Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
  • G02B1/115—Multilayers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
  • G02B1/115—Multilayers
  • G02B1/116—Multilayers including electrically conducting layers

Definitions

• the present invention relates to an antireflection film using a silicon dioxide thin film or a metal oxide thin film.
• Thin films of silicon dioxide exhibiting a low refractive index and thin films of metal oxides such as titanium dioxide and aluminum oxide exhibiting a high refractive index are used for applications such as multilayer reflective films, antireflective films, and photonic crystals in various optical products. ing.
• transparent metal oxide thin films have been manufactured using a vapor deposition method typified by a vapor deposition method or a sputtering method.
• the method for producing a transparent metal oxide thin film by the vapor deposition method requires complicated adjustment of the production equipment, requires fine adjustment for the production operation, and requires relatively long operation time. However, this is not an industrially advantageous production method.
• the sol-gel method is a method for producing a metal oxide comprising hydrolyzing a metal alkoxide dissolved in a solvent, followed by condensation polymerization, and using a simple production facility and a relatively short production process. Since a high quality metal oxide thin film can be obtained, it is widely used as a method for manufacturing an optical thin film formed particularly on the surface of an optical product.
• Anti-reflection film using ultrafine particles written by Atsumi Wakabayashi, 0 Plus E, Vol. 24, No. 11, p. 1 2 3 1-1 2 3 5 (January 2000) , Tin oxide containing antimony It describes an antireflection film formed using nanometer-sized fine particles such as tin-containing indium oxide, so-called ultrafine particles, as a thin film.
• 91-L 293 introduces a technique for manufacturing photonic crystals by using a method in which a mold is immersed in titanium dioxide gel formed from a high concentration of alkoxide, followed by drying and firing.
• the sol-gel method developed as an industrially advantageous thin film manufacturing method to replace the vapor deposition method, metal oxides that can be used as high-quality optical thin films with relatively simple manufacturing equipment and manufacturing processes An object thin film can be obtained.
• the method according to the sol-gel method known so far has not been able to obtain an optical thin film having a sufficiently low refractive index even with a silicon dioxide thin film.
• an optical thin film having a sufficiently high refractive index has not been obtained even with a titanium dioxide thin film or an aluminum oxide thin film.
• the silicon dioxide thin film can be manufactured as an optical thin film having a desired low refractive index by using the air-gel method. Has not yet been sufficiently studied as a production method that can be used industrially.
• optical thin films produced by these methods have reached a level that is sufficiently satisfactory in terms of industrial production. Absent. Further, optical thin films produced by these methods have a problem that sufficient physical strength and surface hardness cannot be obtained. That is, an electo-luminescence (EL) element, particularly an organic electoluminescence. Anti-reflection coatings formed on the surface of optical products such as sensing elements, optical lenses, and displays such as CRTs often need to have high scratch resistance because they often come into contact with human hands and external equipment.
• EL electo-luminescence
• the optical thin film obtained by the sol-gel method or the air-gel method which is a method of adjusting the refractive index by allowing a large number of air bubbles to exist inside, has the problem that it is difficult to have sufficiently high scratch resistance due to the presence of the air bubbles. is there. For the same reason, there is also a problem that the mechanical strength such as the bending resistance of the thin film and the heat resistance are low.
• the present invention provides an anti-reflection film using an amorphous silicon dioxide thin film exhibiting a low refractive index and high scratch resistance, or an amorphous metal oxide thin film exhibiting a high refractive index and high scratch resistance. That is its purpose.
• the present invention provides a gold oxide thin film that is transparent and has a refractive index of light having a wavelength of 500 nm in the range of 1.45 to 1.80 on a substrate;
• An amorphous silicon dioxide thin film containing, having a refractive index of light at a wavelength of 500 nm in the range of 1.01 to 1.43, and having a diameter of 5 nm, which accounts for 80% by volume or more of all the fine voids.
• the following is an antireflection film formed by laminating the following amorphous silicon dioxide thin films.
• the porosity of the amorphous silicon dioxide thin film is 50% or more.
• the diameter of the fine voids occupying 80% by volume or more of the entire fine voids of the amorphous silicon dioxide thin film is 2 nm or less.
• the diameter of the fine voids occupying 90% by volume or more of the entire fine voids of the amorphous silicon dioxide thin film is 2 nm or less.
