Object having multilayer optical thin film including photocatalytic function and its manufacture

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a thin film laminate having a multi-layer structure having a photocatalytic function, that is, a function such as antifouling and antifogging, particularly an optical thin film laminate such as an antireflection film and an article having the thin film laminate.

【0002】

[Conventional technology]

Thin film laminates with a multi-layer structure, especially optical thin film laminates such as antireflection films, are widely used in various areas. For example, an antireflection film is provided on the lens interface of eyeglasses, cameras, binoculars, microscopes, etc. in order to improve the transmittance of the optical system or improve the contrast of the image. Further, when it is desired to increase the reflectance of glass or optical components, which normally has a reflectance of only a few percent, to several tens of percent to 90% or more, or to increase the reflectance without absorption loss, a reflection increasing film is provided. In addition, a band pass filter that transmits only light in a specific narrow wavelength region, a cold filter that transmits only visible light and reflects infrared rays (heat rays), and conversely, reflects only visible light and transmits infrared rays. Various filters such as cold mirrors and other practically important filters are also formed using an optical thin film laminate. Until now, optical thin film laminates have focused only on optical performance. However, in practice, there are many advantages as long as it has functions such as antifouling and antifogging in addition to optical performance. However, it has not been easy to impart functions such as antifouling and antifogging while maintaining the conventional optical performance.

【0003】

[Problems to be Solved by the Invention]

In order to impart functions such as antifouling and antifogging in addition to optical performance, it is necessary to use a thin film having a photocatalytic function such as a titanium oxide film or a composite film containing titanium oxide. However, even a thin film having a photocatalytic function can obtain desired optical characteristics simply by adding a thin film having a photocatalytic function to the surface of a conventional optical thin film laminate having a refractive index peculiar to the thin film. It will disappear. Further, the titanium oxide film or the composite film containing titanium oxide known so far has insufficient wear resistance, and there is a practical problem if these are the outermost surfaces. Therefore, an object of the present invention is a thin film laminate having a multi-layer structure, particularly an optical thin film laminate, which is provided with functions such as antifouling and anti-fog without impairing wear resistance. An object of the present invention is to provide a thin film laminate that maintains its original function. Furthermore, an object of the present invention is to provide various articles having the thin film laminate.

【0004】

[Means for solving problems]

The present invention relates to a thin film laminate having a multi-layer structure, further comprising at least one thin film having a photocatalytic function. Further, the present invention is an optical thin film laminate having a multilayer structure, having a photocatalytic function, and having a film thickness of 0.2 to 0.8λ.₀The present invention relates to an optical thin film laminate characterized by further having at least one layer in the range of. In the thin film laminate of the present invention, the optical thin film laminate can be, for example, an antireflection film. Further, the thin film laminate of the present invention may have a structure in which at least one of the thin film layers constituting the thin film laminate is divided into two, and a layer having a photocatalytic function is inserted between them. Further, in the thin film laminate of the present invention, the layer having a photocatalytic function can be a titanium oxide or a composite film containing titanium oxide. Further, in the optical thin film laminate of the present invention, the thickness from the interface between the thin film having a photocatalytic function and the outer layer thereof to the surface of the outermost layer is preferably in the range of 350 nm or less. The present invention relates to an article made of a base material having the thin film laminate of the present invention on its surface.

【0005】

Titanium oxide having a specific crystal structure is known to have photocatalytic activity, and has antifouling and antifogging functions. However, it was thought that the surface layer must be covered with titanium oxide in order for titanium oxide to exhibit photocatalytic activity. However, since the titanium oxide layer has a relatively high refractive index, when it is placed on the surface layer, the reflection is usually enhanced, and further, the optical characteristics of the thin film laminate under the layer are changed. Further, the above problem can be solved by using a titanium oxide layer instead of the high refractive index layer other than the surface layer of the thin film laminate, but in general, such a state (another layer exists on the surface layer). In the state), it was thought that the photocatalytic activity of titanium oxide could not be expressed. There are also thin film laminates in which there is no layer in which the titanium oxide layer can be used instead.

【0006】

However, under such circumstances, it has recently been found that the photocatalytic activity of the titanium oxide layer, which is the lower layer of the silica film, can be exhibited up to the thickness of the silica film of about 350 μm. That is, even if the photocatalyst layer has an overlay layer such as silica, if the film thickness is not more than a certain level, the photocatalytic activity of the photocatalyst layer existing under the overlay layer surface such as a silica film can be obtained. Further, when a layer having a photocatalytic function such as a titanium oxide film is inserted at an arbitrary place in the thin film laminate, the film thickness of the layer having a photocatalytic function is 1 / 2λ.₀Before and after 0.2 ~ 0.8λ₀It was found that the optical properties inherent in the thin film laminate were not impaired within the range of. The present invention has been completed based on such findings.

