CN1834693A - Optical transparent member and optical system using the same - Google Patents

Abstract

It is an object to provide an optical transparent member capable of maintaining a high-performance antireflection effect for a base over a long period of time, and an optical system using the same, specifically an optical transparent member including on a base, a layer containing SiO 2 as a main component, a layer containing Al 2 O 3 as a main component, and a plate crystal layer formed from plate crystals containing Al 2 O 3 as a main component, wherein the surface of the plate crystal layer has a shape of irregularities, and an optical system using the same.

Description

The optical system of optical clear parts and these optical clear parts of use

Technical field

The present invention relates to a kind of optical system that has the optical clear parts of antireflective property and use these optical clear parts, more specifically, relate to a kind of optical clear parts that are suitable for obtaining for a long time the high antireflective property from the visibility region to the near infrared region, and the optical system of using these optical clear parts.

Especially, optical clear parts of the present invention can be adapted to have the transparent substrates of any refractive index, visible light is demonstrated fabulous anti-reflection effect, and have long-term corrosion resistance, therefore can be used for the optics of the various displays of word processor, computing machine, TV, plasma display panel etc.; The polarising sheet of liquid crystal apparatus; Sunglasses, graduated glasses lens, the view finder lens that are used for camera, prism, fly lens, toric lens and the various light filters of forming by various optical glass materials and transparent plastic and sensor etc.; Further, use the glass pane of the surface of optics, observation optical system, the projection optical system of in liquid crystal projector, using, the scanning optics of in laser printer etc., using, various instruments of various optical lenses of image-pickup optical system of these opticses and automobile, electric train etc. such as binoculars.

Background technology

Known, use the anti-reflection structure of meticulous periodic structure to form meticulous periodic structure, thereby outstanding antireflective property has been shown in wide wavelength region may with suitable degree of tilt and height with visible region wavelength or shorter wavelength.As the method that is used to form meticulous periodic structure, known coating is a kind of wherein to be studded with the method that mean particle dia is equal to or less than the film (Japanese patent application No.03135944) etc. of the finely particulate of wavelength.

Known, allow to want controlled degree of tilt and height by form the method that pattern forms meticulous periodicity structure by fine processing equipment (electron beam Embosser, laser interference exposure sources, semiconductor exposure equipment, etching machines etc.), and make that it is possible may forming the meticulous periodic structure (Japanese Patent Application Publication No.S50-70040) with outstanding antireflective properties.

For with the said method diverse ways, the growth boehmite is that the oxyhydroxide of aluminium is known with the method that obtains anti-reflection effect in substrate.In these methods, form aluminium (aluminium oxide) layer that technology (Jap.P. open No.S61-48124) or liquid phase process (collosol craft) (Japanese Patent Application Publication No.H9-202649) form by vacuum diaphragm and stand steam treatment or hot-water soak processing, so that superficial layer is formed boehmite, forming meticulous periodic structure, thereby and obtain anti-reflective film.

Yet, in the technology of using finely particulate, be difficult to the degree of tilt and the height of the meticulous periodic structure of control, and if acquisition is used to obtain the height of enough anti-reflection effect, degree of tilt increases to cause scattering, on the contrary, light transmission reduces.

The method that forms fine pattern by fine processing equipment has such shortcoming: this formation method of patterning not only needs very large-scale equipment, thereby capital outlay that need be very high, though this method is suitable for forming pattern on flat surfaces, is difficult on the complicated shape such as curvilinear surface and forms pattern.In addition, this method is not suitable for the application to the universal optical parts, because handling capacity is low and the processing on big zone is very difficult.

The method of growth boehmite is very convenient in substrate, and has very high throughput rate, but aluminium oxide and boehmite are amphoteric compounds, thereby is decomposed by bronsted lowry acids and bases bronsted lowry easily.Therefore, when the alkali ion of substrate etc. is moved to the surface, and owing to carrying out exchange interaction when making the surface become alkaline environment, because the decomposition on surface, keep the difform shape difficulty that becomes, thereby performance reduces with airborne water.For refractive index and significantly different substrate of aluminium oxide, the difference of the refractive index at the interface between substrate and the aluminium is so big, to such an extent as to fully do not show antireflective property.

Summary of the invention

Consider above-mentioned correlation technique and make the present invention, and the purpose of this invention is to provide and a kind ofly can keep the optical clear parts of high-performance anti-reflection effect over a long time for any substrate, and the optical system of using these optical clear parts.

The invention provides a kind of optical clear parts that are used to realize above-mentioned purpose that dispose in following described mode.

That is, the invention provides a kind of optical clear parts, it has in substrate: comprise SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and by comprising Al ₂O ₃As the flat crystal layer that the flat crystal of principal ingredient forms, wherein the surface of this flat crystal layer is made of irregularly shaped.

According to comprising SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and by comprising Al ₂O ₃It is preferred that the order of the flat crystal layer that forms as the flat crystal of principal ingredient piles up in substrate.

Comprise Al ₂O ₃As the flat crystal of the flat crystal layer of principal ingredient by with respect to comprising Al ₂O ₃As the layer of principal ingredient more than or equal to 45 ° and to be less than or equal to 90 ° direction setting be preferred.

The erose thickness on the surface of flat crystal layer is for more than or equal to 20nm and to be less than or equal to 1000nm be preferred.

Irregularly shaped for the surface of flat crystal layer, the two dimension of the center line average roughness by having difform surface are extended the average surface roughness Ra ' that obtains and are worth for more than or equal to 5nm and be less than or equal to 100nm, and surface area compares S _r=S/S ₀(S wherein ₀The area of expression when surface measurements is ideal flat, and S represents the surface area on actual measurement surface) be more than or equal to 1.1 and to be less than or equal to 3.5 be preferred.

The refractive index n of substrate _b, comprise SiO ₂As principal ingredient the layer refractive index n _s, and comprise Al ₂O ₃As principal ingredient the layer refractive index n _aSatisfy following relation: n _b〉=n _s〉=n _aBe preferred.

Comprise SiO ₂More than or equal to 5nm and be less than or equal to 100nm, and comprise Al as the thickness of the layer of principal ingredient ₂O ₃As the thickness of the layer of principal ingredient more than or equal to 10nm and to be less than or equal to 120nm be preferred.

In addition, the invention provides a kind of optical system with above-mentioned optical clear parts.

This optical system is that image-pickup optical system, observation optical system, projection optical system or scanning optics are preferred.

Optical clear parts of the present invention have the SiO of comprising ₂As the layer of principal ingredient, this layer is arranged in the substrate, and is comprising Al ₂O ₃Under the layer as principal ingredient, and the refractive index n of substrate _b, comprise SiO ₂As principal ingredient the layer refractive index n _s, and comprise Al ₂O ₃As principal ingredient the layer refractive index n _aSatisfy following relation: n _b〉=n _s〉=n _a, thereby make and may further improve low reflectivity properties by comprising the flat crystal layer that the flat crystal of aluminium oxide as principal ingredient form.

In addition, comprise SiO ₂Suppress alkali become to grade migration from the substrate to the surface as the layer of principal ingredient, and can keep antireflective property for a long time.

