JP2007187780A - Antireflection thin film laminated body and optical display system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection thin film laminated body which can adequately lower reflectivity over a wide range of a visible light region and which is excellent in water repellency, fingerprint wipeability, corrosion resistance, weather resistance and adhesiveness and to provide an optical display system which is provided with the antireflection thin film laminated body at its front face. <P>SOLUTION: A conductive multilayered film constituted by alternatively laminating a high refractive index transparent thin film layer and a metal thin film layer is formed at least on a base material and an antifouling corrosion-protective layer having both an antifouling function and a corrosion-protective function is provided on the outermost layer to constitute the antireflection thin film laminated body. Further the optical display system which is provided with the antireflection thin film laminated body at its front face is also provided. The antireflection thin film laminated body is used as an optical functional filter of an optical article. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection thin film laminate having low light reflectance, high transmittance, excellent visibility, easily wiping off surface dirt, and high corrosion resistance. It is suitably used for the front surface of optical functional filters and optical display devices.

  In an optical display device such as a CRT, a liquid crystal display device, or a plasma display panel (PDP), there is a problem that it becomes difficult to recognize an image due to reflection of external light on a display screen. In recent years, optical display devices have been increasingly taken not only indoors but also outdoors, and the reflection of external light on the display screen has become a more serious problem. Similarly, not only in an optical display device but also in an optical article such as a window glass, glasses, and goggles, there is a problem that reflection of outside light deteriorates visibility. As described above, the optical display device and the optical article are required to reduce the reflection of external light and improve the visibility. Therefore, in order to reduce the reflection of external light, an antireflection thin film laminate having a low reflectance with respect to light in the visible light region is provided on the front surface of the optical display device or optical article.

  Moreover, electromagnetic wave shielding performance can be imparted by imparting conductivity to the antireflection thin film laminate. For example, it is possible to shield unwanted electromagnetic waves generated from the inside of the PDP by providing an antireflection thin film laminate having an electromagnetic wave shielding property on the front surface of the image display unit of the PDP. In addition, it is possible to shield electromagnetic waves entering from the outside of buildings and prevent crosstalk of communication by pasting antireflection thin film laminates with electromagnetic shielding properties on window glass of facilities using wireless LAN. it can.

  As such an antireflection thin film laminate, a high refractive index transparent thin film layer and a metal thin film layer are laminated by repeating the combination of the high refractive index transparent thin film layer and the metal thin film layer once to 6 times or less. Further, those having a laminated structure in which a high refractive index transparent thin film layer is further laminated thereon are known.

  However, in this antireflection laminate, the number of combinations of the high-refractive-index transparent thin film layer and the metal thin film layer is 3 times or more, so that the film becomes thick and the transparency is lowered, and the film forming process is increased. , Productivity becomes worse. On the other hand, if the number of combinations of the high refractive index transparent thin film layer and the metal thin film layer is reduced, the reflectance for light on the low wavelength side and the high wavelength side in the visible light region becomes high, and the wavelength of light at which the reflectance becomes sufficiently low. The range of becomes narrow.

  When silver is used for the metal thin film layer, an antireflection thin film laminate having high transmittance in the visible light region can be obtained. On the other hand, silver is inferior in corrosion resistance and can cause defects due to aggregation, migration, etc. over time. The cause of agglomeration, migration, etc. is due to atmospheric oxygen, sulfur, halogen, alkali, etc., but especially agglomeration, migration, such as high-temperature, high-humidity environments and seaside humid chlorine environments. When there are multiple occurrence factors such as the above, the occurrence frequency tends to be higher than when there is a single factor.

As a method for suppressing the deterioration of the silver thin film, there are a method of adding another metal to silver and a method of providing a protective layer adjacent to the silver thin film layer. With respect to the method of adding other metals to silver, the effect of suppressing the occurrence of aggregation, migration, etc. of the material of elements close to silver on the periodic table of elements is great. With respect to the method of providing a protective layer adjacent to the silver thin film layer, a material is used in which the material of the protective film itself is resistant to intruding substances from the outside or adsorbs the intruding substances. By adding another metal to silver and / or providing a protective layer adjacent to the silver thin film layer, it is possible to extend the time when aggregation, migration, etc. start to occur, and to reduce the frequency of occurrence.

  On the other hand, since the reliability requirements of optical display devices such as CRTs, liquid crystal display devices, and PDPs are increasing year by year, it is an essential task to improve the reliability of optical filters. In addition to the method of adding another metal to silver and the method of providing a protective layer adjacent to the silver thin film layer, there are methods of suppressing the occurrence of silver aggregation, migration and the like due to the anticorrosive agent. Anticorrosives are effective in inhibiting silver degradation. In addition, a wide variety of commercially available materials are available, and the method of use is wide, so it is highly convenient. A further synergistic effect of inhibiting silver deterioration can be obtained by combining with a method of adding another metal to silver and a method of providing a protective layer adjacent to the silver thin film layer.