【0007】

BEST MODE FOR CARRYING OUT THE INVENTION

The thin film laminate having a multilayer structure of the present invention is known by itself, and is composed of, for example, decorative and protective thin film layers for the appearance of various electric products; electronic devices, and deposition of multilayer thin films in semiconductor devices. Examples include integrated circuits and transparent conductive film layers. Further, the optical thin film laminate having a multilayer structure of the present invention is also known by itself, and examples thereof include an antireflection film and an antireflection film. Furthermore, a filter layer provided in a band pass filter that transmits only light in a specific narrow wavelength region, and a filter layer provided in a cold filter that transmits only visible light and reflects infrared rays (heat rays). A filter layer provided on the cold mirror that reflects only visible light and transmits infrared rays, a color temperature correction cold mirror, a color temperature correction filter, a mirror for laser, a selective transmission film, a selective reflection film, a selective absorption film, and the like can be mentioned. it can.

【0008】

The thin film laminate of the present invention further has at least one thin film having a photocatalytic function. That is, the thin film laminate itself has the conventional structure as it is, and further has a structure in which one layer or two or more layers having a photocatalytic function are inserted between the layers constituting the thin film laminate. Alternatively, it may have a structure in which at least one of the thin film layers constituting the thin film laminate is divided into two, and a layer having a photocatalytic function is inserted between them. However, when the thin film laminate is an optical thin film laminate, the film thickness of the layer having a photocatalytic function is 0.2 to 0.8λ.₀It is appropriate from the viewpoint that the optical properties inherent in the optical thin film laminate are not impaired. The film thickness of the layer having a photocatalytic function is preferably 0.2λ.₀Is the range of. Further, the thin film having a photocatalytic function is provided at a position where the thickness from the interface with the outer layer to the surface of the outermost layer is in the range of 350 nm or less, so that the photocatalytic function is satisfactorily exhibited on the surface of the thin film laminate. It is preferable from the viewpoint. The thickness from the thin film having a photocatalytic function to the surface of the thin film laminate is preferably 300 nm or less, and more preferably in the range of 100 to 200 nm when considering the wear resistance of the thin film layer at a practical level. Further, from the viewpoint that the thin film laminate has excellent photocatalytic activity, it is preferable to provide a thin film having two or more photocatalytic functions at a position including the layer directly below the uppermost layer.

【0009】

The layer having a photocatalytic function can be, for example, titanium oxide or a composite film containing titanium oxide. The layer having a photocatalytic function can be formed by, for example, an ion plating method, a sputtering method, a CVD method, a sol-gel method, an aqueous solution method, or the like.

【0010】

The article of the present invention is an article made of a base material having the thin film laminate of the present invention on its surface. The base material constituting the article of the present invention may be made of, for example, glass, plastic, metal or ceramics, or a composite thereof. In addition, SiO on its surface₂, Al₂O₃, ZrO₂, ITO, CaF₂It is also possible to use a thin film formed as a base material. However, the intention is not limited to these. Further, the base material is not limited to spectacle lenses, and is not limited to optical lenses such as camera lenses, binocular lenses, and microscope lenses, and examples thereof include articles having all thin film laminates.

【0011】

The thin film made of a metal oxide having photocatalytic activity of the thin film laminate of the present invention contains a base material having a layer underlying the thin film made of a metal oxide having photocatalytic activity, a fluorometal complex compound and a fluorine trapping agent. It can be formed by a method of precipitating a metal oxide thin film derived from the fluorometal complex compound by immersing it in an aqueous solution. Further, by repeating the above method for the number of thin film layers made of a metal oxide having a photocatalytic activity, a thin film laminate having a plurality of thin film layers made of a metal oxide having a photocatalytic activity can be formed.

【0012】

Examples of the fluorometal complex compound to be contained in the aqueous solution containing the fluorometal complex compound include a compound represented by the following general formula (I). A_aM_{b b}F_c(I) In the formula, A is one or more atoms selected from the group consisting of hydrogen atom, alkali metal atom, ammonium group and coordinated water, M is a metal, and a, b and c are the atoms. It is the number that makes the complex compound electrically neutral. An acid or salt that is soluble in water is used to form this fluorometal complex. A includes hydrogen atoms as well as alkali metal atoms such as lithium, sodium, potassium, rubidium and cesium; as well as ammonium groups and coordinated water. Examples of M (metal) include titanium, silicon, zirconium, niobium, germanium, aluminum, indium, tin, zinc, and copper. However, the metal is not limited to these, but titanium is particularly preferable as M (metal). In this case, the fluorometal complex compound is a fluorotitanium complex compound and the metal oxide is TiO.₂Is. When b is 1, c is usually 6, then a is 2 or 3 depending on the valence of. Typically A₃MF₆Or A₂MF₆Can be represented by. However, it may be a polynuclear complex compound having a plurality of metal atoms (M).