The substrate surface of optics of the present invention is coated with successively and comprises SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and by comprising Al ₂O ₃The flat crystal layer that forms as the flat crystal of principal ingredient, and the outmost surface of flat crystal layer has irregularly shaped.Because by with respect to comprising Al ₂O ₃As the layer of principal ingredient more than or equal to 45 ° and be less than or equal to size random of random and flat crystal of the directivity on interval, plate surface between the setting of 90 ° direction, the plate surface in the layer, the flat crystal layer that is formed by flat crystal forms irregularly shaped, and the thickness of layer is more than or equal to 20nm and be less than or equal to 1000nm.For the density of flat crystal, it is more than or equal to 5nm that the two dimension of the center line average roughness by coating is extended the average surface roughness value Ra ' that obtains, and surface area compares S _r=S/S ₀(S wherein ₀The surface area of expression when surface measurements is ideal flat, and S represents the surface area on actual measurement surface) be more than or equal to 1.1.The thickness of layer of having arranged flat crystal is more than or equal to 20nm and be less than or equal to 1000nm.

The refractive index n of substrate _b, comprise SiO ₂As principal ingredient the layer refractive index n _s, and comprise Al ₂O ₃As principal ingredient the layer refractive index n _aSatisfy following relation: n _b〉=n _s〉=n _a, comprise SiO ₂More than or equal to 5nm and be less than or equal to 100nm, and comprise Al as the thickness of the layer of principal ingredient ₂O ₃As the thickness of the layer of principal ingredient more than or equal to 10nm and be less than or equal to 120nm, thereby the irregularly shaped of the surface of refractive index from substrate to the flat crystal layer that is formed by flat crystal reduces gradually, and the anti-reflection effect of flat crystal layer significantly improves.

Comprise SiO ₂Layer as principal ingredient will comprise the substrate of various compositions and has high response and comprise Al ₂O ₃Layer as principal ingredient is isolated from each other, and suppresses to move to from substrate such as the reacted constituent of alkali and comprise Al ₂O ₃As the layer of principal ingredient, thereby make and to demonstrate anti-reflection effect steadily in the long term.

As mentioned above, optical clear parts of the present invention can demonstrate high anti-reflection effect steadily in the long term.

From following description taken together with the accompanying drawings, other features of the present invention and advantage will become obvious.

Description of drawings

Fig. 1 shows the synoptic diagram of an embodiment of optical clear parts of the present invention;

Fig. 2 shows form in substrate of glass and the photo (scale factor of taking from top surface by FE-SEM in first example: X100000) that have the observed result of meticulous difform layer from the teeth outwards;

Fig. 3 shows the photo (scale factor: X150000) of the observed result of form and the xsect of taking by FE-SEM in first example that have meticulous difform layer on substrate of glass;

Fig. 4 is the front view of the 6th example of the present invention;

Fig. 5 is the cut-open view of the 6th example of the present invention;

Fig. 6 is the front view of the 7th example of the present invention;

Fig. 7 is the cut-open view of the 7th example of the present invention;

Fig. 8 is the front view of the 8th example of the present invention;

Fig. 9 is the cut-open view of the 8th example of the present invention;

Figure 10 is the front view of the 9th example of the present invention;

Figure 11 is the cut-open view of the 9th example of the present invention;

Figure 12 is the cut-open view of the tenth example of the present invention;

Figure 13 is the cut-open view of the 11 example of the present invention;

Figure 14 is the cut-open view of the 12 example of the present invention; And

Figure 15 is the cut-open view of the 13 example of the present invention.

Embodiment

To describe the present invention in detail below.

Fig. 1 shows the synoptic diagram of an embodiment of optical clear parts of the present invention.In Fig. 1, optical clear parts of the present invention have in substrate 21: comprise SiO ₂As the layer 22 of principal ingredient, comprise Al ₂O ₃As the layer 23 of principal ingredient and by comprising Al ₂O ₃The flat crystal layer 24 that forms as the flat crystal of principal ingredient, and the surface of this flat crystal layer 24 has irregularly shaped 25.

Comprise Al ₂O ₃(aluminium oxide) is that oxide by using aluminium or oxyhydroxide or its hydrate form as principal ingredient as the flat crystal of principal ingredient.Particularly preferred crystal is a boehmite.By arranging these flat crystals, their end forms meticulous irregular shape, therefore flat crystal optionally by with respect to laminar surface more than or equal to 45 ° and to be less than or equal to 90 ° direction setting be preferred, be used to increase meticulous difform height and reduce therebetween interval.

The thickness of the crystal layer that is formed by flat crystal is preferably more than or equal to 20nm and is less than or equal to 1000nm, more preferably for more than or equal to 50nm and be less than or equal to 1000nm.If the thickness that forms difform layer is more than or equal to 20nm and be less than or equal to 1000nm, antireflective property by meticulous irregular shape structure is effective, eliminated the possibility of destroying difform physical strength, and meticulous difform structure becomes aspect manufacturing cost and has superiority.More preferably, thickness is more than or equal to 50nm and is less than or equal to 1000nm, thereby further improves antireflective property.

Meticulous difform superficial density of the present invention also is important, and the two dimension by center line average roughness is extended the corresponding average surface roughness Ra ' that obtains and is worth for more than or equal to 5nm, more preferably be more than or equal to 10nm, further more preferably for more than or equal to 15nm and be less than or equal to 100nm, and surface area compares S _rBeing 1.1, more preferably is more than or equal to 1.15, further preferably for more than or equal to 1.2 and be less than or equal to 3.5.

One of method that is used to assess the meticulous irregular shape structure that is obtained is to observe the surface of meticulous irregular shape structure by scanning probe microscope, and, determined that the two dimension of the center line average roughness Ra by layer is extended average surface roughness Ra ' value and the surface area ratio S that obtains by observing _rPromptly, average surface roughness Ra ' value (nm) is to make the center line average roughness Ra that defines among the JIS B0601 be applied to surface measurements and by the value of three-dimensional extension, and Ra ' value is expressed as " being averaged the value that obtains by the absolute value to the deviation from the reference surface to the designated surface ", and is provided by following formula (1).

$R{a}^{\′}=\frac{1}{S_0}{\∫}_{Y_B}^{Y_T}{\∫}_{X_L}^{X_R}|F(X,Y)-Z_0|d_X{d}_Y---\left(1\right)$

Ra ': average surface roughness value (nm),

S ₀: the area when surface measurements is ideal flat, | X _R-X _L| * | Y _T-Y _B|,

F (X, Y): measurement point (wherein X is the X coordinate for X, height Y), and Y is the Y coordinate,

X _L-X _R: the X coordinate range on the surface measurements,

Y _B-Y _T: the Y coordinate range on the surface measurements,

Z ₀: the average height in surface measurements.

