antireflection laminate (1) by changing the film thickness of the antifouling layer (7).

  Next, the said adhesion layer (8) should just transmit the light of the wavelength of a visible light region, and has adhesiveness. The pressure-sensitive adhesive layer (8) preferably has a refractive index of 1.45 to 1.70 for light having a wavelength of 500 to 600 nm and an extinction coefficient of about 0 from the viewpoint of optical performance. Examples of the material of the pressure-sensitive adhesive layer (8) include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives (PVA), ethylene-vinyl acetate adhesives (EVA), polyvinyl ethers, Saturated amorphous polyester, melamine resin, etc. are mentioned.

  In the conductive antireflection laminate (1) described above, the low refractive index transparent thin film layer (6) is composed of two layers of a low density layer (14) and a high density layer (15). The film stress on the entire surface of the low refractive index transparent thin film layer (6) and the surface in contact with the high refractive index transparent thin film layer (13) on the outermost layer of the conductive thin film laminate layer (5) are reduced. Even if a micro-aggregation defect occurs in the metal thin film layer (12) included in the conductive thin film laminate layer (5), there is an effect of relieving stress and suppressing film cracking and defect increase.

  Furthermore, since the low refractive index transparent thin film layer (6) includes the high density layer (15), the low refractive index transparent thin film layer (6) has a high water vapor barrier property of 0.01 cc / m 2 / day or less. In addition, an effect of protecting the metal thin film layer (12) included in the conductive thin film laminate layer (5) from corrosion caused by moisture or solvent containing acid, halogen, alkali or the like can be obtained. Further, by providing the high-density layer (15) on the outer layer side of the conductive antireflection laminate (1), the outermost antifouling layer (7) penetrates into the low refractive index transparent thin film layer (6). And the water repellency, oil repellency and low friction by the antifouling layer (7) are not impaired.

  On the other hand, the low-refractive-index transparent thin-film layer (6) consisting only of the high-density layer (15) has a high film density and a high compressive stress when, for example, silicon oxide is deposited by a sputtering method under a low pressure. A large stress difference is generated between the lower high-refractive-index transparent thin film layer (13), and film cracking is likely to occur. The film crack (crack) generated in this way penetrates moisture and solvent containing acid, halogen, alkali, etc., and increases aggregation and migration of the metal thin film layer (12).

  On the other hand, the low refractive index transparent thin film layer (6) consisting only of the low density layer (14) has a low film density and a porous structure when silicon oxide is deposited by vapor deposition under high pressure, for example. Barrier properties are not sufficiently obtained, and water and solvents containing acids, halogens, alkalis, etc. are likely to penetrate into the metal thin film layer (12) included in the conductive thin film laminate layer (5), causing aggregation and migration. It will increase.

   In addition, the electroconductive antireflection laminate (1) of the present invention is not limited to the electroconductive antireflection laminate (1) in the illustrated example, and at least the base (2) and the high refractive index transparent thin film layer ( Conductive thin film laminate layer (conductive functional layer) (5) in which transparent metal compound layers (11, 13) and metal thin film layers (metal layers) (12) are provided alternately, and low density with low film stress What is necessary is just to have a low refractive index transparent thin film layer (6) which has a layer (14) and a high-density layer (15) with high water vapor | steam barrier property.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited to these.

<Example 1>
On the substrate (2), a triacetyl cellulose film having a thickness of 80 μm (refractive index 1.51 of light having a wavelength of 550 nm) (hereinafter referred to as TAC film), ionizing radiation curable acrylic resin is applied by wet coating. A hard coat layer (3) having a physical film thickness of 5 μm was formed. On the hard coat layer (3), SiOx was deposited by sputtering to form a primer layer (4) having a physical film thickness of 3 nm.

  Subsequently, the conductive thin film laminated body layer (5) which consists of a high refractive index transparent thin film layer (11), a metal thin film layer (12), and a high refractive index transparent thin film layer (13) was formed as follows.

 That is, a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium is deposited on the primer layer (4) by a sputtering method, and a high refractive index transparent thin film layer (11) having a physical film thickness of 27 nm. (The refractive index of light having a wavelength of 550 nm is 2.2 and the extinction coefficient is 0.001). Subsequently, an alloy containing 1.5 atomic% of gold and 0.5 atomic% of copper in silver is deposited on the high refractive index transparent thin film layer (11) by a sputtering method, and a metal thin film layer having a physical thickness of 9 nm is deposited. (12) (Refractive index 0.09 of light with a wavelength of 550 nm, extinction coefficient 3.51) was formed. On the metal thin film layer (12), a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium is deposited by a sputtering method, and a high refractive index transparent thin film layer (13) having a physical film thickness of 20 nm (13) ( A light having a wavelength of 550 nm having a refractive index of 2.2 and an extinction coefficient of 0.001) was formed.