【0013】

The aqueous solution containing the fluorometal complex compound can be prepared by dissolving the target metal oxide in hydrofluoric acid. Alternatively, the hydroxide or oxyhydroxide of the metal of interest is dissolved in an aqueous solution of an alkali metal difluoride such as ammonium hydrogen difluoride or sodium bifluoride to provide the corresponding fluorometal complex. Compounds can also be synthesized. Fluorometal complex compounds usually have a metal content of 10^-9~ 10mol / L, preferably 10^-6~10^-1It is prepared and used in an aqueous solution with a concentration of mol / L. Here, the aqueous solution may be an aqueous solution containing excess hydrogen fluoride used for synthesizing the metal complex compound.

【0014】

The fluoride ion scavenger used in the present invention may be any as long as it can capture fluorine ions from an aqueous solution containing a fluorometal complex compound to precipitate a metal oxide thin film. In general, the fluoride ion scavenger includes a homogeneous system that is used by dissolving it in a liquid phase and a heterogeneous system that is a solid substance. Either one of these may be used or a combination thereof may be used depending on the purpose.

【0015】

The homogeneous fluoride ion scavenger shifts the equilibrium of fluorine ions so as to precipitate a metal oxide thin film by reacting with hydrogen fluoride to form a stable fluorocomplex compound and / or fluoride. is there. In addition to boric acid such as orthoboric acid and metaboric acid: aluminum chloride, sodium hydroxide, aqueous ammonia and the like are exemplified. Such a scavenger is usually used in the form of an aqueous solution, but may be added in the form of a powder and dissolved in the system. The addition of such a scavenger may be performed intermittently at one time or divided into several times, or may be continuously performed at a controlled supply rate, for example, a constant rate.

【0016】

Further, in the production method of the present invention, the seed crystal of the metal oxide to be precipitated can be added to the aqueous solution. By using the seed crystal, all the precipitated metal oxides have a stable phase. The seed crystal should be in the range of 0.001 to 10 μm, preferably as small as 0.001 to 1 μm, and the amount of the seed crystal added can be appropriately determined in consideration of the amount of oxide to be precipitated and the like. In the method of the present invention, a precipitate can be obtained as a stable phase by using a seed crystal of a target metal oxide as a seed crystal. In addition, the precipitation rate can be controlled by selecting the particle size and the amount of the seed crystal added. If necessary, seed crystals can be replenished during precipitation.

【0017】

In the production method of the present invention, the seed crystal of the metal oxide to be precipitated is added to the aqueous solution, and the metal oxide thin film is precipitated in the presence of the seed crystal. By using the seed crystal, all the precipitated metal oxides have a stable phase. The seed crystal should be in the range of 0.001 to 10 μm, preferably in the range of 0.001 to 1 μm, more preferably in the range of 0.001 to 0.15 μm, and the amount of addition thereof is appropriate in consideration of the amount of oxide to be precipitated and the like. Can be decided. In the method of the present invention, a precipitate can be obtained as a stable phase by using a seed crystal of a target metal oxide as a seed crystal. In addition, the precipitation rate can be controlled by selecting the particle size and the amount of the seed crystal added. If necessary, seed crystals can be replenished during precipitation.

【0018】

The filtration of the aqueous solution for precipitation is carried out by using a filter having a pore size sufficient to capture the precipitated particles having a particle size larger than that of the seed crystal, although the seed crystal is permeated, so that the effect of adding the seed crystal is maintained. Moreover, it is preferable from the viewpoint of forming an oxide thin film having a uniform thickness. In particular, from the viewpoint of producing an oxide thin film having a uniform thickness, it is preferable to use a filter having a pore size of 150 nm or less. The pore size of the filter is more preferably 100 nm or less, still more preferably 50 nm or less. Further, the above-mentioned filtration can be performed by continuously or intermittently circulating the aqueous solution for precipitation through the filter. Specifically, a part of the aqueous solution for precipitation is extracted and permeated through the filter. Then, the obtained aqueous solution is returned to the aqueous solution for precipitation again. The amount (circulation amount) of the aqueous solution to be filtered can be appropriately determined in consideration of the composition and temperature of the aqueous solution, the amount of seed crystals added, and the like.

【0019】

In the production method of the present invention, the metal oxide thin film is precipitated by continuously, intermittently or temporarily applying sound waves and / or ultrasonic waves to an aqueous solution containing a fluorometal complex compound and a fluorine scavenger. be able to. A sound wave is a wave having a frequency lower than 20 kHz, and an ultrasonic wave is a wave having a frequency of 20 kHz to 300 MHz. From the viewpoint of effectively obtaining the effects of the present invention, it is preferable to use sound waves and ultrasonic waves in the frequency range of 10 kHz to 100 kHz. Also, a single frequency sound wave or ultrasonic wave can be used, or multiple sound waves and / or ultrasonic waves having different frequencies can be used. The amount (output) of sound waves and / or ultrasonic waves given to the aqueous solution is expressed in terms of sound wave or ultrasonic density (output / bottom area of reaction vessel), for example, 0.01 to 1 W / cm.²Can be in the range of. However, the sound wave or ultrasonic density can be appropriately determined in consideration of the shape and volume of the reaction vessel, the amount of the reaction solution, and the like. In addition, sound waves and / or ultrasonic waves can be applied continuously, intermittently, or temporarily. When sound waves and / or ultrasonic waves are applied to an aqueous solution, the temperature of the aqueous solution tends to rise. Therefore, in consideration of the temperature of the aqueous solution and the effect of the present invention, the time and timing of applying sound waves and / or ultrasonic waves should be set. It can be decided as appropriate.