Pass through S _r=S/S ₀Determine surface area ratio S _r(S ₀: the area when surface measurements is ideal flat.S: the surface area on actual measurement surface).The surface area on actual measurement surface is determined as follows.Surface measurements is divided into the very little triangle of being made up of immediate three data points (A, B, C), then uses vector product to determine each very little leg-of-mutton area Δ S.Δ S (Δ ABC) equals [s (s-AB) is (s-AC) (s-BC)] ^0.5(wherein AB, BC and AC are the length on each limit, and S ≡ 0.5 (AB+BC+AC) keeps), and the summation of area Δ S is surface area S to be determined.If the Ra ' value as meticulous difform superficial density is equal to or greater than 5nm and S _rBe equal to or greater than 1.1, can realize antireflection by irregular shape structure.If Ra ' value is equal to or greater than 10nm and S _rBe equal to or greater than 1.15, then anti-reflection effect becomes and is higher than the anti-reflection effect of afore-mentioned.If Ra ' is equal to or greater than 15nm and S _rBe equal to or greater than 1.2, difform structure has the actual performance of using of tolerance.Yet, if Ra ' value is equal to or greater than 100nm and S _rBe equal to or greater than 3.5, the dispersion effect that irregular shape structure causes is compared with anti-reflection effect and is preponderated, and makes to obtain sufficient anti-reflection effect.

Comprise Al ₂O ₃Layer as principal ingredient can be to comprise Al ₂O ₃As any amorphous oxides coating of principal ingredient, and, can add such as TiO separately as different types of composition ₂, ZrO ₂, SiO ₂, ZnO or MgO oxide, maybe can select, make up and add two or more of these oxides.Particularly, select layer to make the refractive index n of this film _aWith comprise SiO ₂As principal ingredient the layer refractive index n _sBetween relation be n _s〉=n _a, as the result of control component content.In this case, with Al ₂O ₃The preferred mol% of film is than for being equal to or greater than 50% and be equal to or less than 100%, more preferably, is equal to or greater than 70% and be equal to or less than 100%.Therefore, from substrate to the scope at the interface of air in, refractive index reduces continuously, and comprises the effect of aluminium oxide as the layer of the flat crystal of principal ingredient along with having arranged, can realize high antireflective property.

The SiO that comprises of the present invention ₂Layer as principal ingredient can be to comprise SiO ₂As any amorphous oxides coating of principal ingredient, and, can add such as TiO alone or in combination as different types of composition ₂And ZrO ₂Oxide.Particularly, select layer so that can suppress alkali etc. to comprising Al ₂O ₃As the migration of the layer of principal ingredient, and the refractive index n of this film _sRefractive index n with substrate _bBetween relation be n _b〉=n _s, as the result of control component content.In this case, with SiO ₂The preferred mol% of film is than for being equal to or greater than 40% and be equal to or less than 100%, more preferably, is equal to or greater than 60% and be equal to or less than 100%.Therefore, from substrate to the scope at the interface of air in, refractive index reduces continuously, and along with by comprising Al ₂O ₃The flat crystal layer that forms as the flat crystal of principal ingredient and comprise Al ₂O ₃As principal ingredient the layer effect, can realize high antireflective property.Further, by except above-mentioned oxide, adding sour composition such as phosphoric acid, can improve suppress alkali etc. from substrate to comprising Al ₂O ₃The performance of migration effect as the layer of principal ingredient.

Optical clear parts of the present invention can be by known gas phase process such as CVD or PVD, such as the liquid phase process of sol-gel technology, use that the hydrothermal solution of inorganic salts is synthetic etc. to be formed.By this method, can comprise by SiO ₂As directly being provided with after the layer of principal ingredient by comprising the flat crystal that aluminium oxide is formed as the flat crystal of principal ingredient, and formation comprises Al successively ₂O ₃Layer as principal ingredient.Replacedly, on this of each layer is two-layer, form the layer that has only metal A l, or comprise after the metal level of any metal among metal A l and Metal Zn and the metal M g, the surface of this layer can be by being immersed in 50 ℃ or the hotter hot water or being exposed in the water vapor and dissolved or precipitation, so that the flat crystal of aluminium oxide to be provided.Replacedly, comprising SiO ₂Go up formation as the layer of principal ingredient and have only Al ₂O ₃Layer, or comprise Al ₂O ₃, and ZrO ₂, SiO ₂, TiO ₂, among ZnO and the MgO after one or more oxide skin(coating)s of any composition, the surface of layer can optionally dissolve or precipitate, so that the flat crystal of aluminium oxide to be provided.Wherein, preferably a kind of like this method wherein comprises SiO with hot water treatment by applying successively ₂The colloidal sol coating solution and comprise Al ₂O ₃The colloidal sol coating solution and the gel mould that forms, with growth alumina wafer shape crystal.

For from comprising Al ₂O ₃The starting material of the gel mould that obtains of colloidal sol coating solution, use the Al compound, perhaps at least a the and Al compound in the compound of Zr, Si, Ti, Zn and Mg uses jointly.For Al ₂O ₃, ZrO ₂, SiO ₂, TiO ₂, ZnO and MgO starting material, can use the alkoxide compound of each metal and such as the salt compound of chloride and nitrate.From the viewpoint of system film ability, preferably use the metal alkoxide compound, especially for ZrO ₂, SiO ₂And TiO ₂Starting material.

Aluminium compound for example comprises: the oligomer of aluminium ethylate, aluminium isopropoxide, Tributyl aluminate, aluminium secondary butylate, tert-butyl alcohol aluminium, acetoacetate aluminium or these compounds, aluminium nitrate, aluminum chloride, aluminum acetate, aluminum phosphate, aluminium sulphate and aluminium hydroxide.

The object lesson of zirconium alkoxide comprises tetramethyl alcohol zirconium, tetraethoxide zirconium, four zirconium-n-propylates, four zirconium iso-propoxides, four zirconium-n-butylates and four zirconium tert-butoxide.

For alkoxyl silicone, can use by general formula Si (OR) ₄The all cpds of expressing.R is identical or different than low alkylene, for example methyl, ethyl, propyl group, isopropyl, butyl or isobutyl.

Alkoxytitanium for example comprises: tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide and four isobutoxy titaniums.

Zinc compound for example comprises: zinc acetate, zinc chloride, zinc nitrate, zinc stearate, zinc oleate and zinc salicylate, and particularly preferably be zinc acetate and zinc chloride.

Magnesium compound comprises: for example such as alkoxyl magnesium, acetoacetate magnesium and the magnesium chloride of dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium and dibutoxy magnesium.

Organic solvent can be any organic solvent that does not cause such as the starting material gelation of above-mentioned alkoxide compound, and this organic solvent for example comprises: such as the alcohol of methyl alcohol, ethanol, 2-propyl alcohol, butanols, ethylene glycol or ethylene glycol propyl ether; Various aliphatic hydrocarbons or alicyclic hydrocarbon such as hexane, normal octane, cyclohexane, cyclopentane and cyclooctane; Various aromatic hydrocarbons such as toluene, dimethylbenzene and ethylbenzene; Various esters such as ethyl formate, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate and butyl glycol ether acetic acid esters; Various ketone such as acetone, methyl ethyl ketone, methylisobutylketone and cyclohexanone; Various ethers such as dimethoxy-ethane, tetrahydrofuran, dioxane and diisopropyl ether; Various chlorinated hydrocarbons such as chloroform, methylene chloride, phenixin and tetrachloroethane; And such as the aprotic polar solvent of N-methyl noise made in coughing or vomiting ketone (N-methyl pyrolidone), dimethyl formamide, dimethyl acetamide and ethylene carbonate.In above-mentioned all kinds of solvents, aspect solution stable, alcohol is preferred the use.

