JP2009092913A - Optical thin film laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical thin film laminate having decoration properties, metal glossiness, both of light transmittance and light absorbance, and conductivity. <P>SOLUTION: The optical thin film laminate includes a thin film laminate on one surface of a substrate, wherein the thin film laminate includes a lamination structure in which one or more layers of a high refractive index thin film layer and a low refractive index thin film layer are laminated, and a conductive thin film layer is formed on a surface of the substrate opposite to the surface on which the thin film laminate is formed. The surface resistivity of the surface on which the conductive thin film layer is formed is less than 1.00×10<SP>-4</SP>Ω/Square. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention includes an automobile member, a vehicle member, a household appliance member, a mobile phone member, a portable game machine member, a personal computer member, a PDA member, an audio product member, a car navigation member, an office supplies member, a sports article member, a miscellaneous goods member, and glasses.・ Optical thin film laminates used for sunglasses members, camera members, optical article members, measuring instrument members, etc., have decorativeness and metallic luster, have both light transmission and light absorption, and are conductive. The present invention relates to an optical thin film laminate having properties.

  Currently, coating with a paint is generally performed as a means for coloring various members. However, painting is cumbersome because it is necessary to select the paint appropriately depending on the base material, it is difficult to paint with a uniform film thickness and skillful technology is required, and painting on curved surfaces has a different finish from flat There are problems such as that the coating film is easily formed, and that the coating film has defects due to the coating unevenness of the paint and the inclusion of foreign matter.

  In addition, painting requires a large number of processes, requires a special booth for painting, occupies a large area for the installation of the painting booth and paint drying room, and paints more than necessary There are problems such as low energy efficiency due to consumption of the paint, poor recyclability because the painted film is difficult to collect, deterioration of the working environment / safety and health environment due to paint solvents, and contamination. .

  As a method of performing coloring with metallic luster, there are a method by painting and a method of depositing a metal material on a colored film. The former can be performed by mixing metal flakes such as aluminum or mica flakes in the paint. However, the method of mixing metal or mica flakes with the paint has a limit on the mixing ratio of the flakes in the paint, and in order to obtain a certain level of metallic luster and light reflectivity, it is applied to a thick film of about 3 μm. There is a problem that it is necessary, the metallic luster feeling is insufficient, and the appearance is uncomfortable, and further, the drying means requires time and the productivity is inferior.

  On the other hand, in the latter, a thin metallic film is densely formed, so that a sufficient metallic luster is obtained (see Patent Document 1). Aluminum is used as an example of the metal material. Vapor deposition of aluminum is relatively easy, the vapor deposition rate is fast and inexpensive, and it is generally used because platinum color can be easily produced. However, in order to obtain a film having a metallic luster of a desired color by this method, it is necessary to prepare a colored film for each color, which makes process management troublesome. Furthermore, when there is color unevenness in the colored film, there is a problem that the color unevenness is enlarged due to reflection of the metal thin film layer formed on the colored film and becomes noticeable.

Japanese Patent Laid-Open No. 10-139063

  In the present invention, it is an object to provide an optical thin film laminate having decorativeness and metallic luster, having both light transmission and light absorption properties, and further having conductivity.

  In order to solve the above-mentioned problems, the invention according to claim 1 is an optical thin film laminate including a thin film laminate on one surface of a substrate, the thin film laminate being a high refractive index thin film layer, a low refractive index. An optical structure having a laminated structure in which at least one thin film layer is laminated, and a conductive thin film layer is formed on a surface opposite to the surface on which the thin film laminate of the substrate is formed. A thin film laminate was obtained.

The invention according to claim 2 is characterized in that the surface resistivity of the surface on which the conductive thin film layer is formed is less than 1.00 × 10 ⁻⁴ Ω / □. It was set as the optical thin film laminated body of description.

According to a third aspect of the present invention, the conductive thin film layer is formed of indium trioxide (In ₂ O ₃ ), tin dioxide (SnO ₂ ), zinc monoxide (ZnO), cadmium monoxide (CdO), cadmium. _3. The optical thin film laminate according to claim 1 or 2, which does not contain any compound of tin trioxide (CdSnO ₃ ) and cadmium tin tetraoxide (Cd ₂ SnO ₄ ).

  The invention according to claim 4 is characterized in that the high refractive index thin film layer and the low refractive index thin film layer in the thin film laminate are formed by a vacuum film forming method. It was set as the optical thin film laminated body of description.

  An invention according to claim 5 is a molded article comprising the optical thin film laminate according to any one of claims 1 to 4.

  By setting it as the optical thin film laminated body of the said structure, it was able to be set as the optical thin film laminated body which has decorating property and metallic luster, is compatible with light transmittance and light absorptivity, and also has electroconductivity.

The optical thin film laminate of the present invention will be described.
The optical thin film laminate of the present invention comprises a thin film laminate in which at least one high refractive index thin film layer and low refractive index thin film layer are laminated on one surface of a substrate, and the substrate thin film laminate is formed. A conductive thin film layer is provided on the surface opposite to the surface on which the surface is located.

  FIG. 1 shows a schematic cross-sectional view of an example of the optical thin film laminate of the present invention. The optical thin film laminate 1 includes a base material 2, a thin film laminate 3 provided on one surface of the base material 2, and a conductive thin film layer 4 provided on the other surface of the base material 2. Composed.

  In the optical thin film laminate of FIG. 1, the high refractive index thin film layer 5, the low refractive index thin film layer 6, and the high refractive index thin film layer 7 are sequentially formed in order from the side where the thin film laminate 3 is close to the substrate 2. It has a laminated structure. In the present invention, the optical thin film laminate may be provided with at least one high refractive index thin film layer and low refractive index thin film layer, and is not limited to FIG.

  In the optical thin film laminate of the present invention, coloring is provided by optical interference of the high refractive index thin film layer and / or the low refractive index thin film layer of the thin film laminate. Further, the optical thin film laminate of the present invention has a metallic luster due to the material forming the high refractive index thin film layer and / or the low refractive index thin film layer of the thin film laminate.

  Moreover, in this invention, an electroconductive thin film layer is provided on the base material on the opposite side to the side in which the thin film laminated body 3 was provided. By providing the conductive thin film layer, the surface of the conductive thin film layer of the optical thin film laminate can be provided with conductivity. The conductive thin film layer can function as an electrode layer, an antistatic layer, or a radio wave absorption layer. By providing the conductive thin film layer on the surface opposite to the surface on which the thin film laminate is formed, the structure is exposed without being sandwiched between other layers, so that the surface resistivity can be further reduced. The control and reproducibility of the surface resistivity during manufacture is also facilitated.