【0020】

The time for immersing the base material in the aqueous solution of the fluorometal complex compound may be before, at the same time, or after the addition or insertion of the fluoride scavenger. However, when using a substrate that may be attacked by the system, care must be taken in the composition of the solution, the reaction conditions, and the timing of immersion. The reaction temperature can be arbitrarily set within the range in which the system maintains the aqueous solution, and can be, for example, in the range of 5 to 99 ° C, preferably in the range of 10 to 80 ° C, preferably in the range of 30 ° C to 70 ° C. It is more preferable that the range is. The reaction time is also arbitrary, and for example, when the target precipitate is large, the reaction time can be lengthened accordingly.

【0021】

In this way, a metal oxide thin film can be formed on the surface of the base material. The precipitate thus formed can be obtained as a metal oxide thin film crystallized according to conditions without undergoing a heating step such as calcination. However, a heating step may be provided depending on the purpose. The metal oxide thin film obtained by the method of the present invention is an oxide of, for example, titanium, silicon, zirconium, niobium, germanium, aluminum, indium, tin, zinc, and copper, depending on the type of fluorometal complex compound used. It is a thin film containing 1 type or 2 or more types. Further, the metal oxide thin film includes a metal oxide thin film doped with metal ions.

【0022】

The method for producing a metal oxide thin film can be divided into the following three modes, for example. The first aspect is a method of forming a thin film made of a metal oxide derived from a fluorometal complex compound. When forming a thin film composed of a single metal oxide, an aqueous solution containing one kind of fluorometal complex compound is used. Further, when it is desired to form a thin film composed of a plurality of metal oxides, an aqueous solution containing two or more kinds of fluorometal complex compounds is used. In this case, two kinds composed of metal oxides derived from two or more kinds of fluorometal complex compounds are used. It is preferable to carry out in the presence of the above seed crystals. This is because by using the seed crystal of the metal oxide to be precipitated, all the precipitated metal oxides have a stable phase.

【0023】

A second aspect of the present invention is a method for producing a metal oxide thin film derived from a fluorometal complex compound doped with metal ions. In this aspect, the thin film formed is a metal ion-doped metal oxide. Examples of the metal ion doped in the metal oxide include silver ion, copper ion, platinum ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion and the like. However, any metal ion derived from the compound soluble in the aqueous solution containing the fluorometal complex compound can be doped.

【0024】

Examples of the water-soluble metal compound include AgF and xH.₂O, AgNO₃, Rh (NO)₃)₃ 2H₂O, Cu (NO)₃)₂ 3H₂O, Cr (NO₃)₃ XH₂O, CuF₂ 2H₂O, CuCl₂ 2H₂O, PtCl₄ 5H₂O, VOSiO₄ 2H₂O, VOCl₃, Cr₂(SO₄)₃ 18H₂O, CrCl₃ XH₂O, MnCl₂ 4H₂O, MnCl₂, Mn (NO)₃)₂ 6H₂O, MnSO₄ 6H₂O, MnF₂, MnF₃ 3H₂O, FeCl₂ 4H₂O, FeCl₂, FeCl₃ 6H₂O, FeCl₃, Fe (NO)₃)₃ 9H₂O, FeSO₄ 7H₂O, FeSO₄, (NH₄) Fe (SO)₄)₃ XH₂O, Co (NO)₃)₂ 6H₂O, CoSO₄ 7H₂O, NiCl₂ 6H₂O, Ni (NO)₃)₂ 6H₂O, NiSO₄, Cu (NO)₃)₂ 3H₂O, CuSO₄ 5H₂O, CuSO₄, CuCl₂ 2H₂O, CuF₂ 2H₂O, CuCl, Sc (SO₄)₃ XH₂O etc. are exemplified.

【0025】

The concentration of the water-soluble metal compound is, for example, 10 per liter of the treatment liquid, considering the solubility and the amount of doping into the thin film.^-4It can be in the range of ~ 10 mol. Further, the water-soluble metal compound can be supplemented and added during the reaction.

【0026】

A third aspect is a method for producing a thin film containing fine particles in a metal oxide derived from a fluorometal complex compound. This thin film can be formed by adding and dispersing fine particles in an aqueous solution containing a fluorometal complex compound and precipitating the thin film from the aqueous solution. Examples of the fine particles include metal colloid particles, metal oxide colloid particles, and organic particles. Examples of the metal colloidal particles include Cu, Ag, Pt and the like. Examples of the metal oxide colloidal particles include Fe.₂O₃, Cu₂O, CuO, etc. can be mentioned. Examples of the organic particles include polystyrene, polyethylene terephthalate, acrylic, polycarbonate and the like. The particle size of the fine particles and the amount added to the aqueous solution can be appropriately changed depending on the target thin film. However, in consideration of the dispersibility of the fine particles in the aqueous solution and the state of existence in the thin film, the particle size is, for example, 10.^-3It can be in the range of ~ 1 μm. The amount of the fine particles added to the aqueous solution is, for example, 10 per liter of the treatment liquid in consideration of the concentration of the fine particles in the thin film.^-2~10²Can be in the range of g. Further, as in the case of seed crystals, fine particles can be added and replenished during the reaction. Since the method of the present invention uses sound waves and / or ultrasonic waves, it is possible to disperse the fine particles more uniformly in the thin film.