• An amorphous silicon dioxide thin film is a fired product of a thin film formed by a sol-gel method.
• the amorphous silicon dioxide thin film is obtained by converting a silicon alkoxide into an alcoholic solvent in a manner selected from the group consisting of a hydroxyaldehyde derivative, a hydroxycarboxylic acid derivative, an aryl alcohol derivative and a hydroxynitrile derivative.
• This is a thin film formed by a method including a step of forming a sol obtained by hydrolysis and condensation polymerization in the presence of one compound and water into a thin film, and a step of heating and firing the sol thin film.
• the method further comprises a salt of a weak acid and a weak base, a salt of a hydrazine derivative, a salt of a hydroxylamine derivative, and a salt of an amidine derivative in the hydrolysis and condensation polymerization of the silicon alkoxide.
• a salt catalyst selected from the group.
• the metal oxide thin film is an amorphous metal oxide thin film containing a large number of fine voids therein, and the diameter of the fine voids occupying 80% by volume or more of the entire fine voids is 5 nm or less.
• the porosity of the amorphous metal oxide thin film is 50% or more.
• An amorphous metal oxide thin film that is transparent and contains fine voids inside, has a refractive index of 1.8 or more for light with a wavelength of 500 nm, and accounts for 80% by volume or more of the entire fine voids.
• An anti-reflective coating made of an amorphous metal oxide thin film in which the diameter of the microvoids is 5 nm or less.
• the volume of the whole fine void and the ratio (volume%) of the fine void having a specific diameter mean a value measured by the following method.
• the pore volume per mass per specific diameter is determined by a nitrogen adsorption device. Multiplying this by the density determined by the density measuring device gives the pore volume per volume per specific diameter. When this is expressed as a percentage, it is the ratio of the fine voids per specific diameter.
• FIG. 1 is a cross-sectional view illustrating a configuration example of the antireflection film of the present invention. [Detailed description of the invention]
• an amorphous metal oxide thin film to be a constituent material of the antireflection film of the present invention and a method for producing the same will be described.
• Examples of the amorphous metal oxide thin film that can be used for the antireflection film of the present invention include titanium oxide, zirconium oxide, aluminum oxide, tantalum oxide, hafnium oxide, and niobium oxide. And a metal oxide represented by a rare earth metal oxide or a mixture thereof.
• the metal oxide is not limited to the above-mentioned metal oxide as long as a stable metal alkoxide can be obtained and the metal oxide itself is a metal oxide having a high refractive index.
• an amorphous metal oxide thin film which can be used for the antireflection film of the present invention will be described in detail by taking a typical example of an amorphous titanium oxide (amorphous titanium dioxide). I will explain it.
• the amorphous titanium dioxide thin film that can be used for the antireflection film of the present invention has a void (bubble) contained therein at a nanometer level as compared with a titanium dioxide thin film obtained by a conventionally known sol-gel method.
• the main feature is that it is a remarkably small void. That is, in the amorphous titanium dioxide thin film that can be used for the antireflection film of the present invention, a large number of voids exist as very fine voids in the thin film. In addition to exhibiting high transparency, it will exhibit the desired high refractive index and high mechanical strength (especially high scratch resistance and high bending resistance), and heat resistance (heat deformation resistance).
• the amorphous titanium dioxide thin film that can be used for the antireflection film of the present invention is a titanium alkoxide in an alcohol solvent, a salt of a weak acid and a weak base, a salt of a hydrazine derivative, a salt of a hydroxylamine derivative, and a salt of an acetamidine derivative.
• the method for producing a titanium dioxide thin film is already known as a method for producing a titanium dioxide thin film by a sol-gel method, and is put into practical use. Have been.
• a condensation polymerization reaction between the hydrolysates occurs, A condensation polymer is formed. Then, it is formed into a thin film in the state of a low
• an amorphous titanium dioxide thin film which can be used as the antireflection film of the present invention, the following method is used.
• a salt of a weak acid and a weak base a salt of a hydrazine derivative, a hydroxyl
• At least one compound (salt catalyst, condensation polymerization reaction accelerator) selected from the group consisting of a salt of an amamine derivative and a salt of an acetomidine derivative is present.
• salts of a weak acid and a weak base include ammonium carboxylate (eg, ammonium acetate, ammonium formate), ammonium carbonate, and ammonium hydrogencarbonate.