If use the alkoxide compound and the reaction of water height of alkoxide compound starting material, particularly aluminium, zirconium and titanium, and the moisture by adding air or water and rapid hydrolysis causes muddiness and precipitation.Aluminum chloride compound, zinc chloride compound and magnesium chloride compound are difficult to only dissolve in organic solvent, and their solution is stable low.In order to prevent this situation, preferably add stabilizing agent and come stabilizing solution.

Stabilizing agent for example can comprise: such as the beta diketone compound of diacetone, trifluoroacetylacetone (TFA), hexafluoroacetylacetone, benzoyl acetone and dibenzoyl methane; β ketone ester compound such as methyl acetoacetate, ethyl acetoacetate, pyruvic acid allyl ester (allyl ketoacetate), acetoacetate benzene methyl, isopropyl acetoacetate, tert-butyl acetoacetate, isopropyl acetoacetate, acetoacetate root-2-methoxy ethyl (acetoacetate-2-methoxyethyl) and 3-ketone group-positive methylpent acid esters (3-keto-n-methyl-valeriate); And such as the alkanolamine of monoethanolamine, diethanolamine and triethanolamine.The amount of the stabilizing agent that is added is preferably 1 according to the mol ratio with alkoxide compound or salt compound.Add after the stabilizing agent, preferably add catalyzer and be used to promote partial reaction, to form suitable presoma.Catalyzer for example can comprise nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and ammoniacal liquor.

For from comprising SiO ₂The starting material of the gel mould that obtains of colloidal sol coating solution, use the Si compound, perhaps at least a the and Si compound in the compound of Ti and Zr uses jointly.For SiO ₂, TiO ₂And ZrO ₂Starting material, can use the alkoxide compound of each metal and such as the salt compound of chloride and nitrate, but, preferably use the metal alkoxide compound from the viewpoint of system film ability.For the alkoxide compound of metal, solvent, stabilizing agent etc., can use aforesaid compound.Catalyzer as promoting partial reaction preferably uses the acid such as phosphoric acid, is used for catching the alkali that moves at film.Use SiO ₂(n=1.45 of itself), TiO ₂(n=2.20 of itself) and ZrO ₂(itself n=1.90) suitably selects the ratio of components of every kind of composition, makes refractive index n _sRefractive index n with substrate _bWith comprise Al ₂O ₃As principal ingredient the layer refractive index n _aBetween relation be n _b〉=n _s〉=n _aKnown TiO ₂Have high refractive index, and improve the range of control of the refraction coefficient of film, however TiO ₂Can cause from the noncrystal anatase crystal of changing into by the processing that is immersed in the hot water or be exposed in the water vapour.Effect equal angles from keeping the coating homogeney and suppressing the alkali migration preferably reduces the TiO in the film ₂Part turns to anatase crystal to suppress crystal, and the TiO in the film ₂Mol% than preferably less than 40%.More preferably be 30% or still less.

As using the cambial method of above-mentioned colloidal sol coating solution, for example can suitably use known painting method such as dipping method, spin coating method, spraying method, printing process, flow coat (flow coating) method and combination thereof.Film thickness can pass through to change the pulling speed in the dipping method, the substrate rotational speed in the spin coating method etc., and the concentration of change coating solution is controlled.Wherein, can suitably select pulling speed in the dipping method according to the required film thickness degree, but preferably, mention film to relax even velocity after soaking, this relaxes even velocity for example is about 0.1 to arrive 3.0mm/ second.Apply after this layer, can at room temperature make it dry about 30 minutes.This film also can carry out drying or thermal treatment under higher temperature, and heat treatment temperature is high more, the just easy more densification of this film.Comprising Al ₂O ₃Under the situation as the gel mould of principal ingredient, can form bigger difform structure by increasing heat treatment temperature.Comprising SiO ₂Under the situation as the gel mould of principal ingredient, can improve the ability that suppresses migrations such as alkali by increasing heat treatment temperature.

Then, immersion comprises SiO by applying successively in hot water ₂As the colloidal sol coating solution of principal ingredient with comprise Al ₂O ₃The gel mould that forms as the colloidal sol coating solution of principal ingredient, thus precipitation comprises Al ₂O ₃As the flat crystal of principal ingredient, to form the difform shape of outmost surface.By in hot water, soaking, comprise Al by applying successively ₂O ₃The colloidal sol coating solution and the superficial layer of the gel mould that forms bears peptization etc., and some compositions are by elution, but because the difference of the solubleness of various oxyhydroxide in hot water comprises Al ₂O ₃Be deposited in the superficial layer of gel mould as the flat crystal of principal ingredient, and grow.The temperature of hot water is preferably 40 ℃ to 100 ℃.The hot water treatment time is about 5 minutes to about 24 hours.

Comprise Al for having as adding to ₂O ₃As different types of composition of the film of principal ingredient such as TiO ₂, ZrO ₂, SiO ₂, ZnO and MgO the hot water treatment of gel mould of oxide, therefore and Al use the difference of the solubleness of each composition in hot water to carry out crystallization, ₂O ₃The hot water treatment difference of separate constituent film, can be by the composition that changes inorganic constituents in the size of wide region inner control flat crystal.As a result, can be in the difform shape of wide region inner control by flat crystal formation.In addition, if ZnO is as subconstiuent, with Al ₂O ₃Coprecipitation becomes possibility, thereby can be in wideer scope inner control refractive index, thereby makes and may realize fabulous antireflective property.

Comprise SiO ₂Of the present invention layer thickness as principal ingredient is equal to or greater than 5nm and is equal to or less than 100nm, more preferably for being equal to or greater than 5nm and being equal to or less than 80nm.If thickness less than 5nm, then can not obtain to suppress the abundant effect of alkali migration.If thickness is greater than 100nm, owing to disturb etc. former thereby the contribution that reflection reduces effect is reduced.Comprise Al ₂O ₃As principal ingredient the layer thickness for being equal to or greater than 10nm and being equal to or less than 120nm, more preferably for being equal to or greater than 10nm and being equal to or less than 100nm.If thickness is less than 10nm, the adhesiveness of flat crystal reduces, and comprises SiO ₂The gradient variable of difference as refractive index between the layer of principal ingredient and the flat crystal layer is too much, to such an extent as to optical property suffers damage.If thickness is greater than 120nm, owing to disturb etc. former thereby the contribution that reflection reduces effect is reduced.