【0027】

Also in the second and third aspects, the aqueous solution containing the fluorometal complex compound can contain a seed crystal made of a metal oxide formed by the fluorometal complex compound. By using such a seed crystal, a metal oxide can be precipitated as a stable phase. It is also possible to simultaneously form a thin film containing two or more kinds of substances by combining two or more of the above three aspects.

【0028】

[Example]

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In addition, λ in each of the following examples₀Is 500 nm. Example 1 In the optical component of Example 1, the structure of the multilayer optical thin film is a five-layer structure. Board 1 \ SiO₂\ ZrO₂\ SiO₂\ ZrO₂\ SiO₂The optical characteristics are shown by solid lines in Fig. 1. Further, the structure of the multilayer optical thin film according to the present invention is a six-layer structure. Board 1 \ SiO₂\ ZrO₂\ SiO₂\ TiO₂\ ZrO₂\ SiO₂Is. That is, about 1 / 2λ between the substrate and the thin films of the third and fourth layers.₀The photocatalyst thin film of is inserted. Its optical characteristics are shown by broken lines in Fig. 1. Comparing the solid line and the broken line shown in FIG. 1, it can be seen that the multilayer optical thin film according to the present invention in which the photocatalytic thin film is inserted maintains the optical characteristics originally possessed by the multilayer optical thin film.

【0029】

Hereinafter, a method for forming this multilayer film will be described. First, the substrate 1, which is a plastic lens having a hard coat layer produced by the method described later, is heated to 80 ° C. Then, a vacuum vapor deposition method (vacuum degree 2 × 10) is performed on the hard coat layer.^-5By Torr), the first layer SiO₂Layer 0.56λ₀Deposited to some extent. On top of that, the second layer ZrO₂Layer 0.05λ₀Deposited to some extent. On top of the second layer, the third layer SiO₂Layer 0.09λ₀Deposited to some extent. The fourth layer is a photocatalytic thin film layer that provides the antireflection film with a photocatalytic function according to the present invention. In this example, a film was formed using the dispersed seed aqueous solution method. A detailed description is given below. First, a dispersed seed aqueous solution is prepared. Ammonium hexafluorotitanate (NH) as a fluorocomplex metal compound₄)₂TiF₆After dissolving 2.8 g of this in 400 ml of water and stirring, TiO₂The solution in which the anatase fine particles were previously suspended in water was left overnight, and 10 ml of the obtained supernatant was added, and the mixture was homogenized by stirring in the same manner. The treatment liquid prepared as described above was transferred to a 500 ml columnar container and immersed in a constant temperature bath kept at 30 ° C. By quickly immersing 10 g of boron oxide in the above-mentioned treatment liquid, the optical film thickness is 0.47λ.₀Accumulated to the extent. After the film formation is completed, this plastic lens is taken out from the treatment liquid, lightly washed, dried at 50 ° C, and anatase-type TiO.₂A thin film was provided on the lens. Furthermore, on top of the fourth layer, ZrO of the fifth layer₂0.5λ for layers by vacuum deposition₀Deposited to some extent. Further on top of the 5th layer, the 6th layer SiO₂The layer is vacuum-deposited 0.27λ₀Deposited to some extent. The above-mentioned spectacle lens provided with the multilayer film of the present invention was irradiated with ultraviolet rays for 20 hours using a black lamp, and then the decomposition of salad oil was observed. As a result, it was confirmed that the antireflection film obtained above has photocatalytic performance.