  By imparting an antifouling function to the surface of the antireflection thin film laminate, it is possible to repel the substances causing deterioration such as moisture, oil and sweat from the outside, and to improve the wiping performance of the surface. In particular, since moisture and sweat contain chlorides and sulfides that aggregate and migrate silver, imparting antifouling performance is preferable from the viewpoint of reliability. In addition, since the slipping property of the surface is increased by providing the antifouling function, it is advantageous for adhesion evaluation such as a tape peel test and mechanical strength evaluation such as a scratch test.

  There are two processes for imparting an anticorrosion function to the silver thin film layer before or after providing the antifouling layer on the surface of the antireflection thin film laminate. In the latter case, the anticorrosive agent does not penetrate into the silver thin film layer due to the water and oil repellent functions of the antifouling agent, and the anticorrosive function for inhibiting deterioration of the silver thin film layer cannot be expressed. On the other hand, in the former case, the anticorrosive reaches the vicinity of the base material of the antireflection thin film laminate, and the anticorrosive enters excessively at the interface of each layer. As a result, it has been confirmed that the adhesion of the interface is reduced, and the film is easily peeled off as compared with the antireflection thin film laminate that provides only the antifouling function and does not provide the anticorrosion function.

  The present invention has been made in consideration of the above technical background, and can sufficiently reduce the reflectance over a wide range of visible light region, and is water repellent, fingerprint wiping property, corrosion resistance, weather resistance and An object of the present invention is to provide an antireflection thin film laminate having excellent adhesion and an optical display device having the antireflection thin film laminate on the front surface.

  In order to achieve the above object, that is, the invention according to claim 1 is to form a conductive multilayer film formed by alternately laminating a high refractive index transparent thin film layer and a metal thin film layer on at least a substrate. The antireflection thin film laminate is provided with an antifouling and anticorrosive layer having an antifouling function and an anticorrosive function at the outermost layer.

  The invention according to claim 2 is the antireflection thin film laminate according to claim 1, wherein the metal thin film layer is silver or an alloy containing silver.

  The invention according to claim 3 is the antireflection thin film laminate according to claim 1 or 2, wherein a low refractive index transparent thin film layer is provided between the conductive multilayer film and the antifouling and anticorrosion layer. is there.

  The invention according to claim 4 is an antireflection thin film laminate using the antireflection thin film laminate according to any one of claims 1 to 3 as an optical functional filter.

  The invention according to claim 5 is an optical display device characterized in that the antireflection thin film laminate according to any one of claims 1 to 3 is provided on the front surface of the optical display device.

  According to the present invention, the reflectance can be sufficiently lowered over a wide range of visible light region, and an antireflection thin film laminate excellent in water repellency, fingerprint wiping property, corrosion resistance, weather resistance and adhesion can be provided. .

  An optical display device using the antireflection thin film laminate of the present invention on the front surface of an optical display device such as a CRT, a liquid crystal display device, or a PDP can be provided. The antireflection thin film laminate of the present invention is also useful as an optical functional filter provided in optical articles such as window glass, glasses and goggles.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of the antireflection thin film laminate of the present invention. The antireflection thin film laminate 300 is provided on the transparent substrate 2, the hard coat layer 3 provided on the transparent substrate 2, the primer layer 4 provided on the hard coat layer 3, and the primer layer 4. The high refractive index transparent thin film layer 5, the protective layer 6 provided on the high refractive index transparent thin film layer 5, the metal thin film layer 7 provided on the protective layer 6, and the metal thin film layer 7 are provided. Protective layer 8, high refractive index transparent thin film layer 9 provided on protective layer 8, low refractive index transparent thin film layer 10 provided on high refractive index transparent thin film layer 9, and low refractive index transparent thin film layer The functional thin film layer 11 provided on 10 and the pressure-sensitive adhesive layer 1 provided on the other surface of the transparent substrate 2 are roughly configured.

(Base material)
Examples of the transparent substrate 2 include an inorganic compound molded product or an organic compound molded product having transparency. 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 transparent substrate 2 may be a transparent inorganic compound molded body or an organic compound molded body laminate.

  Examples of the inorganic compound molded product having transparency include soda lime glass, borosilicate glass, quartz glass, Pyrex (registered trademark) glass, alkali-free glass, lead glass, and the like.

  An example of the organic compound molding having transparency is plastic. Examples of the plastic include polyester, polyamide, polyimide, polypropylene, polyethylpentene, polyvinyl chloride, polyvinyl acetal, polyurethane, polyethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyether sulfone, polyolefin, polyarylate, polyether ether. Examples thereof include ketones, polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose.