The surface resistivity of the surface on which the conductive thin film layer of the optical thin film laminate of the present invention is formed is preferably 1.00 × 10 ⁻⁴ Ω / □ or less. By making the surface resistivity of the surface on which the conductive thin film layer is formed 1.00 × 10 ⁻⁴ Ω / □ or less, a low resistance conductive function is required, touch panel, inorganic / organic The present invention can be applied to electronic device members such as EL anodes, liquid crystal panel electrodes, and radio wave absorbers.

  In the optical thin film laminate of the present invention, the high refractive index thin film layer and the low refractive index thin film layer forming the thin film laminate, and the conductive thin film layer forming material and the film thickness of each layer are changed, Both light permeability and light absorption can be achieved.

In the optical thin film laminate of the present invention, the conductive thin film layer is made of indium trioxide (In ₂ O ₃ ), tin dioxide (SnO ₂ ), zinc monoxide (ZnO), cadmium monoxide (CdO), or cadmium tin. It is preferable that neither a trioxide (CdSnO ₃ ) nor a cadmium tin tetraoxide (Cd ₂ SnO ₄ ) is contained.

The reason is as follows. That is, indium trioxide (In ₂ O ₃ ) is a problem because the price of indium, which is a rare metal, is rising worldwide due to a shortage of supply worldwide. The market price of indium has increased sharply since 2004, and it was 80-95 US dollars / kg in 2002, but exceeded 200 US dollars / kg in 2004, and 1000 US dollars in 2005. It has reached the point of breaking through the dollar / kg. Although the price has been on a downward trend since 2006, it is still at a high level and is expected to remain high for the time being. Further, regarding tin dioxide (SnO ₂ ), there is a problem that the resistance is not reduced unless the film is thick to some extent, and patterning by wet etching is difficult. With respect to zinc monoxide (ZnO), the resistivity in the atmosphere is unstable over time, and there is a problem that the resistivity is likely to change due to an increase in temperature. Regarding cadmium monoxide (CdO), cadmium tin trioxide (CdSnO ₃ ), and cadmium tin tetroxide (Cd ₂ SnO ₄ ), there is a problem that they are toxic cadmium compounds.

The conductive thin film layer is formed of indium trioxide (In ₂ O ₃ ), tin dioxide (SnO ₂ ), zinc monoxide (ZnO), cadmium monoxide (CdO), cadmium tin trioxide (CdSnO ₃ ), cadmium tin. By not including any of these tetraoxides (Cd ₂ SnO ₄ ), it is possible to provide an optical thin film laminate having conductivity that avoids the above problems.

  In the thin film laminate of the optical thin film laminate of the present invention, the high refractive index thin film layer and the low refractive index thin film layer are preferably formed by a vacuum film forming method. In the optical thin film laminate of the present invention, coloring is provided by optical interference of the high refractive index thin film layer and / or the low refractive index thin film layer of the thin film laminate. Therefore, the high refractive index thin film layer and the low refractive index thin film layer are required to have a uniform film thickness in the plane.

  In the vacuum film formation method, it is possible to form a thin film while maintaining the shape of the substrate surface, and since the size of the thin film forming material deposited by the vacuum film formation method is angstrom order atoms and molecules, for example, Even when a film is formed on a substrate having fine irregularities on the order of micrometer, the original irregularity shape is maintained without filling the concave portions by depositing on the surface with a uniform thickness. Therefore, by forming the high refractive index thin film layer and the low refractive index thin film layer by a vacuum film forming method, the obtained optical thin film laminate can obtain surface decoration without color unevenness.

  Specifically, the optical thin film laminate of the present invention includes a liquid crystal display member, an automobile member, a vehicle member, a household appliance member, a mobile phone member, a personal computer member, an audio product member, a car navigation member, an office supplies member, and a sports article. It is applied to members, sundries members, glasses / sunglasses members, camera members, optical article members, measuring instrument members, etc., and can be used as molded products.

  In particular, the optical thin film laminate of the present invention can be used as a molded product for members of thin portable terminals such as mobile phones, PDAs, smartphones and portable game machines. Thin portable terminals often have a groove or a step between a liquid crystal display unit and a casing unit surrounding the liquid crystal display unit. Due to the presence of the grooves or steps, the display portion is framed like a frame, which is not preferable because the shape design becomes ugly.

  By laminating the optical thin film laminate of the present invention to the casing and the surface of the liquid crystal display, an image can be visually recognized through the color film when the display is turned on, while the casing surrounding the display has the same color tone as the color film when the display is turned off. If it comprises, the color tone of a display part and a housing | casing part will become the same, and it can produce the unification feeling of a color design.

  The color of the liquid crystal element when the liquid crystal display is turned off is dark gray, but the color of the liquid crystal element itself cannot be colored, and the liquid crystal display and the surrounding enclosure lose a sense of unity in color design. It is not preferable. By using the optical thin film laminate of the present invention, the color tone of the liquid crystal display and the casing is integrated when the light is turned off, and can be hidden so as not to be aware of the presence of the display unit. On the other hand, when it is lit, the display unit becomes bright and the screen can be lifted.

  Moreover, the optical thin film laminated body of this invention can be used as a molded article of a touch panel member. The optical thin film laminate of the present invention has a decorative property and a metallic luster, has both light transmission and light absorption properties, and has electrical conductivity. It is possible to expand the selection of functions on the display and produce a variety of entertainment.

  The method for producing the optical thin film laminate of the present invention will be described below.

(Base material)
The substrate in the present invention is not particularly limited as long as it has transparency, and examples thereof include plastic, glass, or a composite material of these.
Examples of plastic materials include polyester, polyamide, polyimide, polypropylene, polyethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetal, polyvinyl alcohol, polyurethane, polyethyl methacrylate, polycarbonate, polystyrene, polyphenylene sulfite, and polyethersulfide. Hong, polyethersulfone, polyolefin, polyarylate, polysulfone, polyparaxylene, polyetheretherketone, polyethylene terephthalate, polyethylene naphthalate, polyphenyl oxide, triacetylcellulose, cellulose acetate, silicon resin, fluororesin, acrylic resin, phenol Resin, epoxy resin, ABS resin, ABS alloy, etc. Not intended to be constant.
Examples of the glass material include, but are not limited to, soda lime glass, borosilicate glass, quartz glass, Pyrex (registered trademark) glass, alkali-free glass, lead glass, and the like.
Further, a material obtained by combining these plastic materials and glass materials may be used.