【0030】

[Substrate 1: Fabrication of plastic lens with hard coat] Process 1. Preparation of hard coat liquid SiO in a stainless steel container with a stirring function kept at 10 ° C to 15 ° C₂280 parts by weight of water-dispersed colloidal silica (cataroid SI-40 manufactured by Catalytic Chemical Industry Co., Ltd.) having a concentration of 40% was added, and 4 parts by weight of 0.6 N hydrochloric acid and 60 parts by weight of acetic acid were added while stirring. Then, 150 parts by weight of γ-glycidoxypropyltrimethoxysilane was added dropwise, and the mixture was stirred for 24 hours. Further, while stirring, 100 parts by weight of methyl cellosolve, 300 parts by weight of isopropyl alcohol, and 100 parts by weight of n-butanol were added in this order, and when they became uniform, 15 parts by weight of aluminum acetylacetone was added as a curing agent. Further, stirring was continued for one day and night to obtain a hard coat liquid. Process 2. Fabrication of lens substrate Add 3 parts by weight of diisopropylperoxydicarbonate as a polymerization initiator and 0.03 part by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber to 100 parts by weight of diethylene glycol bisallyl carbonate, and thoroughly stir and mix. Then, the monomer is injected into a lens molding mold composed of a glass mold and a resin gasket prepared in advance. The lens molding mold infused with the monomer was placed in an electric furnace, and the temperature was gradually raised from 40 ° C to 90 ° C over 20 hours and maintained at 90 ° C for 1 hour for polymerization. Then, it was taken out from an electric furnace and the gasket and the mold were removed to obtain a lens. Process 3. Applying a hard coat The lens obtained in step 2 is immersed in a 5% sodium hydroxide aqueous solution at 40 ° C for 5 minutes, thoroughly washed, and the hard coat solution obtained in step 1 is applied by the dipping method to 120 ° C. A plastic lens with a hard coat film was obtained by heat treatment for 1 hour.

【0031】

Example 2 In the optical component of Example 2, the structure of the multilayer optical thin film is a five-layer thin film structure. Board 2 \ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ SiO₂Is. The optical characteristics are shown by solid lines in Fig. 2. Further, the structure of the multilayer optical thin film according to the present invention is a six-layer thin film structure. Board 2 \ SiO₂\ Ta₂O₅\ SiO₂\ TiO₂\ Ta₂O₅\ SiO₂Is. That is, about 0.39λ between the HC-60ih (hard coat layer) and the thin films of the third and fourth layers.₀The photocatalytic thin film of was inserted. Its optical characteristics are shown by broken lines in Fig. 2. From the results shown in FIG. 2, it can be seen that the multilayer optical thin film maintains the original optical characteristics.

【0032】

Hereinafter, a method for forming this multilayer film will be described. First, a plastic lens having a hard coat layer produced by the method described later is used as the substrate 2, and this is heated to 80 ° C. Then, a vacuum vapor deposition method (vacuum degree 2 × 10) is performed on the hard coat layer.^-5By Torr), the first layer SiO₂Layer 0.55λ₀Deposited to some extent. On top of that, the second layer Ta₂O₅Layer 0.05λ₀Deposited to some extent. On top of the second layer, the third layer SiO₂Layer 0.13λ₀Deposited to some extent. The fourth layer is a photocatalytic thin film layer (in this example, TiO) that provides a photocatalytic function to the multilayer optical thin film according to the present invention.₂In). In this example, a film was formed using the dispersed seed aqueous solution method. A detailed description is given below. First, a dispersed seed aqueous solution is prepared. Ammonium hexafluorotitanate (NH) as a fluorocomplex metal compound₄)₂TiF₆After dissolving 2.8 g of this in 400 ml of water and stirring, TiO₂A solution in which anatase fine particles were previously suspended in water was left overnight, and 10 ml of the obtained supernatant was added, and the mixture was homogenized by stirring in the same manner. The treatment liquid prepared as described above was transferred to a 500 ml columnar container and immersed in a constant temperature bath kept at 30 ° C. Immersing 10 g of boron oxide in the above-mentioned treatment liquid quickly, the optical film thickness is 0.39λ.₀Accumulated to the extent. After the film formation is completed, the plastic lens is taken out from the treatment liquid, lightly washed, dried at 50 ° C, and anatase-type TiO.₂A thin film was provided on the lens. Furthermore, on top of the fourth layer, the fifth layer Ta₂O₅0.55λ layer by vacuum deposition method₀Deposited to some extent. Furthermore, on top of the 5th layer, the 6th layer SiO₂The layer is vacuum-deposited 0.28λ₀Deposited to some extent. The spectacle lens provided with the multilayer film obtained above was irradiated with ultraviolet rays for 20 hours using a black lamp, and then the decomposition of the salad oil was observed. As a result, it was confirmed that the obtained antireflection film has photocatalytic performance.