  The thickness of the transparent substrate 2 is appropriately selected according to the intended use, and 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.

(Hard coat layer)
The hard coat layer 3 is a layer that protects each layer formed on the surface of the transparent substrate 2 or on the transparent substrate 2 from mechanical injuries such as scratches by a pencil or the like and scratches by steel wool. 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 acrylic resins 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, tri Methylolethane tri (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, tetradecanethylene 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) acrylo ilio Xylmethyl) 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, Examples include butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, and hexyltrimethoxysilane.

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

  Transparent hard particles having an average particle diameter of 0.01 to 3 μm may be dispersed in the hard coat layer 3 and subjected to a process called antiglare. The fine particles in the hard coat layer 3 have fine irregularities on the surface, improving the light diffusibility and further reducing the reflection of light.

  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, high frequency discharge plasma treatment, sputtering treatment, ion beam treatment, atmospheric pressure glow discharge plasma treatment, and alkali treatment. Method, acid treatment method and the like.

(Primer layer)
The primer layer 4 is a layer that improves the adhesion between the hard coat layer 3 and the conductive multilayer film 100. Examples of the material of 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; Products, fluorides, sulfides, nitrides and the like. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as adhesion is improved.

The thickness of the primer layer 4 should just be a grade which does not impair the transparency of the transparent base material 2, Preferably it is 0.1-10 nm by a physical film thickness.
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, or a chemical vapor deposition (CVD) method.

(Conductive multilayer film)
The antireflection thin film laminate 300 according to the present invention provides the conductive multilayer film 100 with electromagnetic wave shielding properties and infrared cut properties, and a high refractive index transparent thin film layer and a metal thin film layer are alternately provided one by one. The number of high refractive index transparent thin film layers is n + 1, and the number of metal thin film layers is n (where n is an integer of 1 or more). The illustrated conductive multilayer film 100 is an example where n = 1. The conductive multilayer film 100 includes a high refractive index transparent thin film layer 5, a protective layer 6, a metal thin film layer 7, a protective layer 8 and a high refractive index transparent thin film layer 9 in order from the transparent substrate 2 side.

  The high refractive index transparent thin film layers 5 and 9 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.

  The materials for the high refractive index transparent thin film layers 5 and 9 include indium, tin, titanium, silicon, zinc, zirconium, niobium, magnesium, bismuth, cerium, chromium, tantalum, aluminum, germanium, gallium, antimony, neodymium, lanthanum, Metals such as thorium and hafnium; oxides, fluorides, sulfides, and nitrides of these metals; oxides, fluorides, sulfides, and mixtures of nitrides. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as the chemical composition maintains transparency.

  The high-refractive-index transparent thin film layer 5 and the high-refractive-index transparent thin film layer 9 are not necessarily the same material, and are appropriately selected according to the purpose. The high refractive index transparent thin film layers 5 and 9 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.

  The metal thin film layer 7 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 7 include metals such as gold, silver, copper, platinum, aluminum, and palladium; alloys containing two or more of these metals; oxides, fluorides, sulfides, and nitrides of these metals. A mixture of oxides, fluorides, sulfides, nitrides, and the like. 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 ratio of the extinction coefficient to the refractive index is larger than that of other metals, the metallicity is high, that is, the electrical conductivity is high.

  A silver thin film is easily deteriorated by oxygen, sulfur, halogen, alkali, and the like, and as a result, aggregation, migration, and the like occur. 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. , Yttrium, hafnium and the like. Two or more of these metal elements may be contained in silver. In the case where these metal elements are contained in silver, the content thereof may be a level that contributes to corrosion resistance without deteriorating the optical performance of the metal thin film layer 7 or the antireflection thin film laminate 300, and is 0.1 atom. % To about 20 atomic%.

The metal thin film layer 7 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. When the sputtering method is used, film formation is possible with a direct current power source, and a high film formation rate is obtained, so that productivity is excellent.

  The protective layers 6 and 8 are layers for protecting the metal thin film layer 7 from corrosion. Examples of the material of the protective layers 6 and 8 include metals such as zinc, silicon, nickel, chromium, gold, platinum, aluminum, magnesium, niobium, ruthenium, rhenium, rhodium, antimony, titanium, palladium, bismuth, and tin; Alloys containing two or more of these metals; oxides, fluorides, sulfides and nitrides of these metals.

  When providing a protective layer on both surfaces of the metal thin film layer 7, these protective layers may not be the same material, the same film-forming method, and the same film thickness. In addition, the position where the protective layer is provided is not limited between the high refractive index transparent thin film layer and the metal thin film layer as in the illustrated example, and may be provided between the transparent substrate and the antifouling layer. Further, when a material having excellent corrosion resistance is used for the metal thin film layer 7, a protective layer may not be provided.