  The shape of the substrate is not particularly limited as long as the surface is smooth, and examples thereof include a plate shape and a roll shape.

  The surface of the substrate may be subjected to a surface treatment according to the purpose before forming the thin film laminate. As the surface treatment method, for example, corona treatment method, vapor deposition treatment method, electron beam treatment method, high frequency discharge plasma treatment method, sputtering treatment method, ion beam treatment method, atmospheric pressure glow discharge plasma treatment method, alkali treatment method, acid treatment Law.

  The thickness of the substrate is appropriately selected according to the intended use, and is usually 5 μm or more and 10 mm or less. The plastic material may contain a known additive, for example, an ultraviolet absorber, a plasticizer, a lubricant, a colorant, an antioxidant, a flame retardant and the like.

(Thin film laminate)
The thin film laminate in the present invention is formed by laminating at least one thin film layer of a high refractive index thin film layer and a low refractive index thin film layer.

  FIG. 1 shows a thin film laminate 3 in which three layers of a high refractive index thin film layer 5, a low refractive index thin film layer 6, and a high refractive index thin film layer 7 are sequentially laminated from the side close to the substrate 2. However, this is only an example, and if at least one of a high refractive index thin film layer and a low refractive index thin film layer is laminated on one surface of the substrate 2, even if it is a single layer, There may be two or more layers, and the number of layers is not limited.

(High refractive index thin film layer)
The high refractive index thin film layer in the present invention is a layer having a refractive index of 1.75 or more at a light wavelength of 550 nm.
In the case of a high refractive index thin film layer excellent in light transmittance, the extinction coefficient in the visible light region should be less than 0.01, while on the other hand, a high refractive index thin film layer having light absorption The extinction coefficient in the visible light region may be 0.01 or more.

As a material for the high refractive index thin film layer, for example,
Lead telluride (PbTe) (refractive index 1.75, extinction coefficient 2.90),
Yttrium trioxide (Y ₂ O ₃ ) (refractive index 1.79, extinction coefficient 0),
Thorium dioxide (ThO ₂ ) (refractive index 1.80, extinction coefficient 0),
Nickel (Ni) (refractive index 1.87, extinction coefficient 3.32),
Bismuth trioxide (Bi ₂ O ₃ ) (refractive index 1.91, extinction coefficient 0),
Gadolinium trioxide (Gd ₂ O ₃ ) (refractive index 1.93, extinction coefficient 0),
Lanthanum trioxide (La ₂ O ₃ ) (refractive index 1.95, extinction coefficient 0),
₁₁ praseodymium oxide (Pr ₆ O ₁₁ ) (refractive index 1.95, extinction coefficient 0),
Rhodium (Rh) (refractive index 1.97, extinction coefficient 5.02),
Hafnium dioxide (HfO ₂ ) (refractive index 1.99, extinction coefficient 0),
Neodymium trioxide (Nd ₂ O ₃ ) (refractive index 2.00, extinction coefficient 0),
Silicon monoxide (SiO) (refractive index 2.00, extinction coefficient 0.03),
Antimony trioxide (Sb ₂ O ₃ ) (refractive index 2.04, extinction coefficient 0),
Silicon mononitride (SiN) (refractive index 2.06, extinction coefficient 0),
Zirconium dioxide (ZrO ₂ ) (refractive index 2.06, extinction coefficient 0),
Platinum (Pt) (refractive index 2.13, extinction coefficient 3.71),
Tantalum pentoxide (Ta ₂ O ₅ ) (refractive index 2.14, extinction coefficient 0),
Cerium dioxide (CeO ₂ ) (refractive index 2.20, extinction coefficient 0),
Chromium trioxide (Cr ₂ O ₃ ) (refractive index 2.24, extinction coefficient 0.07),
Niobium pentoxide (Nb ₂ O ₅ ) (refractive index 2.27, extinction coefficient 0),
Titanium dioxide (TiO ₂ ) (refractive index 2.32, extinction coefficient 0),
Zinc monosulfide (ZnS) (refractive index 2.35, extinction coefficient 0),
Tantalum (Ta) (refractive index 2.48, extinction coefficient 1.83),
Titanium (Ti) (refractive index 2.54, extinction coefficient 3.34),
Silicon monocarbide (SiC) (refractive index 2.66, extinction coefficient 0),
Zinc selenide (ZnSe) (refractive index 2.69, extinction coefficient 0.02),
Iron (Fe) (refractive index 2.89, extinction coefficient 3.35),
Antimony trisulfide (Sb ₂ S ₃ ) (refractive index 3.00, extinction coefficient 0),
Chromium (Cr) (refractive index 3.12, extinction coefficient 4.42),
Tungsten (W) (refractive index 3.24, extinction coefficient 2.49),
Molybdenum (Mo) (refractive index 3.79, extinction coefficient 3.51),
Germanium (Ge) (refractive index 3.95, extinction coefficient 1.98),
Silicon (Si) (refractive index 4.08, extinction coefficient 0.04),
Or the mixture of these materials is mentioned. The refractive index and the extinction coefficient are values at a light wavelength of 550 nm.

  In the case of a high refractive index thin film layer having light absorptivity, a material having an extinction coefficient in the visible light region of 0.01 or more may be used. It is necessary to. If the film thickness is too thick, it becomes a layer without light transmission, and conversely, if the film thickness is too thin, it becomes a layer with insufficient light absorption. A preferable film thickness that achieves both light transmission and light absorption is 0.3 nm or more and 100 nm or less.

  Here, the high-refractive-index thin film layers 5 and 7 shown in FIG. 1 are not necessarily the same material, and are appropriately selected according to the purpose.

(Low refractive index thin film layer)
The low refractive index thin film layer in the present invention is a layer having a refractive index of less than 1.75 at a light wavelength of 550 nm. In the case of a low refractive index thin film layer excellent in light transmittance, the extinction coefficient in the visible light region should be less than 0.01, while on the other hand, a low refractive index thin film layer having light absorptivity. The extinction coefficient in the visible light region may be 0.01 or more.