The substrate of Shi Yonging in the present invention comprises glass, resin, glass reflector and the catoptron that is formed from a resin.The exemplary of resin base comprises such as the film of the thermoplastic resin of polyester, triacetyl cellulose, cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene, polycarbonate, polymethylmethacrylate, ABS resin, polyphenylene oxide, polyurethane, tygon and Polyvinylchloride and moulded product; The cross linking membrane and the crosslinked moulded product that obtain from various thermoset resins such as unsaturated polyester resin, phenolic resin, cross-linked polyurethane, crosslinked acryl resin and crosslinked saturated polyester resin.The object lesson of glass can comprise alkali-free glass and aluminosilicate glass.The substrate of Shi Yonging in the present invention can be made with any material that can finally form the shape that is suitable for application target, and this shape comprises flat board, film and sheet, and can have two dimension or three-dimension curved surface.Can suitably determine thickness, and thickness is approximately and is equal to or less than 5mm, but be not limited thereto.

Except above-mentioned layer, optical clear parts of the present invention can further be provided with the layer that is used to give various functions.For example, the hardness that hard coat is used to improve film can be set on the flat crystal layer, the fluoroalkyl silanes (fluoroalkyl silane) or the water barrier of alkyl silane perhaps can be set be used for imparting water repellency.For accumulation of preventing pollutant etc., refractive index can be set be lower than and comprise Al ₂O ₃As the layer of the refractive index materials of the flat crystal of principal ingredient, perhaps by amphoteric compound forms layer.In order to improve substrate and to comprise SiO ₂As the stickability between the layer of principal ingredient, can use adhesive coating or prime coat.In substrate with comprise SiO ₂The refractive index of other layers that are provided with between the layer as principal ingredient preferably substrate refractive index and comprise SiO ₂As principal ingredient the layer refractive index between intermediate value.

To specifically describe the present invention in conjunction with example.Yet, the invention is not restricted to this example.By the assessment of following method from each example and comparative example acquisition and have meticulous difform hyaline membrane from the teeth outwards.

(1) shape of observation coating

(FE-SEM that the Hitachi produces S4500) observes the surface (accelerating potential of the superficial layer of coating by camera style to use scanning electron microscope; 10.0kV, zoom factor; 30000).Use scanning probe microscope (SPM, the DFM type is by the SPI3800 of Seiko Electronics Industry Company production), determined to extend average surface roughness Ra ' value and the surface area ratio S that obtains by the two dimension of the center line average roughness of definition in JIS B 0601 _r

(2) measurement of transmissivity

Use automated optical parts measuring equipment (ART-25GD that JASCO produces), in the scope from the visibility region to the near infrared region, measure transmissivity.Use the plate-like glass plate.Angle of light in transmissivity and albedo measurement is respectively 0 ° and 10 °.

(3) measurement of film refractive index

Ellipsometer VASE by Japanese J.A.Woollam Co., Ltd. produces measures in the wavelength coverage of 800nm at 380nm.

Example 1

Be of a size of the float glass that about 100mm * 100mm and thickness are about 2mm (clear-float glass) substrate (component: sodium-calcium-silicate type, refractive index n g=1.52) carries out ultrasonic cleaning by isopropyl alcohol, drying, and with the glass substrate that acts on coating.

Tetraethoxysilane (TEOS) is dissolved in the ethanol (EtOH), and the phosphate aqueous solution of 0.01M is added in the solution of gained as catalyzer, and the gained potpourri was stirred 6 hours.This moment, the mol ratio of each composition was TEOS: EtOH: H ₃PO ₄Aq=1: 40: 2.Normal butyl alcohol titanium (TBOT) is dissolved in the ethanol, then ethyl acetoacetate (EAcAc) is added in the gained solution as stabilizing agent, and the gained potpourri at room temperature stirs 3 hours.The mol ratio of each composition is TBOT: EtOH: EAcAc=1: 20: 1.TiO ₂Sol solution adds aforementioned SiO to ₂In the sol solution, make to obtain SiO ₂: TiO ₂=95: 5 mol ratio, and the gained potpourri at room temperature stirred 2 hours, and then as SiO ₂-TiO ₂Coating solution.Then, aforementioned coated glass substrate is immersed in this coating solution, and coated film is formed on the surface of glass substrate by dipping method (with the 0.5mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous SiO ₂/ TiO ₂Film applies thereon.

Measure the thickness and the refractive index of gained film, and measurement result illustrates thickness d _sBe d _s=20nm, and refractive index is n _s=1.48.

Then, aluminium secondary butylate (Al (O-sec-Bu) ₃) be dissolved among the IPA, EAcAc adds in the gained solution as stabilizing agent, and the potpourri of gained at room temperature stirred about 3 hours.After this, 0.01M[HCl aq.] add in the gained solution, and the gained potpourri at room temperature stirred about 3 hours, to prepare Al ₂O ₃Sol solution.At this, the mol ratio of solution is Al (O-sec-Bu) ₃: IPA: EAcAc: HClaq.=1: 20: 1: 1.Aforementioned coated substrate is immersed in this coating solution, and coated film is formed on the surface of glass substrate by dipping method (with the 2mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, transparent amorphous Al ₂O ₃Film applies thereon.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as shown in Figure 2.Observe xsect by FE-SEM, wherein comprise Al as shown in Figure 3 to observe ₂O ₃As the flat crystal of principal ingredient optionally with the direction of the Surface Vertical of layer on the image arranged.Orlop among Fig. 3 is the glass xsect of substrate, and the middle layer is by comprising SiO ₂As the layer of principal ingredient with comprise Al ₂O ₃The layer of forming as the layer of principal ingredient, and the flat crystal layer formed by flat crystal of the superiors.By the SPM surface measurements, and measurement result average surface roughness Ra ' value (nm) is shown is Ra '=28nm, and surface area ratio S _rBe S _r=1.9.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test as accelerated test, with the permanance of check optical property, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 2

The S-TIH53 glass substrate (being produced refractive index n=1.84 by OHARA company) that is of a size of about 50mm * 50mm and thickness and is about 1mm carries out ultrasonic cleaning by isopropyl alcohol, drying, and with the glass substrate that acts on coating.

TiO ₂Sol solution adds aforementioned SiO to ₂In the sol solution, make to obtain SiO ₂: TiO ₂=7: 3 mol ratio, and the gained potpourri at room temperature stirred 2 hours, and then as SiO ₂-TiO ₂Coating solution is described in example 1.Then, aforementioned coated glass substrate is immersed in this coating solution, and coated film is formed on the surface of glass substrate by dipping method (with the 0.5mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous SiO ₂/ TiO ₂Film applies thereon.Measure the thickness and the refractive index of the film obtained, and measurement result illustrates, thickness is that 28nm and refractive index are n _sBe 1.67.

Then, aforementioned coated substrate is immersed in the Al as example 1 ₂O ₃In the coating solution, then coated film is formed on the surface of glass substrate by dipping method (with the 2mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃Film applies thereon.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=27nm, and surface area ratio S _rBe S _r=1.9.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 3

Use S-TIH53 glass substrate (by OHARA company the produce refractive index n=1.84) usefulness identical to act on the glass substrate of coating with example 2.

Apply SiO ₂/ TiO ₂(7/3), then forms transparent amorphous SiO in the mode identical with example 2 ₂/ TiO ₂Film.Measure the thickness and the refractive index of the film obtained, and measurement result illustrates, thickness is 28nm and refractive index n _sBe 1.67.