  Note that the conductive multilayer film is not limited to the conductive multilayer film 100 having a three-layer structure (n = 1) excluding the protective layer as shown in the illustrated example, and the high refractive index transparent thin film layer, the metal thin film layer, Are alternately provided, and if the uppermost layer and the lowermost layer are high refractive index transparent thin film layers, three high refractive index transparent thin film layers and two metal thin film layers are alternately provided. It may have a layer structure (n = 2) or 7 layers or more (n is 3 or more).

(Low refractive index transparent thin film layer)
The low refractive index transparent thin film layer 6 is a layer in which the refractive index of light having a wavelength of 550 nm is less than 1.7 and the extinction coefficient of light having a wavelength of 550 nm is 0.5 or less.

  Examples of the material for the low refractive index transparent thin film layer 10 include silicon oxide, aluminum oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, cerium fluoride, hafnium fluoride, lanthanum fluoride, sodium fluoride, Examples thereof include aluminum fluoride, lead fluoride, strontium fluoride, ytterbium fluoride and the like. The low refractive index transparent thin film layer 10 can be formed by a method such as vapor deposition, sputtering, ion plating, ion beam assist, CVD, or wet coating.

  By providing the low-refractive-index transparent thin film layer 10, the range of the wavelength of light at which the reflectance is sufficiently low can be expanded over a wide range of 380 to 780 nm.

(Functional thin film layer)
The functional thin film layer 11 is a layer having both antifouling and anticorrosive functions. The functional thin film layer 11 is provided with both antifouling and anticorrosive functions by simultaneously forming an antifouling agent and an anticorrosive agent.

  By imparting antifouling properties, it is easy to wipe off water droplets, fingerprints and the like on the surface of the antireflection thin film laminate 1, and also prevent external damage such as scratches due to impact on the surface. Examples of the antifouling agent include fluorine-containing silicon compounds having a silicon atom bonded to a reactive functional group as having water repellency, oil repellency and low friction.

Examples of the reactive functional group include a hydrolyzable group and a halogen atom. Examples of hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, and ethoxyethoxy groups; alkenyloxy groups such as allyloxy and isopropenoxy groups An acyloxy group such as an acetoxy group, a propionyloxy group, a butylcarbonyloxy group or a benzoyloxy group; a ketoxime group such as a dimethylketoxime group, a methylethylketoxime group, a diethylketoxime group, a cyclopentanoxime group or a cyclohexanoxime group; Amino groups such as N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, N-cyclohexylamino group; N -Methylacetamide , N- ethyl acetamide group, an amido group such as N- methylbenzamide group; N, N- dimethylamino group, N, an amino group, such as N- diethylamino group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Of these, a methoxy group, an ethoxy group, and an isopropenoxy group are preferable.

  The water repellency of the antifouling agent is manifested by having a perfluoroalkylene group, a perfluoro (poly) oxyalkylene group or the like in the molecular chain of the antifouling agent. Since most of the structure of the molecular chain is occupied by these groups, water is surely repelled.

  When the fluorine-containing silicon compound having a silicon atom contains an ether bond in the molecular structure, the compound has flexibility at the ether bond portion, and as a result, the degree of freedom in the form of the molecular chain is increased. Since the fluorine-containing silicon compound having various forms covers the surface, the film becomes dense and the antifouling performance such as water repellency and wiping properties such as fingerprints is improved.

  The anti-corrosion property is imparted to suppress the deterioration of the metal thin film layer due to corrosion. JIS Z0103-2004 defines corrosion as "a phenomenon in which a metal is chemically or electrochemically eroded or deteriorated by the environmental material surrounding it." Furthermore, the corrosion resistance is “the property that the metal resists corrosion”, and the anticorrosion is “to prevent the metal from corroding”. Therefore, any material can be used as the anticorrosive used in the present invention as long as it has a performance to prevent corrosion of metals.

  Anticorrosive agents include amines and derivatives thereof, those having a pyrrole ring, those having a triazole ring, those having a pyrazole ring, those having a thiazole ring, those having an imidazole ring, those having an indazole ring, copper chelate compounds It is desirable to select at least one of thioureas, thioureas, mercapto group-containing products, naphthalene series, or a mixture thereof.

  Examples of amines and derivatives thereof include ethylamine, laurylamine, tri-n-butylamine, O-toluidine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, monoethanolamine, diethanolamine, triethanolamine, 2N- Dimethylethanolamine, 2-amino-2-methyl-1,3-propanediol, acetamide, acrylamide, benzamide, p-ethoxychrysidine, dicyclohexylammonium nitrite, dicyclohexylammonium salicylate, monoethanolamine benzoate, dicyclohexylammonium benzoate, diisopropyl Ammonium benzoate, diisopropylammonium nitrite Cyclohexylamine carbamate, nitronaphthalene nitrite, cyclohexylamine benzoate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylamine cyclohexane carboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate, or mixtures thereof.