• the hydrazine derivative salt, hydroxylamine derivative salt and acetamidine derivative salt are described in Japanese Patent Application Laid-Open No. 2000-26849. Compounds can be used.
• the hydrolysis of titanium alkoxide and the condensation polymerization reaction in the presence of a condensation polymerization reaction accelerator allow the production of the hydrolyzate of titanium alkoxide. It is considered that the condensation polymerization is promoted, and a matrix structure in which the polymer chains extend in three dimensions is more likely to be preferentially generated than in the case where the polymer chains extend in one dimension and a long chain polymer is generated. You. It is presumed that, due to the formation of the matrix structure in which the polymer chains preferentially extend in the three-dimensional direction, the voids formed in the condensed polymer to be formed become fine voids on the molecular order.
• the sol obtained by hydrolysis and condensation polymerization of titanium alkoxide is then formed into a thin film.
• the sol thin film is formed by, for example, applying the sol uniformly on the substrate by a method such as spin coating, or dip coating the substrate by immersing the substrate in the sol and then lifting the bow. It can be performed using a known method. It is desirable that the substrate used be subjected to a surface treatment such as a plasma treatment in the presence of oxygen gas.
• the sol thin film is then heated and fired to form an amorphous titanium dioxide thin film.
• the heating and baking are usually performed at a temperature in the range of 100 to 110 ° C.
• the porosity of the resulting amorphous titanium dioxide thin film is adjusted by changing the conditions such as the mixing temperature and the stirring time during the formation of the sol, or by selecting the heating and firing temperature. And also the refractive index can be adjusted at the same time.
• amorphous silicon dioxide thin film which is a constituent material of the antireflection film of the present invention and a method for producing the same will be described.
• the amorphous silicon dioxide thin film that can be used for the antireflection film of the present invention has a larger number of voids (bubbles) inside the nanometer than the silicon dioxide thin film obtained by the conventionally known sol-gel method. Its main feature is that it has a size of the torr level and a remarkably small void. In this amorphous silicon dioxide thin film, many voids are present as very fine voids in the thin film. Therefore, this amorphous silicon dioxide thin film not only shows high transparency but also has a desired low level. It shows refractive index and high mechanical strength (especially high scratch resistance and ⁇ ⁇ bending resistance) and heat resistance (heat deformation resistance).
• the amorphous silicon dioxide thin film that can be used for the antireflection film of the present invention is a silicon alkoxide in an alcohol solvent, which is selected from the group consisting of a hydroxyaldehyde derivative, a hydroxyacetic acid derivative, an aryl alcohol derivative, and a hydroxynitrile derivative. Hydrolysis in the presence of at least one selected compound and water The sol (low-viscosity liquid mixture) obtained by the condensation polymerization is formed into a thin film, and the sol thin film is heated and calcined. it can.
• At the time of hydrolysis and condensation polymerization of silicon alkoxide at least one salt catalyst selected from the group consisting of a salt of a weak acid and a weak base, a salt of a hydrazine derivative, a salt of an amidine derivative, and a salt of a hydroxylamine derivative is present.
• a salt catalyst selected from the group consisting of a salt of a weak acid and a weak base, a salt of a hydrazine derivative, a salt of an amidine derivative, and a salt of a hydroxylamine derivative is present.
• a salt catalyst selected from the group consisting of a salt of a weak acid and a weak base, a salt of a hydrazine derivative, a salt of an amidine derivative, and a salt of a hydroxylamine derivative is present.
• a method for producing a silicon dioxide thin film comprising the steps of hydrolyzing silicon alkoxide in an alcohol solvent and subjecting it to condensation polymerization to obtain a sol, forming the sol into a thin film, and then heating and firing the sol thin film. It is already known as a method for producing a silicon dioxide thin film by the sol-gel method, and has been put to practical use.
• a tetraalkoxysilicone such as butoxysilicon or its derivative in a lower aliphatic alcohol solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol or isobutanol
• the hydrolysis and condensation polymerization of a silicon alkoxide require the addition of a hydroxyaldehyde derivative (or hydroxyketone derivative) and a hydroxycarboxylic acid derivative.
• At least one compound (hydrolysis accelerator) selected from the group consisting of a compound, an aryl alcohol derivative, and a hydroxynitrile derivative.