Next, low-density SiO ₂ is deposited on the high-refractive-index transparent thin film layer (13) by an evaporation method, and a low-density layer (14) having a physical film thickness of 30 nm (refractive index of light of wavelength 550 nm 1.45, extinction) A coefficient of 0) was formed. Further, high-density SiO ₂ is deposited on the low-density layer (14) by a sputtering method to obtain a high-density layer (15) having a physical film thickness of 15 nm (a refractive index of 1.46 for light having a wavelength of 550 nm, an extinction coefficient). 0) to form a low refractive index transparent thin film layer (6) having a total physical film thickness of 45 nm.

  Further, a fluorine-based material (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KP801M) is deposited on the low refractive index transparent thin film layer (6) by a vacuum evaporation method, and the antifouling layer (7) having a physical film thickness of 6 nm. Formed. On the other surface of the TAC film, an acrylic adhesive was applied to form an adhesive layer (8) to obtain a conductive antireflection laminate (1).

  Below, the comparative example of this invention is demonstrated.

<Comparative Example 1>
In Example 1, as the low-refractive-index transparent thin film layer (6), SiO ₂ was deposited by sputtering to form a high-density layer (15) having a physical film thickness of 45 nm. The antireflective laminate (1) was obtained.

<Comparative example 2>
In Example 1, the low-refractive-index transparent thin film layer (6) was conductive in the same manner as in Example 1 except that SiO ₂ was deposited by vapor deposition to form a low-density layer (14) having a physical film thickness of 45 nm. The antireflective laminate (1) was obtained.

<Evaluation 1>
The following evaluation was performed on the electroconductive antireflection laminate (1) obtained in Example 1, Comparative Example 1 and Comparative Example 2. The results are shown in Tables 1-3.
(1) 1% NaCl aqueous solution immersion test: A 200 mm × 200 mm sample was bonded onto a 200 mm × 200 mm quartz glass substrate so that the adhesive layer (8) side was the quartz glass substrate side, and this was 1% by mass. It was immersed in an aqueous NaCl solution. The change with time of the conductive antireflection layer was observed, and the aggregation points of silver in the metal thin film layer were visually counted. During the immersion of the sample, the temperature of the aqueous NaCl solution was kept at 20 ° C.
(2) 5% NaCl aqueous solution immersion test: The silver aggregation points of the metal thin film layers were visually counted in the same manner as (1) except that the 1% by mass NaCl aqueous solution was changed to a 5% by mass NaCl aqueous solution.
(3) Moisture and heat resistance test: A 200 mm × 200 mm sample was bonded onto a 200 mm × 200 mm quartz glass substrate so that the adhesive layer (8) side was the quartz glass substrate side, and this was 60 ° C.-90% RH. Was placed in a constant temperature and humidity chamber, and a moisture and heat resistance test was conducted for up to 1000 hours. The change with time of the conductive antireflection layer was observed, and the aggregation points of silver in the metal thin film layer were visually counted.

表１は、実施例１および比較例１〜２について、（１）１％ＮａＣｌ水溶液浸漬試験での導電性反射防止層の経時変化を観察し、金属薄膜層の銀の凝集点を目視により数えた評価結果を示した表である。

Table 1 shows, for Example 1 and Comparative Examples 1 and 2, (1) Observe the time-dependent change of the conductive antireflection layer in the 1% NaCl aqueous solution immersion test, and visually count the aggregation point of silver in the metal thin film layer. It is the table | surface which showed the evaluation result.

表２は、実施例１および比較例１〜２について、（２）５％ＮａＣｌ水溶液浸漬試験での導電性反射防止層の経時変化を観察し、金属薄膜層の銀の凝集点を目視により数えた評価結果を示した表である。

Table 2 shows Example 1 and Comparative Examples 1 and 2, (2) Observing the time-dependent change of the conductive antireflection layer in a 5% NaCl aqueous solution immersion test, and visually counting the aggregation point of silver in the metal thin film layer. It is the table | surface which showed the evaluation result.

表３は、実施例１および比較例１〜２について、（３）耐湿熱性試験での導電性反射防止層の経時変化を観察し、金属薄膜層の銀の凝集点を目視により数えた評価結果を示した表である。

Table 3 shows an evaluation result of Example 1 and Comparative Examples 1 and 2 in which (3) the time-dependent change of the conductive antireflection layer in the heat and humidity resistance test was observed, and the silver aggregation points of the metal thin film layer were visually counted. It is the table | surface which showed.