【0033】

[Substrate 2: Fabrication of plastic lens with hard coat layer] Process 1. Preparation of hard coat liquid A stainless steel container with a stirring function maintained at 0 ° C to 5 ° C was coated with a stannic oxide / zirconium oxide composite sol dispersed in methanol with a solid content of 30% with a tungsten oxide / stannic oxide composite sol. While adding 400 parts by weight of a composite sol (manufactured by Nissan Chemical Co., Ltd.) and stirring, 125 parts by weight of γ-glycidoxypropyltrimethoxysilane was added dropwise, and after stirring for 5 hours, 30 parts by weight of 0.001N hydrochloric acid was added. Was added dropwise with stirring. After continuing stirring for 40 hours, 257 parts by weight of propylene glycol monomethyl ether and 19 parts by weight of diacetone alcohol were added dropwise in this order, and when they became uniform, 5 parts by weight of aluminum acetylacetone was added as a curing agent. Further, stirring was continued for 3 days and nights to obtain a hard coat liquid. Process 2. Fabrication of lens substrate 1,3-Diisocyanatomethylcyclohexane 47.5 parts by weight, 0.45 parts by weight of dimethyltin dichloride as a polymerization catalyst, 0.16 parts by weight of acidic phosphoric acid ester JP-506 (manufactured by Johoku Chemical Industry Co., Ltd.) as a release agent, UV absorption Add 0.1 part by weight of UV5411 (manufactured by American Syanamide) as an agent, and stir and mix thoroughly. Then, 52.5 parts by weight of an equal equivalent mixture of pentaerythritol tetrakis mercaptoacetate and 2,5-dimercaptomethyl 1,4-dithiane is added, and the mixture is sufficiently mixed and stirred. Next, the monomer is injected into a lens molding mold composed of a glass mold and a resin gasket prepared in advance. The lens molding mold infused with the monomer was placed in an electric furnace, and the temperature was gradually raised from 20 ° C to 120 ° C over 20 hours and maintained at 120 ° C for 3 hours for polymerization. Then, it was taken out from an electric furnace and the gasket and the mold were removed to obtain a lens. Process 3. Applying a hard coat The lens obtained in step 2 is immersed in a 5% sodium hydroxide aqueous solution at 40 ° C for 5 minutes, thoroughly washed, and the hard coat solution obtained in step 1 is applied by the dipping method to 120 ° C. A lens coated with a hard coat film was obtained by heat treatment for 1 hour.

【0034】

Example 3 In the optical component of Example 3, the structure of the multilayer optical thin film is a seven-layer thin film structure. Board 3 \ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ SiO₂The optical characteristics are shown by solid lines in Fig. 3. The structure of the multilayer optical thin film according to the present invention is an eight-layer thin film structure. Board 3 \ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ SiO₂\ TiO₂\ Ta₂O₅\ SiO₂Is. That is, about 0.23λ between the substrate and the thin films of the 5th and 6th layers.₀The photocatalytic thin film of was inserted. Its optical characteristics are shown by broken lines in Fig. 3. From the results shown in FIG. 3, it can be seen that the multilayer optical thin film having an eight-layer thin film structure according to the present invention maintains the optical characteristics inherent in the multilayer optical thin film.

【0035】

Hereinafter, a method for forming this multilayer film will be described. A LHI lens substrate (code: 702-402) manufactured by Hoya Corporation is used as the substrate 3, and this is heated to 80 ° C. After that, the vacuum deposition method (vacuum degree 2 × 10) is performed on this substrate 3.^-5By Torr), the first layer SiO₂Layer 0.10λ₀Deposited to some extent. On top of that, the second layer Ta₂O₅Layer 0.03λ₀Deposited to some extent. On top of the second layer, the third layer SiO₂Layer 0.63λ₀Deposited to some extent. On top of the third layer, the fourth layer Ta₂O₅Layer 0.06λ₀Deposited to some extent. On top of the 4th layer, the 5th layer SiO₂Layer 0.12λ₀Deposited to some extent. The sixth layer is a photocatalytic thin film layer (TiO in this embodiment) that provides a photocatalytic function to the multilayer optical thin film according to the present invention.₂Membrane). In this example, a film was formed using the dispersed seed aqueous solution method. A detailed description is given below. First, a dispersed seed aqueous solution is prepared. Ammonium hexafluorotitanate (NH) as a fluorocomplex metal compound₄)₂TiF₆After dissolving 2.8 g of this in 400 ml of water and stirring, TiO₂A solution in which anatase fine particles were previously suspended in water was left overnight, and 10 ml of the obtained supernatant was added, and the mixture was homogenized by stirring in the same manner. The treatment liquid prepared as described above was transferred to a 500 ml columnar container and immersed in a constant temperature bath kept at 30 ° C. By quickly immersing 10 g of boron oxide in the above-mentioned treatment liquid, the optical film thickness is 0.23λ.₀Accumulated to the extent. After the film formation is completed, the plastic lens is taken out from the treatment liquid, lightly washed, dried at 50 ° C, and anatase-type TiO.₂A thin film was provided on the lens. Further, on the 6th layer, the 7th layer Ta₂O₅The layer is vacuum-deposited 0.43λ₀Deposited to some extent. Furthermore, on top of the 7th layer, the 8th layer SiO₂The layer is vacuum-deposited 0.27λ₀Deposited to some extent. The spectacle lens provided with the multilayer film thus obtained was irradiated with ultraviolet rays for 20 hours using a black lamp, and then the decomposition of the salad oil was observed. As a result, it was confirmed that this antireflection film has photocatalytic performance.

【0036】

Example 4 In Example 1, Example 2, and Example 3, the insertion position of the photocatalytic functional thin film layer was between two thin films made of different materials. However, in some cases, the film thickness of the thin film layer on the photocatalytic function thin film layer may be too thick to exhibit the photocatalytic function, or the film thickness of the thin film layer on the photocatalyst function thin film layer may be too thin. It is assumed that good design results may not be obtained due to insufficient hardness of the thin film layer. In Example 4, one thin film layer constituting the laminate is divided into two layers, and the photocatalytic function thin film layer is inserted between the divided layers. By adopting this method, it is possible to produce a thin film layer having sufficient hardness and photocatalytic function even in the above-mentioned cases.