• hydroxy aldehyde derivatives (or hydroxy ketone derivatives) include hydroxyacetone, acetoin, 3-hydroxy-3-methyl-2-butanone, and fructose.
• hydroxy carboxylic acid derivatives include glycol.
• Acid lactic acid, hydroxyisobutyric acid, thioglycolic acid, glycolic acid ester, lactate ester, 2-hydroxyisobutyrate ester, thioglycolate ester, malic acid, tartaric acid, cunic acid, malate ester, tartaric acid ester, and que Acid esters
• aryl alcohol derivatives include 1-buten-3-ol, 2-methyl-3-buten-1-ol, 1-penten-3-ol, and 1-hexen-1-ol Crotyl alcohol, 3-methyl-2-buten-l-ol, and tinamyl alcohol.
• hydroxynitrile derivatives include acetonecyanohydrin.
• At the time of hydrolysis and condensation polymerization of silicon alkoxide at least one salt selected from the group consisting of a salt of a weak acid and a weak base, a salt of a hydrazine derivative, a salt of an amidine derivative, and a salt of a hydroxylamine derivative.
• a salt of a weak acid and a weak base Preferably, two compounds (salt catalysts) are present.
• the salt of a weak acid and a weak base include ammonium carbonate (eg, ammonium acetate, ammonium formate), ammonium carbonate, and ammonium hydrogen carbonate.
• At least one salt catalyst selected from the group consisting of a salt of a hydrazine derivative, a salt of an amidine derivative, and a salt of a hydroxylamine derivative, and the function thereof are described in JP-A-2000-202.
• Japanese Patent Application Publication No. 6-649 describes a titanium oxide gel having photochromic properties and a salt catalyst used in the production of glass products.
• the hydrolysis of silicon alkoxide is promoted by the presence of a hydrolysis accelerator in the hydrolysis and condensation polymerization of silicon alkoxide, and a plurality of alkoxide groups of each silicon alkoxide are formed.
• the sol obtained by hydrolysis and condensation polymerization of silicon alkoxide is then formed into a thin film.
• a thin film of sol for example, The metal oxide thin film formed on the substrate) is coated uniformly by a method such as spin coating, or by using a known method such as a dip coating method in which the substrate is immersed in a sol and then pulled up. Can do it.
• the substrate to be used is preferably subjected to a surface treatment such as a plasma treatment in the presence of oxygen gas.
• the sol film is then heated and fired to form an amorphous silicon dioxide film.
• the heating and baking are usually performed at a temperature in the range of 100 to 110 ° C.
• the porosity of the resulting amorphous silicon dioxide thin film is adjusted by changing the conditions such as the temperature of stirring and mixing during the formation of the sol and the stirring time, or by selecting the temperature of heating and firing. And the refractive index can be adjusted at the same time.
• the antireflection film is formed on the surface of an optical lens, a display such as a CRT, or an optical product such as an electroluminescent element.
• the antireflection film is formed by laminating one or two or more optical thin films on the surface of the object (substrate in the present invention) requiring such antireflection.
• a transparent substrate eg, a glass plate or an optical lens
• the antireflection film is formed on the substrate by the above-described amorphous metal oxide thin film (eg, amorphous titanium dioxide thin film) or non-reflective film.
• amorphous metal oxide thin film eg, amorphous titanium dioxide thin film
• non-reflective film e.g, amorphous titanium dioxide thin film
• Xm n is the refractive index of the thin film with respect to light of wavelength ⁇ , where m is an integer of 1 or more. And particularly preferably an odd number).
• a thin film having a refractive index lower than the refractive index of the substrate (either the amorphous metal oxide thin film or the amorphous silicon dioxide thin film described above is selected according to the refractive index of the substrate).
• a thin film having a refractive index lower than the refractive index of the substrate (either the amorphous metal oxide thin film or the amorphous silicon dioxide thin film described above is selected according to the refractive index of the substrate).
• the antireflection film has a low reflectivity and the surface thereof has a high scratch resistance.
• the anti-reflection film can also be formed by alternately laminating two or more optical thin films having a high refractive index and optical thin films having a low refractive index on the surface of the substrate.