As a material for the low refractive index thin film layer, for example,
Silver (Ag) (refractive index 0.055, extinction coefficient 3.32),
Gold (Au) (refractive index 0.331, extinction coefficient 2.32),
Copper (Cu) (refractive index 0.670, extinction coefficient 2.86),
Aluminum (Al) (refractive index 0.834, extinction coefficient 6.03),
Titanium mononitride (TiN) (refractive index 1.25, extinction coefficient 2.10),
Cryolite (Na ₃ AlF ₆ ) (refractive index 1.35, extinction coefficient 0),
Magnesium difluoride (MgF ₂ ) (refractive index 1.38, extinction coefficient 0),
Lithium monofluoride (LiF) (refractive index 1.39, extinction coefficient 0),
Calcium difluoride (CaF ₂ ) (refractive index 1.43, extinction coefficient 0),
Silicon dioxide (SiO ₂ ) (refractive index 1.46, extinction coefficient 0),
Strontium difluoride (SrF ₂ ) (refractive index 1.46, extinction coefficient 0),
Barium difluoride (BaF ₂ ) (refractive index 1.48, extinction coefficient 0),
Ytterbium trifluoride (YbF ₃ ) (refractive index 1.52, extinction coefficient 0),
Tungsten and titanium nitride (TiN _x W _y ) (refractive index 1.54, extinction coefficient 1.52),
Thorium tetrafluoride (ThF ₄ ) (refractive index 1.56, extinction coefficient 0),
Hafnium tetrafluoride (HfF ₄ ) (refractive index 1.57, extinction coefficient 0),
Lanthanum trifluoride (LaF ₃ ) (refractive index 1.58, extinction coefficient 0),
Neodymium trifluoride (NdF ₃ ) (refractive index 1.60, extinction coefficient 0),
Cerium trifluoride (CeF ₃ ) (refractive index 1.64, extinction coefficient 0),
Palladium (Pd) (refractive index 1.64, extinction coefficient 3.85),
Aluminum trioxide (Al ₂ O ₃ ) (refractive index 1.67, extinction coefficient 0),
Magnesium monoxide (MgO) (refractive index 1.74, extinction coefficient 0),
Or the mixture of these materials is mentioned. The refractive index and the extinction coefficient are values at a light wavelength of 550 nm.

  In the case of a low refractive index thin film layer having light absorption, a material having an extinction coefficient in the visible light region of 0.01 or more may be used. It is necessary to. If the film thickness is too thick, it becomes a layer without light transmission, and conversely, if the film thickness is too thin, it becomes a layer with insufficient light absorption. A preferable film thickness that achieves both light transmission and light absorption is 0.3 nm or more and 100 nm or less.

  The high refractive index thin film layer and the low refractive index thin film layer of the thin film laminate in the present invention can be formed by a vacuum film forming method such as an evaporation method, a sputtering method, a plasma CVD method, an ion plating method, or an ion beam assist method. preferable.

  In the vacuum film formation method, it is possible to form a thin film while maintaining the shape of the substrate surface. Since the size of the thin film forming material deposited by the vacuum film formation method is angstrom order atoms / molecules, for example, even if a film is formed on a substrate having fine irregularities of micrometer order, the surface has a uniform thickness Since the original concave / convex shape is maintained without being deposited by filling up the concave portion, it is possible to obtain a surface decorating property without color unevenness.

  When corrosive or degradable metal materials are used for the high refractive index thin film layer and the low refractive index thin film layer, a protective layer is provided adjacent to the high refractive index thin film layer and the low refractive index thin film layer to prevent corrosion and deterioration. It may be formed. 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 may be used as the anticorrosive used in the protective layer as long as it has a performance to prevent corrosion of metals.

  Examples of anticorrosives 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 Examples thereof include chelate compounds, thioureas, products having a mercapto group, at least one naphthalene group, or a mixture thereof.

  In addition to wet processes such as spraying, microgravure, screen coating, and dip coating, the method for applying the anticorrosive is to form a film by a vacuum dry process such as vapor deposition, CVD, or plasma polymerization. Can do. The effective range of the anticorrosive component includes not only the case where the component exists on the surface of the portion where the anticorrosive film is formed, but also the case where the component permeates into the interior and also exists at a location other than the surface.

  The thin film laminate in the present invention is formed by laminating at least one high refractive index thin film layer and low refractive index thin film layer. According to this, the optical thin film laminated body which has coloring, metallic luster, light transmittance, and light absorptivity can be obtained.

  In the optical thin film laminate of the present invention, a measurement light source is installed on the side on which the thin film laminate is formed, and L * of CIELAB (conforming to JIS Z 8729) in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light. Is preferably 15 or more and 75 or less, a * is 10 or more and 80 or less, and b * is preferably −80 or more and 80 or less. According to this, it can be set as the optical thin film laminated body which has metallic luster and red coloring.

  In the optical thin film laminate of the present invention, a measurement light source is installed on the side on which the thin film laminate is formed, and L * of CIELAB (conforming to JIS Z 8729) in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light. Is preferably from 15 to 60, a * is from -20 to 70, and b * is preferably from -80 to -10. According to this, it can be set as the optical thin film laminated body which has metallic luster and blue coloring.

  In the optical thin film laminate of the present invention, a measurement light source is installed on the side on which the thin film laminate is formed, and L * of CIELAB (conforming to JIS Z 8729) in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light. Is preferably from 15 to 80, a * is from -35 to 35, and b * is preferably from -20 to 20. According to this, it can be set as the optical thin film laminated body which has a metallic luster and silver or black coloring.

  In the optical thin film laminate of the present invention, a measurement light source is installed on the side on which the thin film laminate is formed, and L * of CIELAB (conforming to JIS Z 8729) in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light. Is preferably 15 to 80, a * is preferably −30 to 30 and b * is preferably 5 to 70. According to this, it can be set as the optical thin film laminated body which has metallic luster and yellow coloring.

  In the optical thin film laminate of the present invention, a measurement light source is installed on the side on which the thin film laminate is formed, and L * of CIELAB (conforming to JIS Z 8729) in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light. Is preferably from 15 to 80, a * is from −75 to −5, and b * is preferably from −45 to 45. According to this, it can be set as the optical thin film laminated body which has metallic luster and green coloring.

  The lightness L *, hue / saturation a *, and b * of CIELAB in the optical thin film laminate of the present invention conform to JIS Z 8729 using a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light. The surface of the conductive thin film layer opposite to the side on which the thin film laminate 4 is formed is painted black, and the measurement light source is installed on the side of the substrate on which the thin film laminate is formed.

(Conductive thin film layer)
The conductive thin film layer according to the present invention is obtained by forming a single thin film layer selected from a high refractive index thin film layer and a low refractive index thin film layer on the surface of the substrate opposite to the side on which the thin film laminate is formed. is there.