Aluminium secondary butylate [Al (O-sec-Bu) ₃] be dissolved in 2 propyl alcohol [IPA], ethyl acetoacetate [EAcAc] adds in the solution of gained as stabilizing agent, and the potpourri of gained at room temperature stirred about 3 hours, to prepare Al ₂O ₃Sol solution.At this, the mol ratio of this solution is Al (O-sec-Bu) ₃: IPA: EAcAc=1: 20: 1.Normal butyl alcohol titanium [Ti (O-n-Bu) ₄] also be dissolved among the IPA, EAcAc adds in the gained solution, and the gained potpourri stirred about 3 hours, to prepare TiO ₂Sol solution.The mol ratio of this solution is Ti (O-n-Bu) ₄: IPA: EAcAc=1: 20: 1.This TiO ₂Sol solution adds aforementioned Al to ₂O ₃In the sol solution, make to obtain Al ₂O ₃: TiO ₂=8: 2 weight ratio, about 30 minutes of gained solution stirring is then with 0.01M[HCl aq.] add in the gained potpourri, and the gained potpourri at room temperature stirred about 3 hours.By this way, all set as Al ₂O ₃/ TiO ₂The coating solution of colloidal sol.At this, the amount of the HCl aq. that is added is Al (O-sec-Bu) according to mol ratio ₃And Ti (O-n-Bu) ₄The twice of amount.

Then, as example 1, aforementioned coated substrate is immersed in Al ₂O ₃/ TiO ₂In the coating solution, and coated film is formed on the surface of glass substrate by dipping method (with the 1mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃/ TiO ₂Film applies thereon.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=18nm, and surface area ratio S _rBe S _r=1.5.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 4

Use the S-TIH53 glass substrate identical (by the production of OHARA company, refractive index n with example 2 _b=1.84) as the glass substrate that is used to apply.

Apply SiO ₂/ TiO ₂(7/3), then forms amorphous Si O in the mode identical with example 2 ₂/ TiO ₂Film.Measure the thickness and the refractive index of the film obtained, and measurement result illustrates, thickness is that 28nm and refractive index are n _sBe 1.67.

Aluminium secondary butylate [Al (O-sec-Bu) ₃] be dissolved in 2 propyl alcohol [IPA], ethyl acetoacetate [EAcAc] adds in the gained solution as stabilizing agent, and the potpourri of gained at room temperature stirred about 3 hours, to prepare Al ₂O ₃Sol solution.At this, the mol ratio of this solution is Al (O-sec-Bu) ₃: IPA: EAcAc=1: 20: 0.5.2 hydration zinc acetate [Zn (CH ₃COO) ₂2H ₂O] also be dissolved in [IPA], [MEA] adds in the gained solution with monoethanolamine, and the gained potpourri stirred about 3 hours, to prepare the ZnO sol solution.The mol ratio of this solution is Zn (CH ₃COO) ₂2H ₂O: IPA: MEA=1: 10: 1.This ZnO sol solution adds aforementioned Al to ₂O ₃In the sol solution, make to obtain Al ₂O ₃: ZnO=0.8: 0.2 weight ratio, and the gained potpourri stirred about 30 minutes.By this way, all set as Al ₂O ₃The coating solution of-ZnO colloidal sol.

Then, as example 1, aforementioned coated substrate is immersed in Al ₂O ₃In/ZnO the coating solution, then, coated film is formed on the surface of glass substrate by dipping method (with the 2mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃/ ZnO film applies thereon.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=32nm, and surface area ratio S _rBe S _r=2.0.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 5

Use is of a size of the S-TIH1 glass substrate that about 50mm * 50mm and thickness are about 1mm and (is produced refractive index n by OHARA company _b=1.71) as the glass substrate that is used to apply.

Zirconium-n-butylate (ZBOT) is dissolved in the ethanol, and ethyl acetoacetate (EAcAc) adds in the gained solution as stabilizing agent, and the potpourri of gained at room temperature stirred about 3 hours.The mol ratio of each composition is ZBOT: EtOH: EAcAc=1: 20: 1.As example 1, TiO ₂Sol solution then is ZrO ₂Sol solution adds SiO to ₂In the sol solution, make to obtain SiO ₂: TiO ₂: ZrO ₂=7: 1: 2 mol ratio, and the gained potpourri at room temperature stirred 2 hours, and then as SiO ₂-TiO ₂-ZrO ₂Coating solution.Then, aforementioned coated glass substrate is immersed in this coating solution, and coated film is formed on the surface of glass substrate by dipping method (with the 0.5mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous SiO ₂/ TiO ₂/ ZrO ₂Film applies thereon.Measure the thickness and the refractive index of the film obtained, and measurement result illustrates, thickness is that 25nm and refractive index are n _s=1.62.

Aluminium secondary butylate [Al (O-sec-Bu) ₃] be dissolved in 2 propyl alcohol [IPA], ethyl acetoacetate [EAcAc] adds in the gained solution as stabilizing agent, and the potpourri of gained at room temperature stirred about 3 hours, to prepare Al ₂O ₃Sol solution.At this, the mol ratio of this solution is Al (O-sec-Bu) ₃: IPA: EAcAc=1: 20: 0.5.2 hydration zinc acetate [Zn (CH ₃COO) ₂2H ₂O] also be dissolved in [IPA], [MEA] adds in the gained solution with monoethanolamine, and the gained potpourri stirred about 3 hours, to prepare the ZnO sol solution.The mol ratio of this solution is Zn (CH ₃COO) ₂2H ₂O: IPA: MEA=1: 10: 1.This ZnO sol solution adds aforementioned Al to ₂O ₃In the sol solution, make to obtain Al ₂O ₃: ZnO=0.9: 0.1 weight ratio, and the gained potpourri stirred about 3 hours.By this way, all set as Al ₂O ₃The coating solution of-ZnO colloidal sol.

Then, as example 1, aforementioned coated substrate is immersed in Al ₂O ₃In/ZnO the coating solution, then, coated film is formed on the surface of glass substrate by dipping method (with the 1mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃/ ZnO film applies thereon.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=30nm, and surface area ratio S _rBe S _r=1.9.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 6

For with example 5 in identical substrate, use the S-TIH1 glass substrate of producing by OHARA company (refractive index n=1.71) as the glass substrate that is used to apply, apply employed SiO in the example 2 ₂-TiO ₂Coating solution, and then form transparent amorphous SiO ₂/ TiO ₂Film.Measure the thickness and the refractive index of the film obtained, and measurement result illustrates, thickness is 28nm, and refractive index is n=1.67.