  Examples of the compound having a pyrrole ring include N-butyl-2,5-dimethylpyrrole, N-phenyl-2,5dimethylpyrrole, N-phenyl-3-formyl-2,5-dimethylpyrrole, N-phenyl-3, 4-diformyl-2,5-dimethylpyrrole, etc., or a mixture thereof.

  Examples of the compound having a triazole ring include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 3- Methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, 4-methyl-1,2,3-triazole, Benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 4,5,6,7-tetrahydrotriazole, 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4- Triazole, carboxybenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5) -Tert-butylphenyl) benzotriazole, 2- (2'-hydroxy3'5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-4-octoxyphenyl) benzotriazole, or the like, or These mixtures are mentioned.

  Examples of the compound having a pyrazole ring include pyrazole, pyrazoline, pyrazolone, pyrazolidine, pyrazolidone, 3,5-dimethylpyrazole, 3-methyl-5-hydroxypyrazole, 4-aminopyrazole, and the like, or a mixture thereof.

  Examples of the compound having a thiazole ring include thiazole, thiazoline, thiazolone, thiazolidine, thiazolidone, isothiazole, benzothiazole, 2-N, N-diethylthiobenzothiazole, P-dimethylaminobenzallodanine, 2-mercaptobenzothiazole, etc. Or a mixture thereof.

  Examples of the compound having an imidazole ring include imidazole, histidine, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methyl. Imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 2-phenyl-4-methyl-5-hydromethylimidazole, 2-phenyl-4,5 dihydroxymethylimidazole, 4-formylimidazole, 2-methyl-4-formylimidazole, 2-phenyl-4-form Ruimidazole, 4-methyl-5-formylimidazole, 2-ethyl-4-methyl-5-formylimidazole, 2-phenyl-4-methyl-4-formylimidazole, 2-mercaptobenzimidazole, etc., or these Of the mixture.

  Examples of the substance having an indazole ring include 4-chloroindazole, 4-nitroindazole, 5-nitroindazole, 4-chloro-5-nitroindazole, and a mixture thereof.

  Examples of the copper chelate compounds include acetylacetone copper, ethylenediamine copper, phthalocyanine copper, ethylenediaminetetraacetate copper, hydroxyquinoline copper, and a mixture thereof.

  Examples of thioureas include thiourea, guanylthiourea, and the like, or a mixture thereof.

As a product having a mercapto group, if the above-mentioned materials are added, mercaptoacetic acid, thiophenol, 1,2-ethanediol, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto -1,2,4-triazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, glycol dimercaptoacetate, 3-mercaptopropyltrimethoxysilane, and the like, or a mixture thereof.

  Examples of the naphthalene type include thionalide.

  The antifouling and anticorrosion layer can be formed by a vacuum dry process such as a vapor deposition method (co-evaporation method), a CVD method, or a plasma polymerization method using the above-mentioned antifouling material or anticorrosive material as a raw material. Specifically, there are a method of depositing a mixed gas of a mixture of antifouling material and anticorrosive material on an object, a method of introducing a gas as a raw material, and depositing it on the object while reacting. .

  As described above, when the anti-stain and anti-corrosion function is provided in one layer, the anti-stain agent and the anti-corrosion agent can be simultaneously formed to have excellent adhesion and do not cause delamination. .

(Adhesive layer)
The adhesive layer 1 only needs to transmit light having a wavelength in the visible light region and have adhesiveness. From the viewpoint of optical performance, the adhesive layer 1 has a refractive index of 1.45 to 500 nm.
It is preferably 1.7 and the extinction coefficient is preferably almost zero. Examples of the material for the pressure-sensitive adhesive layer 1 include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives (PVA), ethylene-vinyl acetate adhesives (EVA), polyvinyl ether, and saturated amorphous. Examples include polyester and melamine resin.

  Hereinafter, the present invention will be described with specific examples.