The conductive thin film layer is composed of indium trioxide (In ₂ O ₃ ), tin dioxide (SnO ₂ ), zinc monoxide (ZnO), cadmium monoxide (CdO), cadmium tin trioxide (CdSnO ₃ ), cadmium tin. It is preferable that none of these tetraoxides (Cd ₂ SnO ₄ ) is contained.

As a material of the conductive thin film layer, for example,
Silver (Ag) (refractive index 0.055, extinction coefficient 3.32),
Gold (Au) (refractive index 0.331, extinction coefficient 2.32),
Copper (Cu) (refractive index 0.670, extinction coefficient 2.86),
Aluminum (Al) (refractive index 0.834, extinction coefficient 6.03),
Titanium mononitride (TiN) (refractive index 1.25, extinction coefficient 2.10),
Tungsten and titanium nitride (TiN _x W _y ) (refractive index 1.54, extinction coefficient 1.52),
Palladium (Pd) (refractive index 1.64, extinction coefficient 3.85),
Nickel (Ni) (refractive index 1.87, extinction coefficient 3.32),
Rhodium (Rh) (refractive index 1.97, extinction coefficient 5.02),
Platinum (Pt) (refractive index 2.13, extinction coefficient 3.71),
Tantalum (Ta) (refractive index 2.48, extinction coefficient 1.83),
Titanium (Ti) (refractive index 2.54, extinction coefficient 3.34),
Chromium (Cr) (refractive index 3.12, extinction coefficient 4.42),
Tungsten (W) (refractive index 3.24, extinction coefficient 2.49),
Molybdenum (Mo) (refractive index 3.79, extinction coefficient 3.51),
Germanium (Ge) (refractive index 3.95, extinction coefficient 1.98),
Or the mixture of these materials is mentioned. The refractive index and the extinction coefficient are values at a light wavelength of 550 nm.

  When a conductive thin film layer having a light absorption property is used, a material having an extinction coefficient in the visible light region of 0.01 or more may be used. There is a need to. If the film thickness is too thick, it becomes a layer without light transmission, and conversely, if the film thickness is too thin, it becomes a layer with insufficient light absorption. A preferable film thickness that achieves both light transmission and light absorption is 0.3 nm or more and 50 nm or less.

  The conductive thin film layer can be formed by a dry process or a wet process. In the case of a dry process, the film can be formed by, for example, a vapor deposition method, a sputtering method, a plasma CVD method, an ion plating method, an ion beam assist method, or the like.

In the case of a wet process, the film can be formed by, for example, a spray method, a micro gravure method, a screen coating method, a dip coating method, or the like, using a solution in which a conductive material is dispersed in a transparent resin. Of course, a film in which a conductive material is dispersed may be scattered by a vacuum deposition method.

When a corrosive or degradable metal material is used for the conductive thin film layer, a protective layer may be formed adjacent to the conductive thin film layer in order to prevent corrosion or deterioration. As the anticorrosive used in the protective layer, any material may be used as long as it has a performance to prevent corrosion of metals, and examples thereof include the materials described above or mixtures.

  In addition to wet processes such as spraying, microgravure, screen coating, and dip coating, the method for applying the anticorrosive is to form a film by a vacuum dry process such as vapor deposition, CVD, or plasma polymerization. Can do. In the case where the conductive thin film layer is formed by a wet process, an anticorrosive agent may be added to the solution for forming the conductive thin film layer. The effective range of the anticorrosive component includes not only the case where the component exists on the surface of the portion where the anticorrosive film is formed, but also the case where the component permeates into the interior and also exists at a location other than the surface.

  The optical constants of the refractive index and the extinction coefficient can be obtained by measuring the change in the polarization state of the light reflected from the surface of the thin film layer sample using a spectroscopic ellipsometry method. Regarding the extinction coefficient, light absorption increases when it is 0.01 or more, while light absorption decreases when it is less than 0.01. Therefore, a light-absorbing thin film having light absorptivity and transparent with excellent light transmittance. It is possible to properly use the thin film depending on the extinction coefficient.

The optical thin film laminate of the present invention preferably has an absorptance of 2% or more and 70% or less for light having a wavelength of 550 nm in 5 ° incidence and regular reflection light defined by the following formula.
(Expression) Absorbance (%) = 100% −Transmittance (%) − Reflectance (%)
By setting the absorptivity of the optical thin film laminate to 2% or more and 70% or less, it is possible to provide performance that achieves both light absorption and light transmission. When the absorption rate of the optical thin film laminate exceeds 70%, the light transmittance becomes insufficient. For example, when it is applied to a liquid crystal display member, the visibility of the image on the display screen is deteriorated, which becomes a problem. . On the other hand, when the optical thin film laminate has an absorptance of less than 2%, the light absorptivity becomes insufficient. For example, the optical thin film laminate of the present invention is disposed around the liquid crystal display section of a thin portable terminal. When pasting together so as to cover the entire surface of the enclosing casing, the color tone of the display section and the casing is different, which makes it impossible to produce a unified color design.

  Specifically, the optical thin film laminate of the present invention includes an automobile member, a vehicle member, a household appliance member, a mobile phone member, a portable game machine member, a personal computer member, a PDA member, an audio product member, a car navigation member, and office supplies. It is applied to members, sporting goods members, miscellaneous goods members, glasses / sunglasses members, camera members, optical goods members, measuring equipment members, and the like.

  By laminating the optical thin film laminate of the present invention on the liquid crystal display part of a thin portable terminal such as a mobile phone, PDA, smart phone, portable game machine, etc. When the display is lit, the image on the display screen can be seen through the optical thin film laminate. Furthermore, by covering not only the liquid crystal display part but also the casing around the display part, including the display part, with the optical thin film laminate of the present invention, the appearance of the display part and the casing is integrated when the display is turned off. It becomes possible to. In other words, since the image on the display unit emerges and can be viewed only when the display is lit, the design of the display unit and the surrounding housing unit can have a sense of unity.

In addition, if the optical thin film laminate of the present invention is bonded so as to cover the entire surface of the liquid crystal display part of the thin portable terminal and the casing part surrounding it, the liquid crystal display part and the casing part surrounding the liquid crystal display part There will be no gaps or steps between them, and it will be smooth and the shape design will have a clean and unified feeling. By integrating the shape of the display unit and the casing unit surrounding the display unit, the structural volume can be reduced, so that the thin portable terminal can be further reduced in thickness.