 The samples of Comparative Example 1 and Comparative Example 2 in the evaluations (1) to (3) were subjected to elemental analysis of the places where silver aggregation occurred. As a result, the high refractive index transparent thin film layer and the metal in all the evaluation samples Chlorine was detected in the thin film layer. On the other hand, in the sample of Example 1, chlorine was not detected in the high refractive index transparent thin film layer and the metal thin film layer. Moreover, when the silver aggregation part was observed about the sample of the comparative example 1, the low-refractive-index transparent thin film layer cracked, and peeling had occurred between the high-refractive-index transparent thin film layer and the metal thin film layer. From the above, it was confirmed that the conductive antireflection laminate of the present invention suppresses the penetration of water containing salt and the like into the metal thin film layer.

<Evaluation 2>
The following evaluation was performed on the electroconductive antireflection laminate (1) obtained in Example 1, Comparative Example 1 and Comparative Example 2. The results are shown in Table 4.
(4) Contact angle measurement with pure water: Measured using a contact angle meter CA-X manufactured by Kyowa Interface Chemical Co., Ltd. (5) Contact angle measurement with oleic acid: Measured using a contact angle meter CA-X manufactured by Kyowa Interface Chemical Co., Ltd.

表４は、実施例１および比較例１〜２について、純水の接触角およびオレイン酸の接触角を示した表である。

Table 4 is a table showing the contact angle of pure water and the contact angle of oleic acid for Example 1 and Comparative Examples 1 and 2.

  From the results of Table 4, it can be seen that Example 1 is superior to Comparative Example 2 in water repellency and oil repellency. This is because the film density of the low refractive index transparent thin film layer of Comparative Example 2 is low, and the antifouling layer has penetrated into the film. Example 1 and Comparative Example 1 are the low refractive index transparent thin film layers on the surface. It was found that since the film density was high, the water repellency and oil repellency of the antifouling layer were not impaired.

  Furthermore, about the electroconductive antireflection laminated body (1) obtained in Example 1, the spectral reflectance measurement was performed by U-4000 type self-recording spectrophotometer [made by Hitachi, Ltd.] as an optical characteristic. The results are shown in FIG.

  From the results of FIG. 3, it was found that the conductive antireflection laminate (1) according to the present invention has a sufficiently low luminous reflectance as the antireflection laminate.

It is a sectional side view which shows one Example of the layer structure of the electroconductive antireflection laminated body which concerns on this invention. It is a sectional side view which shows the other Example of the layer structure of the electroconductive antireflection laminated body which concerns on this invention. It is a spectral reflection curve figure of the electroconductive antireflection laminated body which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Conductive antireflection laminated body 2 ... Base material 3 ... Hard coat layer 4 ... Primer layer 5 ... Conductive thin film laminated body layer (conductive functional layer)
6 ... Transparent film with low refractive index 7 ... Antifouling layer 8 ... Adhesive layer 11 ... Transparent thin film layer with high refractive index (transparent metal oxide layer)
12 ... Metal thin film layer (metal layer)
13 ... High refractive index transparent thin film layer (transparent metal oxide layer)
14 ... Low density layer 15 ... High density layer

Claims (3)

At least a conductive thin film laminate layer in which a base material, a metal thin film layer composed of a high refractive index transparent thin film layer and a silver-containing alloy layer are alternately provided, a low refractive index transparent thin film layer, and an antifouling layer The low-refractive-index transparent thin film layer is composed of two layers , a low-density layer having a low film stress and a high-density layer having a water vapor barrier property. A conductive antireflection laminate , wherein the density layer is made of low-density SiO ₂ , the high-density layer is made of high-density SiO ₂ , and the high-density layer is located on the outermost layer side. The high refractive index transparent thin film layer is made of a mixture of indium oxide, cerium oxide, tin oxide and titanium oxide, and the physical film thickness of the low refractive index transparent thin film layer is 15 to 70 nm. The conductive antireflection laminate as described. A step of depositing a mixture of indium oxide, cerium oxide, tin oxide and titanium oxide on a substrate by a sputtering method to form a first high refractive index transparent thin film layer;
Forming a metal thin film layer by depositing an alloy containing silver on the first high refractive index transparent thin film layer by a sputtering method;
A step of depositing a mixture of indium oxide, cerium oxide, tin oxide and titanium oxide on the metal thin film layer by a sputtering method to form a second high refractive index transparent thin film layer;
On the second high refractive index transparent thin film layer, low density SiO ₂ Forming a low density layer by depositing by vapor deposition;
High density SiO on the low density layer ₂ Forming a high-density layer by depositing by sputtering method;
A step of depositing a fluorine-based material on the high-density layer by a vacuum evaporation method to form an antifouling layer;
A method for producing a conductive antireflection laminate, comprising:

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