[Example 1]
Wet coating of UV curable acrylic resin (trade name: PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) on a triacetyl cellulose film (hereinafter referred to as TAC film) having a thickness of 80 μm, which is a transparent substrate 2 To form a hard coat layer 3 having a physical thickness of 5 μm. On the hard coat layer 3, SiOx was deposited by a sputtering method to form a primer layer 4 having a physical film thickness of 3 nm. On the primer layer 4, a transparent conductive oxide material (ITO) containing 10% by weight of tin oxide in indium oxide was deposited by a sputtering method to form a high refractive index transparent thin film layer 5 having a physical film thickness of 27 nm. Nichrome was deposited on the high refractive index transparent thin film layer 5 by a sputtering method to form a protective layer 6 having a physical thickness of 0.8 nm. On the protective layer 6, an alloy containing 1.5 atomic% of gold and 0.5 atomic% of copper in silver was deposited by sputtering to form a metal thin film layer 7 having a physical thickness of 9 nm. Nichrome was deposited on the metal thin film layer 7 by sputtering to form a protective layer 8 having a physical thickness of 0.8 nm. On the protective layer 8, ITO containing 10% by weight of tin oxide in indium oxide was deposited by a sputtering method to form a high refractive index transparent thin film layer 9 having a physical film thickness of 20 nm. Next, a low refractive index transparent thin film layer 10 made of SiO ₂ was deposited on the high refractive index transparent thin film layer 9 by a sputtering method to form a physical film thickness of 40 nm.

  Furthermore, the functional thin film layer 11 as an antifouling anticorrosive layer was formed on the low refractive index transparent thin film layer 10 as follows.

An evaporation apparatus having a substrate rotation mechanism having a structure as shown in FIG. 2 was used, the antifouling agent was installed in the vacuum chamber, and the anticorrosive agent was introduced into the vacuum chamber through the flow rate control device 16. A fluorine-containing silicon compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KP801M) was used as the antifouling agent. A solution prepared by dissolving 2-heptadecylimidazole in a methanol solvent was used as the anticorrosive, and the mixture was kept heated at 30 ° C. When the inside of the vacuum chamber 12 is exhausted to 1.0E-3 Pa, the antifouling agent is heated, and at the same time, the gas valve 17 connected between the vacuum chamber 12 and the flow rate control device 16 is opened so that the antifouling agent and the anticorrosive agent are transparent. The functional thin film layer 11 was formed by simultaneously depositing on the substrate 20. The anticorrosive agent was adjusted to the flow rate using the flow rate control device 16 so that the antifouling effect and the anticorrosive effect were sufficiently exhibited, and the film interface of the antireflection thin film laminate was not deteriorated. During vapor deposition, the substrate holder 19 with a rotation mechanism was rotated at a constant rotation speed.

  The adhesive layer 1 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain an antireflection thin film laminate 300.

[Example 2]
Except for the functional thin film layer 11, an antireflection thin film laminate before forming the functional thin film layer 11 as an antifouling and anticorrosion layer was produced in the same manner as in Example 1.

  An antifouling agent and an anticorrosive were formed using a CVD apparatus having a substrate rotation mechanism having a structure as shown in FIG. A fluorine-containing silicon compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KP801M) was used as the antifouling agent. A solution prepared by dissolving 2-heptadecylimidazole in a methanol solvent was used as the anticorrosive. First, after evacuating the vacuum chamber 12 to 1.0E-4 Pa, the antifouling agent and the gas of the anticorrosive previously heated to 30 ° C. are introduced into the vacuum chamber 12 using the respective flow rate control devices 16. did. The pressure at the time of introduction was adjusted to 2.0 Pa. The partial pressures of the antifouling agent and the anticorrosive were adjusted so that the antifouling effect and the anticorrosive effect were sufficiently exhibited, and the film interface of the antireflection thin film laminate was not deteriorated. The RF power source 22 is used to apply high-frequency power with an excitation frequency of 13.56 MHz to the electrodes 24 for forming the antifouling agent and for forming the anticorrosive agent, so that glow discharge is simultaneously generated. An antifouling agent and an anticorrosive agent were formed on the film. During film formation, the substrate holder 19 with a rotation mechanism was rotated at a constant rotation number.

  The adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain an antireflection thin film laminate 300.

[Example 3]
A functional thin film in the same manner as in Example 1, except that the physical film thickness of each layer and the material of the high refractive index transparent thin film layer were changed to a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium. The following antireflection thin film laminate before forming the layer was produced.

TAC film (80 μm) / hard coat (5 μm) / SiOx (3 nm) / ICO (25 nm) / NiCr (0.8 nm) / silver alloy (9 nm) / NiCr (0.8 nm) / ICO (19 nm) / SiO ₂ ( 48 nm).

  Furthermore, the functional thin film layer 11 as an antifouling anticorrosive layer was formed on the low refractive index transparent thin film layer 10 as follows.