  Furthermore, since the optical thin film laminate of the present invention has conductivity, it can be used as a touch panel member. In particular, in the case of not using indium trioxide, tin dioxide, zinc monoxide, cadmium monoxide, cadmium tin trioxide, cadmium tin tetroxide as the conductive material, it is inexpensive and stable in production and supply. It is possible to provide conductive members that are easy to pattern by wet etching, have stable resistivity in the atmosphere, are non-toxic, have decorative properties, metallic luster, light transmission, and light absorption. It is.

  Examples of the present invention will be specifically described below.

[Example 1]
As shown in FIG. 2, a high refractive index thin film layer 5, a low refractive index thin film layer 6, and a high refractive index thin film layer are formed on one surface of a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as a base material 2. 7. A thin film laminate 3 composed of a low refractive index thin film layer 8 and a high refractive index thin film layer 9 was formed as follows.

First, titanium dioxide (TiO ₂ ) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 5 having a physical film thickness of 30 nm.

Silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 6 having a physical film thickness of 15 nm.

On the low refractive index thin film layer 6, titanium dioxide (TiO ₂ ) was deposited by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 55 nm.

Silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 7 by a vacuum vapor deposition method using an electron beam, thereby forming a low refractive index thin film layer 8 having a physical film thickness of 65 nm.

Titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 8 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 9 having a physical film thickness of 10 nm, thereby completing the thin film laminate 3. I let you.

  Next, on the surface opposite to the surface on which the thin film laminate 3 of the substrate 2 was formed, the conductive thin film layer 4 composed of one thin film layer was formed as follows.

  Nickel (Ni) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a conductive thin film layer 4 having a physical film thickness of 7 nm, thereby completing the optical thin film stack 1.

  About the obtained optical thin film laminated body 1, the electroconductive thin film layer 4 surface on the opposite side to the side which formed the thin film laminated body 3 was painted black, and the measurement light source was installed in the side in which the thin film laminated body 3 of the base material 2 was formed. At that time, L * was 35.9, a * was 0.6, and b * was 0.2 for CIELAB (conforming to JIS Z 8729) in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light.

  For the obtained optical thin film laminate 1, when a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 ° visual field, luminous average transmittance Y in transmitted light Was 46.6%.

The absorptance of the optical thin film laminate 1 in light having an incident angle of 5 ° and a wavelength of 550 nm defined by the following formula was 48.1%.

(Expression) Absorbance (%) = 100% −Transmittance (%) − Reflectance (%)

  When the obtained optical thin film laminate 1 was bonded to a liquid crystal display, it was confirmed that a silver metallic luster was produced when the display was turned off, and that the liquid crystal element was excellent in concealment. On the other hand, when the display was turned on, an image projected on the display through the optical thin film laminate 1 emerged, and the image was visible.

  The above-mentioned spectroscopic measurement was performed using U-4000 type self-recording spectrophotometer (made by Hitachi, Ltd.). The measurement procedure is as follows. First, in the case of reflected lightness and reflected hue / saturation, the entire surface of the conductive thin film layer 4 opposite to the side on which the thin film stack 3 of the optical thin film stack 1 is formed is filled with black paint so as not to cause unevenness. It was. The base material 2 painted with black paint was held over natural light of sunlight or artificial light such as a fluorescent lamp, and it was confirmed whether light leaked through the base material 2. The surface side of the base material 2 that was not painted black was placed toward the measurement light source of the U-4000 type self-recording spectrophotometer. At this time, it was installed so that the measurement light was incident on the surface of the base material 2 at an angle of 5 ° with respect to the vertical line on the surface of the base material 2 on which the thin film laminate was formed. A spectrophotometer is installed in the direction of the light that is regularly reflected on the surface of the base material 2 and at a position that becomes a 2 ° field of view, and the spectral reflectance in the visible light region (380 to 780 nm) is measured, and specified in JIS Z 8701 The tristimulus values X, Y, Z to be obtained were determined. Tristimulus values X, Y, and Z were calculated at 5 nm intervals. Subsequently, the lightness L *, hue / saturation a *, and b * of the L * a * b * color system defined in JIS Z 8729 were determined using tristimulus values.

  Next, in the case of the luminous average transmittance Y, the side on which the thin film laminate 3 of the optical thin film laminate 1 was formed was placed toward the measurement light source of the U-4000 type self-recording spectrophotometer. At this time, it was installed so that the measurement light was incident on the surface of the base material 2 at an angle of 5 ° with respect to the vertical line on the surface of the base material 2 on which the thin film laminate was formed. A photometer is installed in the direction of the light transmitted through the substrate 2 and at a position where the 2 ° field of view is set, and the spectral transmittance in the visible light region (380 to 780 nm) is measured, and three as defined in JIS Z 8701 Stimulus values X, Y and Z were determined. Tristimulus values X, Y, and Z were calculated at 5 nm intervals.

  Furthermore, regarding the absorptance, each value at the wavelength of 550 nm out of the spectral reflectance in the visible light region (380 to 780 nm) and spectral transmittance measured in advance was subtracted from the percentage. Regarding the measurement of the spectral reflectance when obtaining the absorptance, the surface of the conductive thin film layer 4 on the side opposite to the side on which the thin film stack 3 of the optical thin film stack 1 is formed is not painted black. The side on which the thin film laminate 3 was formed was installed facing the measurement light source of the U-4000 type self-recording spectrophotometer.

  The lightness L *, hue / saturation a *, and b * of CIELAB in the present invention are measured in accordance with JIS Z 8729 under the conditions of a D65 light source, 5 ° incidence, and 2 ° visual field.

Further, the surface resistivity of the obtained optical thin film laminate 1 on the conductive thin film layer 4 side was measured and found to be 6.93 × 10 ⁺¹ Ω / □.

  The above-described surface resistivity was measured using Loresta-HP (manufactured by Mitsubishi Chemical Corporation). A four-probe probe (probe pin interval 5 mm) was used as the probe. The measurement procedure was based on JIS K 7194-1994.

[Example 2]
As shown in FIG. 3, a high refractive index thin film layer 5, a high refractive index thin film layer 7, and a low refractive index thin film layer are formed on one surface of a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. 6. The thin film laminate 3 composed of the high refractive index thin film layer 9 was formed as follows.

  Nickel (Ni) was deposited on the base material 2 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 5 having a physical film thickness of 1.5 nm.

Titanium dioxide (TiO ₂ ) was deposited on the high refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 40 nm.