Then, this glass substrate is immersed in the Al that uses in the example 4 ₂O ₃Among/the ZnO, then coated film is formed on the surface of glass substrate with the pulling speed of 1mm/ second.Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃/ ZnO film applies thereon.Then, glass substrate further is immersed in the Al that uses in the example 1 ₂O ₃In the coating solution, and coated film is with the 1mm/ pulling speed formation of second.Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃Film applies thereon.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=23nm, and surface area ratio S _rBe S _r=1.7.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 7

On the float glass substrate that in example 1, uses, use magnetron sputtering apparatus to form the SiO of thickness as 30nm ₂Film.The refractive index of this film is 1.45.Then, glass substrate is immersed in the Al that uses in the example 1 ₂O ₃In the coating solution, then, coated film forms with the pulling speed of 2mm/ second.Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃Film applies thereon.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=22nm, and surface area ratio S _rBe S _r=1.6.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 8

On the float glass substrate that in example 1, uses, use magnetron sputtering apparatus to form the SiO of thickness as 30nm ₂Film.The refractive index of this film is 1.45.Then, by the magnetron sputtering apparatus coating thickness be the Al metal film of 35nm.Then, glass substrate soaked 30 minutes in 100 ℃ hot water.In a few minutes after immersion, the metallic luster of Al disappears, and after lifting, hyaline membrane is stayed on the superficial layer.Afterwards, this glass substrate is following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=57nm, and surface area ratio S _rBe S _r=2.6.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 9

In example 2, on the employed TIH53 substrate, use double magnetron sputtering apparatus to form the wherein SiO of thickness as 40nm ₂With ZrO ₂Ratio of component be 7: 3 synthetic transparent oxide film.The refractive index of film is 1.65.Then, by double sputter form thickness be 50nm, Al ₂O ₃With the ratio of component of ZnO be 8: 2 film.By the magnetron sputtering coating thickness is the Al metal film of 25nm.Then, glass substrate soaked 30 minutes in 100 ℃ hot water.In a few minutes after immersion, the metallic luster of Al disappears, and after lifting, hyaline membrane is stayed on the superficial layer.Afterwards, this glass substrate is following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=42nm, and surface area ratio S _rBe S _r=2.2.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Example 10

On example 5 employed TIH01 substrates, use double magnetron sputtering apparatus to form the wherein SiO of thickness as 40nm ₂With ZrO ₂Ratio of component be 8: 2 synthetic transparent oxide film.The refractive index of film is 1.61.Then, forming thickness by double sputter is 50nm's and Al ₂O ₃With the ratio of component of ZnO be 9: 1 film.By the magnetron sputtering coating thickness is the Al metal film of 200nm.Then, glass substrate soaked 30 minutes in 100 ℃ hot water.In a few minutes after immersion, the metallic luster of Al disappears, and after lifting, hyaline membrane is stayed on the superficial layer.Afterwards, this glass substrate is following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=45nm, and surface area ratio S _rBe S _r=2.3.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Comparative example 1

The float glass substrate that uses in example 1 is immersed in the Al that uses in the example 1 ₂O ₃In the sol solution, then, coated film is formed on the surface of glass substrate by dipping method (with the 2mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, transparent amorphous Al ₂O ₃Film applies thereon.Then, this glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=28nm, and surface area ratio S _rBe S _r=1.9.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Comparative example 2

The S-TIH53 substrate (refractive index n=1.84) that uses in example 2 is immersed in the Al that uses in the example 3 ₂O ₃/ TiO ₂In the sol solution, and coated film is formed on the surface of glass substrate by dipping method (with the 1mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and apply transparent amorphous Al thereon ₂O ₃/ TiO ₂Film.Then, glass substrate soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=18nm, and surface area ratio S _rBe S _r=1.5.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Comparative example 3

The float glass substrate (component: sodium-calcium-silicate type, refractive index n=1.52) that uses in the example 1 carries out ultrasonic cleaning by isopropyl alcohol, drying, and with the glass substrate that acts on coating.

With TiO ₂Sol solution adds aforementioned SiO to ₂In the sol solution, to obtain SiO ₂: TiO ₂=3: 7 mol ratio, and the gained potpourri at room temperature stirred 2 hours, then as SiO ₂-TiO ₂Coating solution is as example 1.Then, aforementioned coated glass substrate is immersed in this coating solution, and coated film is formed on the surface of substrate of glass by dipping method (with the 0.5mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the substrate of glass drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous SiO ₂/ TiO ₂Film applies thereon.

Measure the thickness and the refractive index of the film obtained, and measurement result illustrates, thickness is 28nm, and refractive index is 2.05.

Then, this glass substrate is immersed in the Al that uses in the example 1 ₂O ₃In the sol solution, then, coated film is formed on the surface of substrate of glass by dipping method (with the 2mm/ pulling speed of second, and 20 ℃ and 56%R.H.).Make the glass substrate drying, and the then baking thermal treatment by 400 ℃ one hour, and transparent amorphous Al ₂O ₃Film applies thereon.Then, substrate of glass was soaked 30 minutes in 100 ℃ hot water, and is then following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=28nm, and surface area ratio S _rBe S _r=1.9.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

Comparative example 4

On the float glass substrate that in example 1, uses, be the Al metal film of 25nm by the magnetron sputtering coating thickness.Then, glass substrate soaked 30 minutes in 100 ℃ hot water.In a few minutes after immersion, the metallic luster of Al disappears, and after lifting, hyaline membrane is stayed on the superficial layer.Afterwards, this glass substrate is following dry 10 minutes at 100 ℃.

The surface of the film that obtains by FE-SEM observation post to find meticulous difform structure, wherein comprises Al ₂O ₃As the flat crystal of principal ingredient at random and intricately tangle, as example 1.For by FE-SEM to the observation that xsect carries out, observe almost the structure identical with example 1.Measurement result by SPM illustrates, and average surface roughness Ra ' value (nm) is Ra '=32nm, and surface area ratio S _rBe S _r=2.1.

Then, for the film that is obtained, use oval meter to measure film thickness and refractive index.The thickness and the refractive index of each film are shown in table 1.

For this substrate, carry out temperature and be 60 ℃ and humidity and be 90% high-temperature and high humility test, and the zero hour, 250 hours after and measured transmissivity in 500 hours afterwards.It the results are shown in table 1.

[table 1]

	Substrate	Oval meter measurement result						Transmissivity measurement result (550nm)
											Refractive index n b	Comprise SiO 2Film as principal ingredient		Comprise Al 2O 3Film as principal ingredient		Comprise Al 2O 3Crystal layer as the flat crystal of principal ingredient		High-temperature and high humility test
	Thickness (nm)	Refractive index n a	Thickness (nm)	Refractive index n a	Thickness (nm)	Refractive index n a	The zero hour	250 hours	500 hours
										Example 1		1.52	20	1.48	100	1.42	230	1.42-1.0	99.6	99.6	99.5
Example 2	1.84	28	1.67	100	1.42	220	1.42-1.0	99.3	99.2		99.2
										Example 3		1.84	28	1.67	30	1.60	180	1.42-1.0	99.2	99.2	99.1
Example 4	1.84	28	1.67	80	1.55	300	1.53-1.0	99.5	99.5		99.3
										Example 5		1.71	25	1.62	80	1.50	300	1.49-1.0	99.4	99.4	99.4
Example 6	1.71	28	1.67	90	1.58	200	1.42-1.0	99.6	99.6		99.5
										Example 7		1.52	30	1.45	100	1.42	250	1.42-1.0	99.3	99.3	99.3
Example 8	1.52	30	1.45	30	1.42	500	1.42-1.0	99.8	99.8		99.6
										Example 9		1.84	40	1.65	40	1.58	400	1.54-1.0	99.4	99.3	99.3
Example 10	1.71	40	1.6	30	1.54	420	1.51-1.0	99.5	99.5		99.4
										Comparative example 1		1.52	-	-	100	1.42	230	1.42-1.0	99.4	98.0	93.5
Comparative example 2	1.84	-	-	30	1.60	180	1.42-10	97.2	93.8		89.6
										Comparative example 3		1.52	28	2.05	100	1.42	230	1.42-1.0	93.8	92.1	87.8
Comparative example 4	1.52	-	-	30	1.42	380	1.42-10	99.6	95.0		91.6