【0037】

In the optical component of Example 4, the structure of the multilayer optical thin film is a seven-layer thin film structure. Board 3 \ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ SiO₂Is. The optical characteristics are shown by solid lines in Fig. 4. The structure of the multilayer optical thin film according to the present invention is a 9-layer thin film structure. Board 3 \ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ SiO₂\ Ta₂O₅\ TiO₂\ Ta₂O₅\ SiO₂Is. That is, Ta which is the sixth layer from the substrate 3₂O₅The layer is divided into two layers to form a sixth layer and an eighth layer, and a photocatalytic functional layer (TiO) as a seventh layer between them.₂Layer) about 0.76λ₀It was inserted with the film thickness of. The membrane structure has nine layers. The optical characteristics are shown by broken lines in Fig. 4. From the results of FIG. 4, it can be seen that the multilayer optical thin film of the present invention maintains the optical characteristics inherent in the multilayer optical thin film.

【0038】

Hereinafter, a method for forming this multilayer film will be described. First, the substrate 3 is heated to 80 ° C, and then a vacuum deposition method (vacuum degree 2 × 10) is performed on it.^-5By Torr), the first layer SiO₂Layer 0.09λ₀Deposited to some extent. On top of that, the second layer Ta₂O₅Layer 0.05λ₀Deposited to some extent. On top of the second layer, the third layer SiO₂Layer 0.60λ₀Deposited to some extent. On top of the third layer, the fourth layer Ta₂O₅Layer 0.08λ₀Deposited to some extent. On top of the 4th layer, the 5th layer SiO2 layer 0.10λ₀Deposited to some extent. On top of the 5th layer, the 6th layer Ta₂O₅Layer 0.14λ₀Deposited to some extent. The seventh layer is a photocatalytic thin film layer (TiO in this embodiment) that provides a photocatalytic function to the multilayer optical thin film according to the present invention.₂Membrane). In this example, a film was formed using the dispersed seed aqueous solution method. A detailed description is given below. First, a dispersed seed aqueous solution is prepared. Ammonium hexafluorotitanate (NH) as a fluorocomplex metal compound₄)₂TiF₆After dissolving 2.8 g of this in 400 ml of water and stirring, TiO₂A solution in which anatase fine particles were previously suspended in water was left overnight, and 10 ml of the obtained supernatant was added, and the mixture was homogenized by stirring in the same manner. The treatment liquid prepared as described above was transferred to a 500 ml columnar container and immersed in a constant temperature bath kept at 30 ° C. Immersing 10 g of boron oxide in the above-mentioned treatment liquid quickly, the optical film thickness was 0.76λ.₀Accumulated to some extent. After the film formation is completed, the plastic lens is taken out from the treatment liquid, lightly washed, dried at 50 ° C, and anatase-type TiO.₂A thin film was provided on the lens. Furthermore, on top of the 7th layer, Ta of the 8th layer₂O₅Layer 0.09λ by vacuum deposition₀Deposited to some extent. Furthermore, on top of the 8th layer, the 9th layer SiO₂The layer is vacuum-deposited 0.29λ₀Deposited to some extent. The spectacle lens provided with the multilayer film thus obtained was irradiated with ultraviolet rays for 20 hours using a black lamp, and then the decomposition of the salad oil was observed. As a result, it was confirmed that this antireflection film has photocatalytic performance.

【0039】

[Effect of the invention]

According to the present invention, a thin film laminate having a multi-layer structure, particularly an optical thin film laminate, which is provided with functions such as antifouling and anti-fog without impairing wear resistance, is essentially an optical thin film laminate. It is possible to provide a thin film laminate that maintains its function. Further, according to the present invention, it is possible to provide various articles having a thin film laminate having the above-mentioned excellent physical characteristics.

[Simple explanation of drawings]

[Figure 1]

It is a figure which shows the optical spectroscopic characteristic before and after inserting the photocatalyst layer produced in Example 1. The solid line is the spectral characteristic of the original thin film system, and the broken line is the spectral characteristic according to the present invention.

[Figure 2]

It is a figure which shows the optical spectroscopic characteristic before and after inserting the photocatalyst layer produced in Example 2. The solid line is the spectral characteristic of the original thin film system, and the broken line is the spectral characteristic according to the present invention.

[Fig. 3]

It is a figure which shows the optical spectroscopic characteristic before and after inserting the photocatalyst layer produced in Example 3. The solid line is the spectral characteristic of the original thin film system, and the broken line is the spectral characteristic according to the present invention.

[Fig. 4]

It is a figure which shows the optical spectroscopic characteristic before and after inserting the photocatalyst layer produced in Example 4. The solid line is the spectral characteristic of the original thin film system, and the broken line is the spectral characteristic according to the present invention.