On the high refractive index thin film layer 7, silicon dioxide (SiO ₂ ) was deposited by a vacuum evaporation method using an electron beam to form a low refractive index thin film layer 6 having a physical film thickness of 50 nm.

Titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 6 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 9 having a physical film thickness of 15 nm, thereby completing the thin film laminate 3. I let you.

  Next, on the surface opposite to the surface on which the thin film laminate 3 of the substrate 2 was formed, the conductive thin film layer 4 composed of one thin film layer was formed as follows.

  Chromium (Cr) was deposited on the substrate 2 by a vacuum evaporation method using an electron beam to form a conductive thin film layer 4 having a physical film thickness of 10 nm, thereby completing the optical thin film stack 1.

  When the surface of the conductive thin film layer 4 opposite to the side on which the thin film laminate 3 is formed is painted black, and a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 CIELAB (according to JIS Z 8729) in visual field and specular reflection light had L * of 54.5, a * of -0.5, and b * of -0.9.

  For the obtained optical thin film laminate 1, when a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 ° visual field, luminous average transmittance Y in transmitted light Was 15.5%.

  The absorptance of the optical thin film laminate 1 with respect to light having an incident angle of 5 ° and a wavelength of 550 nm was 65.6%.

  When the obtained optical thin film laminate 1 was bonded to a liquid crystal display, a black metallic luster was produced when the display was turned off, and it was confirmed that the liquid crystal element was excellent in concealment. On the other hand, when the display was turned on, an image projected on the display through the optical thin film laminate 1 emerged, and the image was visible.

When the surface resistivity of the obtained optical thin film laminate 1 on the conductive thin film layer 4 side was measured, it was 1.17 × 10 ⁺³ Ω / □.

[Example 3]
As shown in FIG. 4, a high refractive index thin film layer 5, a low refractive index thin film layer 6, and a high refractive index thin film layer are formed on one surface of a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. 7. A thin film laminate 3 composed of a low refractive index thin film layer 8 and a high refractive index thin film layer 9 was formed as follows.

First, titanium dioxide (TiO ₂ ) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 5 having a physical film thickness of 70 nm.

  Titanium mononitride (TiN) was deposited on the high refractive index thin film layer 5 by a vacuum evaporation method using an electron beam to form a low refractive index thin film layer 6 having a physical film thickness of 15 nm.

On the low refractive index thin film layer 6, titanium dioxide (TiO ₂ ) was deposited by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 55 nm.

  Titanium mononitride (TiN) was deposited on the high refractive index thin film layer 7 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 8 having a physical film thickness of 15 nm.

Titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 8 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 9 having a physical film thickness of 35 nm, thereby completing the thin film laminate 3. I let you.

  Next, on the surface opposite to the surface on which the thin film laminate 3 of the substrate 2 was formed, the conductive thin film layer 4 composed of one thin film layer was formed as follows.

  On the base material 2, an alloy containing 2.5 atomic percent of gold (Au) in silver (Ag) is deposited by a vacuum vapor deposition method using an electron beam to form a conductive thin film layer 4 having a physical thickness of 9 nm. Formed.

  Further, a protective layer 10 is formed on the conductive thin film layer 4 by applying a solution prepared by dissolving the anticorrosive agent 2-heptadecylimidazole in a methanol solvent by a microgravure method, thereby completing the optical thin film laminate 1. It was.

About the obtained optical thin film laminated body 1, the electroconductive thin film layer 4 surface on the opposite side to the side which formed the thin film laminated body 3 was painted black, and the measurement light source was installed in the side in which the thin film laminated body 3 of the base material 2 was formed. L65 of CIELAB (conforming to JIS Z 8729) for D65 light source, 5 ° incidence, 2 ° field of view, and specularly reflected light was 38.5, a * was −29.5, and b * was 0.4. .

  For the obtained optical thin film laminate 1, when a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 ° visual field, luminous average transmittance Y in transmitted light Was 25.0%.

  The absorptance of the optical thin film laminate 1 in light having an incident angle of 5 ° and a wavelength of 550 nm was 62.2%.

  When the obtained optical thin film laminate 1 was bonded to a liquid crystal display, it was confirmed that a green metallic luster was produced when the display was turned off, and that the liquid crystal element was excellent in concealment. On the other hand, when the display was turned on, an image projected on the display through the optical thin film laminate 1 emerged, and the image was visible.

The surface resistivity of the obtained optical thin film laminate 1 on the conductive thin film layer 4 side was measured and found to be 1.15 × 10 ⁺¹ Ω / □.

[Example 4]
As shown in FIG. 3, a high refractive index thin film layer 5, a high refractive index thin film layer 7, and a low refractive index thin film layer are formed on one surface of a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. 6. The thin film laminate 3 composed of the high refractive index thin film layer 9 was formed as follows.

  On the base material 2, nickel (Ni) was deposited by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 5 having a physical film thickness of 2.0 nm.

Titanium dioxide (TiO ₂ ) was deposited on the high refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 65 nm.

Silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 7 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 6 having a physical film thickness of 65 nm.

Titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 6 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 9 having a physical thickness of 30 nm, thereby completing the thin film stack 3. I let you.

  Next, on the surface opposite to the surface on which the thin film laminate 3 of the substrate 2 was formed, the conductive thin film layer 4 composed of one thin film layer was formed as follows.

  Nickel (Ni) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a conductive thin film layer 4 having a physical film thickness of 5 nm, thereby completing the optical thin film stack 1.

  When the surface of the conductive thin film layer 4 opposite to the side on which the thin film laminate 3 is formed is painted black, and a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 CIELAB (according to JIS Z 8729) in visual field and specular reflection light had L * of 47.5, a * of 0.7, and b * of −40.0.

  For the obtained optical thin film laminate 1, when a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 ° visual field, luminous average transmittance Y in transmitted light Was 41.2%.

  The absorptance of the optical thin film laminate 1 with respect to light having an incident angle of 5 ° and a wavelength of 550 nm was 44.0%.

  When the obtained optical thin film laminate 1 was bonded to a liquid crystal display, a blue metallic luster was produced when the display was extinguished, and it was confirmed that the liquid crystal element was excellent in concealment. On the other hand, when the display was turned on, an image projected on the display through the optical thin film laminate 1 emerged, and the image was visible.

It was 2.67 * 10 < ⁺² > ohm / square when the surface resistivity by the side of the conductive thin film layer 4 of the obtained optical thin film laminated body 1 was measured.