  A roll-to-roll CVD apparatus having a structure as shown in FIG. 4 was used. A solution obtained by dissolving benzimidazole in an ethanol solvent was used as the anticorrosive agent, and a fluorine-containing silicon compound (trade name: KP801M, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the antifouling agent. First, after evacuating the vacuum chamber 12 to 1.0E-4 Pa, a mixed gas of the antifouling agent and the anticorrosive previously heated to 30 ° C. was introduced into the vacuum chamber 12 using the flow rate control device 27. . The pressure at the time of introduction was adjusted to 2.0 Pa. The partial pressures of the antifouling agent and the anticorrosive were adjusted so that the antifouling effect and the anticorrosive effect were sufficiently exhibited, and the film interface of the antireflection thin film laminate was not deteriorated. A high frequency power having an excitation frequency of 13.56 MHz was applied to the electrode 24 using the RF power source 22 to generate glow discharge, and an antifouling agent and an anticorrosive agent were formed on the low refractive index transparent thin film layer 10.

  The adhesive layer 1 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain an antireflection thin film laminate 300.

[Comparative Example 1]
In forming the functional thin film layer 11 using the apparatus of FIG. 2, an antireflection thin film laminate 300 similar to that of Example 1 was produced except that only an antifouling agent was used and no anticorrosive agent was used.

[Comparative Example 2]
In forming the functional thin film layer 11 using the apparatus of FIG. 2, the anticorrosive agent was first formed, and the antifouling agent was subsequently formed after the formation of the anticorrosive agent was completed. A similar antireflection thin film laminate 300 was produced.

[Comparative Example 3]
In forming the functional thin film layer 11 using the apparatus of FIG. 3, an antireflection thin film laminate 300 similar to that of Example 2 was produced except that only an antifouling agent was used and no anticorrosive agent was used.

[Comparative Example 4]
In forming the functional thin film layer 11 using the apparatus of FIG. 3, the anticorrosive agent was formed first, and after the film formation of the anticorrosive agent was completed, the antifouling agent was subsequently formed. A similar antireflection thin film laminate 300 was produced.

[Comparative Example 5]
In forming the functional thin film layer 11 using the apparatus of FIG. 4, an antireflection thin film laminate 300 similar to that of Example 3 was produced except that only an antifouling agent was used and no anticorrosive agent was used.

[Comparative Example 6]
In forming the functional thin film layer 11 using the apparatus of FIG. 4, the anticorrosive agent was first formed, and the antifouling agent was subsequently formed after the formation of the anticorrosive agent. A similar antireflection thin film laminate 300 was produced.

  The following evaluation was performed about the antireflection thin film laminated body 300 obtained in Examples 1 and 2 and Comparative Examples 1 to 6.

(1) 5 wt% 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 1 side was on the quartz glass substrate side, and the 5 wt% NaCl aqueous solution was applied for 24 hours. Soaked. The antireflection thin film laminate 300 after immersion was observed over time, and the silver aggregation points of the metal thin film layer 7 were visually counted. During the immersion of the sample, the temperature of the NaCl aqueous solution was kept at 20 ° C. The results are shown in Table 1.

(2) Moisture and heat resistance test A 200 mm x 200 mm sample was bonded onto a 200 mm x 200 mm quartz glass substrate so that the adhesive layer 1 side was on the quartz glass substrate side, and placed in a constant temperature and humidity chamber at 65 ° C-95% RH. I put it in. A heat and humidity resistance test for up to 1000 hours was performed, the change with time of the antireflection thin film laminate 300 was observed, and the silver aggregation points of the metal thin film layer 7 were visually counted. The results are shown in Table 2.

(3) Contact angle measurement with pure water The contact angle with pure water on the functional thin film layer 11 side of the antireflection thin film laminate 300 was measured using a contact angle meter CA-X manufactured by Kyowa Interface Chemical Co., Ltd. The results are shown in Table 3.

(4) Cross-Cut Tape Peel Test 100 1 mm × 1 mm grid-like cuts are made on the 10 mm × 10 mm portion on the surface of the functional thin film layer 11 of the antireflection thin film laminate 300, and cellophane tape is attached to the grid portion. Next, the number of wrinkles remaining without peeling when the cellophane tape was peeled off was counted. The results are shown in Table 4. In Table 4, 100/100 indicates that no wrinkles were peeled off.

  Regarding the 5% by weight NaCl aqueous solution immersion test, Aggregation of silver in the metal thin film layer 7 occurred in Examples 1 to 3 and Comparative Examples 2, 4, and 6 in which the antifouling agent and the anticorrosive agent were used for the functional thin film layer 11. I did not. On the other hand, in Comparative Examples 1, 3, and 5 in which only the antifouling agent was used and no anticorrosive agent was used, aggregation of silver in the metal thin film layer 7 occurred and the silver was corroded.

  Regarding the wet heat resistance test, in Examples 1 to 3 and Comparative Examples 2, 4, and 6, aggregation of silver in the metal thin film layer 7 was not confirmed even after 1000 hours had passed. On the other hand, Aggregation of silver was confirmed in Comparative Examples 1, 3, and 5 after 240 hours. Furthermore, the number of silver aggregates continued to increase after 240 hours.