• the basic configuration of such an antireflection film is already known. By laminating two or more optical thin films on a substrate, reflection of light in a wide wavelength range can be effectively prevented. More than two layers When the above optical thin films are laminated, the amorphous silicon dioxide thin film or the amorphous metal oxide thin film described above is used as an optical thin film to be laminated at least at the last, so that an antireflection film exhibiting sufficiently high scratch resistance can be obtained. Is obtained.
• the number of layers of the optical thin film to be laminated on the substrate is preferably two since the production is easy.
• an antireflection film is formed by laminating two layers of optical thin films on a substrate, usually, an optical thin film having a high refractive index and an optical thin film having a low refractive index are sequentially laminated from the substrate side.
• the antireflection film of the present invention having a low reflectance and a high scratch resistance is formed.
• FIG. 1 is a cross-sectional view illustrating a configuration example of the antireflection film of the present invention.
• the anti-reflection film 10 of FIG. 1 is a metal oxide thin film 1 on a substrate 11 which is transparent and has a refractive index of light having a wavelength of 500 nm in a range of 1.45 to 1.80.
• amorphous silicon dioxide thin film that is transparent and contains a large number of fine voids therein, and has a refractive index of light having a wavelength of 50 O nm in a range of 1.01 to 1.43;
• An amorphous silicon dioxide thin film 13 occupying 80% by volume or more of the entire fine voids and having a diameter of the fine voids of 5 nm or less is laminated in this order.
• the anti-reflection film 10 of FIG. 1 shows high scratch resistance because the above-mentioned amorphous silicon dioxide thin film 13 is used. Therefore, as the metal oxide layer 12 of the antireflection film 10, the above-mentioned amorphous metal oxide thin film or a metal oxide thin film other than the above-mentioned amorphous metal oxide thin film can be used.
• the metal oxide thin film 12 is formed by a known thin film manufacturing method such as a sol-gel method or a sputtering method.
• the thicknesses of the metal oxide thin film 12 and the amorphous silicon dioxide thin film 13 of the antireflection film 10 in FIG. 1 are respectively ( ⁇ / 4 ⁇ ) ( ⁇ of the wavelength ( ⁇ ) of light to be reflected. It is preferably a thickness corresponding to (the refractive index of the thin film with respect to light having a wavelength ⁇ ) or a thickness in the vicinity thereof.
• This mixture sol was applied on a glass substrate using a spin coater to form a uniform coating film.
• the mixed sol coating film was heated and baked at 150 ° C. for 1 hour to obtain an amorphous titanium dioxide thin film having a film thickness of 78 nm.
• the refractive index (wavelength 500 nm) of this amorphous titanium dioxide thin film was 1.6.
• the amorphous titanium dioxide thin film contained fine voids, and the diameter of the fine voids occupying 90% by volume or more of the entire fine voids was 2 nm or less.
• the surface of the amorphous titanium dioxide thin film showed high scratch resistance.
• the mixture sol was applied onto the above-mentioned amorphous titanium dioxide thin film using a spin coater to form a uniform coating film.
• the mixed sol coating film was heated and baked at 450 ° C. for 2 hours to obtain an amorphous silicon dioxide thin film having a thickness of 95 nm.
• the refractive index of this amorphous silicon dioxide thin film (wavelength 500 nm) was 1.3.
• the amorphous silicon dioxide thin film contains a large number of fine voids, the porosity is 85%, and the diameter of the fine voids occupying 90% by volume or more of the entire fine voids is 2 nm or less.
• the surface of this amorphous silicon dioxide thin film showed high scratch resistance. Constructed using this amorphous titanium dioxide thin film and amorphous silicon dioxide thin film The reflectance of the antireflection film at a wavelength of 50 nm was measured and found to be 0.9%. [Industrial applicability]
• an anti-reflection film using an amorphous silicon dioxide thin film having a low refractive index and high scratch resistance, or an amorphous metal oxide thin film having a high refractive index and high scratch resistance be able to.
• the antireflection film of the present invention is required to have low reflectance and high scratch resistance formed on the surface of an optical lens, a display such as a CRT, or an optical product such as an electroluminescent device (especially an organic electroluminescent device). Can be advantageously used as an antireflection film.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Surface Treatment Of Optical Elements (AREA)
• Surface Treatment Of Glass (AREA)
• Liquid Crystal (AREA)
• Oxygen, Ozone, And Oxides In General (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Laminated Bodies (AREA)

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