[Example 5]
As shown in FIG. 2, a high refractive index thin film layer 5, a low refractive index thin film layer 6, and a high refractive index thin film layer are formed on one surface of a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as a base material 2. 7. A thin film laminate 3 composed of a low refractive index thin film layer 8 and a high refractive index thin film layer 9 was formed as follows.

Titanium dioxide (TiO ₂ ) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 5 having a physical film thickness of 85 nm.

Silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 6 having a physical film thickness of 90 nm.

On the low refractive index thin film layer 6, titanium dioxide (TiO ₂ ) was deposited by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 25 nm.

Silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 7 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 8 having a physical thickness of 40 nm.

Titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 8 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 9 having a physical film thickness of 20 nm, thereby completing the thin film laminate 3. I let you.

  Next, on the surface opposite to the surface on which the thin film laminate 3 of the substrate 2 was formed, the conductive thin film layer 4 composed of one thin film layer was formed as follows.

  Tungsten (W) was deposited on the base material 2 by a vacuum vapor deposition method using an electron beam to form a conductive thin film layer 4 having a physical film thickness of 7 nm, thereby completing the optical thin film stack 1.

About the obtained optical thin film laminated body 1, the electroconductive thin film layer 4 surface on the opposite side to the side which formed the thin film laminated body 3 was painted black, and the measurement light source was installed in the side in which the thin film laminated body 3 of the base material 2 was formed. When
L65 of CIELAB (conforming to JIS Z 8729) in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light was 32.6, a * was −0.7, and b * was 43.0.

  For the obtained optical thin film laminate 1, when a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 ° visual field, luminous average transmittance Y in transmitted light Was 30.2%.

  The absorptance of the optical thin film laminate 1 with respect to light having an incident angle of 5 ° and a wavelength of 550 nm was 39.0%.

  When the obtained optical thin film laminate 1 was bonded to a liquid crystal display, it was confirmed that a yellow metallic luster was produced when the display was turned off, and that the liquid crystal element was excellent in concealment. On the other hand, when the display was turned on, an image projected on the display through the optical thin film laminate 1 emerged, and the image was visible.

The surface resistivity of the obtained optical thin film laminate 1 on the conductive thin film layer 4 side was measured and found to be 3.50 × 10 ⁺¹ Ω / □.

[Example 6]
As shown in FIG. 2, a high refractive index thin film layer 5, a low refractive index thin film layer 6, and a high refractive index thin film layer are formed on one surface of a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as a base material 2. 7. A thin film laminate 3 composed of a low refractive index thin film layer 8 and a high refractive index thin film layer 9 was formed as follows.

Titanium dioxide (TiO ₂ ) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 5 having a physical film thickness of 100 nm.

Silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 6 having a physical film thickness of 115 nm.

On the low refractive index thin film layer 6, titanium dioxide (TiO ₂ ) was deposited by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 60 nm.

Silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 7 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 8 having a physical film thickness of 150 nm.

Titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 8 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 9 having a physical film thickness of 85 nm, thereby completing the thin film laminate 3. I let you.

  Next, on the surface opposite to the surface on which the thin film laminate 3 of the substrate 2 was formed, the conductive thin film layer 4 composed of one thin film layer was formed as follows.

  On the base material 2, nickel (Ni) was deposited by a vacuum vapor deposition method using an electron beam to form a conductive thin film layer 4 having a physical film thickness of 7.5 nm, thereby completing the optical thin film stack 1.

  About the obtained optical thin film laminated body 1, the electroconductive thin film layer 4 surface on the opposite side to the side which formed the thin film laminated body 3 was painted black, and the measurement light source was installed in the side in which the thin film laminated body 3 of the base material 2 was formed. When D65 light source, 5 ° incidence, 2 ° field of view, CIELAB (conforms to JIS Z 8729) in specular reflection light, L * was 60.5, a * was 48.6, and b * was -0.1. .

  For the obtained optical thin film laminate 1, when a measurement light source is installed on the side of the substrate 2 on which the thin film laminate 3 is formed, a D65 light source, 5 ° incidence, 2 ° visual field, luminous average transmittance Y in transmitted light Was 34.8%.

  The absorptance of the optical thin film laminate 1 with respect to light having an incident angle of 5 ° and a wavelength of 550 nm was 45.4%.

  When the obtained optical thin film laminate 1 was bonded to a liquid crystal display, a red metallic luster was produced when the display was turned off, and it was confirmed that the liquid crystal element was excellent in concealment. On the other hand, when the display was turned on, an image projected on the display through the optical thin film laminate 1 emerged, and the image was visible.

When the surface resistivity of the obtained optical thin film laminate 1 on the conductive thin film layer 4 side was measured, it was 4.84 × 10 ⁺¹ Ω / □.

It is a cross-sectional schematic diagram of an example of the optical thin film laminated body of this invention. It is a cross-sectional schematic diagram which shows the optical thin film laminated body of Examples 1, 5, and 6. FIG. It is a cross-sectional schematic diagram which shows the optical thin film laminated body of Example 2, 4. 6 is a schematic cross-sectional view showing an optical thin film laminate of Example 3. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical thin film laminated body 2 Base material 3 Thin film laminated body 4 Conductive thin film layer 5 High refractive index thin film layer 6 Low refractive index thin film layer 7 High refractive index thin film layer 8 Low refractive index thin film layer 9 High refractive index thin film layer 10 Protective layer

Claims (5)

An optical thin film laminate comprising a thin film laminate on one surface of a substrate,
The thin film laminate has a laminated structure in which at least one high refractive index thin film layer and low refractive index thin film layer are laminated, and
An optical thin film laminate, wherein a conductive thin film layer is formed on a surface opposite to a surface on which the thin film laminate of the substrate is formed. 2. The optical thin film laminate according to claim 1, wherein the surface resistivity of the surface on which the conductive thin film layer is formed is less than 1.00 × 10 ⁻⁴ Ω / □. The conductive thin film layer is composed of indium trioxide (In ₂ O ₃ ), tin dioxide (SnO ₂ ), zinc monoxide (ZnO), cadmium monoxide (CdO), cadmium tin trioxide (CdSnO ₃ ), cadmium. The optical thin film laminate according to claim 1 or 2, wherein any compound of tin tetraoxide (Cd ₂ SnO ₄ ) is not contained.   The optical thin film laminate according to any one of claims 1 to 3, wherein the high refractive index thin film layer and the low refractive index thin film layer in the thin film laminate are formed by a vacuum film forming method.   A molded article comprising the optical thin film laminate according to any one of claims 1 to 4.

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