  The reason why Examples 1 to 3 and Comparative Examples 2, 4, and 6 showed good results with respect to the NaCl aqueous solution immersion test and the heat and humidity resistance test was due to aggregation of silver by imparting hydrophobicity with an antifouling agent. The action of preventing corrosion of silver by adding corrosion resistance with an anticorrosive agent worked effectively, as the NaCl aqueous solution and moisture were repelled by the functional thin film layer 11 and reached the metal thin film layer 7. This is presumed to be due to this.

  Regarding the contact angle measurement with pure water, both the example and the comparative example exceeded 100 °, and good results were shown. Examples 1-3 using both antifouling agents and anticorrosives, and Comparative Examples 2, 4, 6 were used with Comparative Examples 1, 3, 5 and 5 using only antifouling agents and not using anticorrosive agents. In comparison, the contact angle tended to be small. The reason is presumed that the anticorrosive agent interferes with the development of hydrophobic performance by the antifouling agent.

  Regarding the cross-cut tape peel test, Examples 1 to 3 and Comparative Examples 1, 3, and 5 showed better results than Comparative Examples 2, 4, and 6. In Comparative Examples 2, 4, and 6, the antifouling agent was formed after forming the anticorrosive agent. However, since the antifouling agent and anticorrosive film forming steps were separated, the components of the anticorrosive agent were the interfaces of each layer of the antireflection thin film laminate. It is presumed that the adhesiveness at the interface deteriorated due to excessive penetration. On the other hand, in Examples 1 to 3, by forming the antifouling agent and the anticorrosive agent at the same time, the anticorrosive agent penetrates to the silver alloy thin film of the metal thin film layer, but reaches each interface from the silver alloy thin film layer to the base material. In addition, it is presumed that the function of the antifouling agent was not hindered. In Comparative Examples 1, 3, and 5, the function of the functional thin film layer 11 was only antifouling, and thus the adhesion was good.

  From the above results, it is possible to provide an antireflection thin film laminate that can sufficiently reduce the reflectance over a wide range in the visible light region and is excellent in water repellency, fingerprint wiping property, corrosion resistance, weather resistance, and adhesion. it can.

An optical display device using the antireflection thin film laminate of the present invention on the front surface of an optical display device such as a CRT, a liquid crystal display device, or a PDP can be provided. The antireflection thin film laminate of the present invention is also useful as an optical functional filter provided in optical articles such as window glass, glasses and goggles.

It is sectional drawing which shows an example of a structure of the antireflection thin film laminated body of this invention. It is the schematic of the vapor deposition apparatus used for preparation of Example 1 and Comparative Examples 1 and 2 of the antireflection thin film laminate of the present invention. It is the schematic of the CVD apparatus used for preparation of Example 2 and Comparative Examples 3 and 4 of the antireflection thin film laminated body of this invention. It is the schematic of the CVD apparatus of the roll-to-roll system used for preparation of Example 3 and Comparative Examples 5 and 6 of the antireflection thin film laminate of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Adhesive layer 2 ... Transparent base material 3 ... Hard-coat layer 4 ... Primer layer 5 ... High refractive index transparent thin film layer 6 ... Protective layer 7 ... Metal thin film layer 8 ... Protective layer 9 ... High refractive index transparent thin film layer 10 ... Low refractive index transparent thin film layer 11 ... Functional thin film layer 12 ... Vacuum tank 13 ... Material installation boat 14 ... Antifouling agent 15a: anticorrosive inlet 15b ... antifoulant inlet 16 ... flow control device 17 ... gas valve 18 ... gas shower head 19 ... with rotation mechanism Substrate holder 20 ... transparent substrate 21 ... exhaust port 22 ... RF power supply 23 ... matching device 24 ... electrode 25 ... roller 26 ... transparent film substrate 27 ... prevention Flow rate control device 100 of mixed gas of dirt and anticorrosive agent ... conductive multilayer film 200 ... conductive antireflection laminate 3 0 ... anti-reflective thin film laminate

Claims (5)

  An anti-fouling film is formed on at least a base material by forming a conductive multilayer film by alternately laminating a high refractive index transparent thin film layer and a metal thin film layer, and the outermost layer has an anti-fouling function and an anti-corrosion function. An antireflection thin film laminate comprising an anticorrosion layer.   2. The antireflection thin film laminate according to claim 1, wherein the metal thin film layer is silver or an alloy containing silver.   3. The antireflection thin film laminate according to claim 1, wherein a low refractive index transparent thin film layer is provided between the conductive multilayer film and the antifouling and anticorrosion layer.   An antireflection thin film laminate according to any one of claims 1 to 3 is used as an optical functional filter.   An optical display device comprising the antireflection thin film laminate according to claim 1 provided on a front surface of the optical display device.

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