The refractive index of the crystal layer of (notes) flat crystal shows the starting point of graded index part and the value of end point.For example, the refractive index 1.42-1.0 in the example 1 shows refractive index from 1.42 to 1.0 reductions continuously in the thickness of 230nm.

[Performance Evaluation]

If the transmissivity of the transparent component that comparison 550nm makes in the place, initial performance in the example 1,7 and 8 and comparative example 1 and 4 are much at one, and show high value.Yet the accelerated durability test for high-temperature and high humility has the SiO of comprising ₂Example 1,7 and 8 as the layer of principal ingredient shows constant high value, and in not having the comparative example 1 and 4 of this layer, performance passs in time and descends significantly.Further, for the substrate with high index of refraction, example 2,3,4,5,6,9 and 10 has demonstrated high transmissivity after starting stage and accelerated durability test, and does not have the SiO of comprising ₂As principal ingredient the layer comparative example 2 and in lower level, have the TiO of comprising ₂As the layer of principal ingredient rather than comprise SiO ₂As the layer of principal ingredient and do not satisfy in the comparative example 3 of relation of nb 〉=ns 〉=na, transmissivity is just low from the starting stage, and performance descends significantly along with the carrying out of accelerated test.

Example 11

Fig. 4 is the front view of the optics of example 11.In this figure, optics 1 is concavees lens, and substrate 2 is provided with optical clear parts 3.

Fig. 5 shows the xsect of the optics of example 11 along the cutting of the 5-5 section among Fig. 4.Comprise SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged and comprise Al ₂O ₃Layer as the flat crystal of principal ingredient is formed on the optical surface, and the optical clear parts 3 with difform shape are formed on the outmost surface, thereby reduces the reflection of light on this optical surface.

In this example, optics is concavees lens, but the present invention is not restricted to this, and these lens can be convex lens or semilune lens.

Example 12

Fig. 6 is the front view of the optics of example 12.In this figure, optics 1 is a prism, and substrate 2 is provided with optical clear parts 3.

Fig. 7 shows the xsect of the optics of example 12 along the cutting of the 7-7 section among Fig. 6.Comprise SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged and comprise Al ₂O ₃Layer as the flat crystal of principal ingredient is formed on the optical surface, and the optical clear parts 3 with difform shape are formed on the outmost surface, thereby reduces the reflection of light on this optical surface.

In this example, the angle that the optical surface of prism forms is 90 ° and 45 °, but the present invention is not restricted to this, and the optical surface of prism can form any angle.

Example 13

Fig. 8 is the front view of the optics of example 13 of the present invention.In this figure, optics 1 is the fly's eye integraph, and substrate 2 is provided with optical clear parts 3.

Fig. 9 shows the xsect of the optics of example 13 along the cutting of the 9-9 section among Fig. 8.Comprise SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged and comprise Al ₂O ₃Layer as the flat crystal of principal ingredient is formed on the optical surface, and the optical clear parts 3 with difform shape are formed on the outmost surface, thereby reduces the reflection of light on this optical surface.

Example 14

Figure 10 is the front view of the optics of example 14 of the present invention.In this figure, optics 1 is f θ lens, and substrate 2 is provided with optical clear parts 3.

Figure 11 shows the xsect of the optics of example 14 along the cutting of the 11-11 section among Figure 10.Comprise SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged Al ₂O ₃Layer as the flat crystal of principal ingredient is formed on the optical surface, and the optical clear parts 3 with difform shape are formed on the outmost surface, thereby reduces the reflection of light on this optical surface.

Example 15

In the observation optical system, use the example of optics of the present invention to be depicted as example 15 of the present invention.Figure 12 shows the xsect of one of a pair of optical system of binoculars.

In this figure, reference number 4 expression object lens, reference number 5 expressions are used for the prism (illustrating with folded form not) of flipped image, and reference number 7 presentation videos form the surface, and reference number 8 expression pupil planes (assessment face).In this figure, reference number 3 (indicating scheming) expression is about optical clear parts of the present invention, wherein forms to comprise SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged and comprise Al ₂O ₃As the layer of the flat crystal of principal ingredient, and outmost surface has difform shape, thereby reduces the reflection of light on this optical surface.In this example, the optical clear parts of being made up of meticulous irregular shape structure 3 neither are arranged on the optical surface 9 of the nearest object lens of object, also are not arranged on the optical surface 10 of the nearest eyepiece of assessment face.It is that its performance will reduce owing to contacting in use that optical clear parts 3 are not arranged on these lip-deep reasons, but the present invention is not restricted to this, and optical clear parts 3 can be set on optical surface 9 and 10.

Example 16

The example that optics of the present invention is used for imaging optical system illustrates as example 16 of the present invention.Figure 13 show camera etc. capture lens (shown in this figure for taking the photograph lens far away) xsect.

In this figure, reference number 7 expression is as the film of image formation surface, perhaps such as the solid state image pickup device (photo-electric conversion element) of CCD or CMOS, and reference number 11 expression diaphragms.In this figure, reference number 3 (indicating scheming) expression is about optical clear parts of the present invention, wherein forms to comprise SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged and comprise Al ₂O ₃As the layer of the flat crystal of principal ingredient, and outmost surface has difform shape, thereby reduces the reflection of light on each optical surface.In this example, the optical clear parts of being made up of meticulous irregular shape structure 3 are not arranged on the optical surface 9 of the nearest object lens of object.It is that its performance will reduce owing to contacting in use that optical clear parts 3 are not arranged on this lip-deep reason, but the present invention is not restricted to this, and optical clear parts 3 can be set on the optical surface 9.

Example 17

The example that optics of the present invention is used for projection optical system (projector) illustrates as example 17 of the present invention.Figure 14 shows the xsect of projection machine optical system.

In this figure, reference number 12 expression light sources, reference number 13a and 13b represent the fly's eye integraph, reference number 14 expression polarization conversion devices, reference number 15 expression convergent lenses, reference number 16 expression catoptrons, reference number 17 expression field lenses, reference number 18a, 18b, 18c and 18d represent prism, and reference number 19a, 19b and 19c represent optical modulation element, and reference number 20 expression projecting lens.In the figure, reference number 3 (indicating scheming) the expression optical clear parts relevant with the present invention, wherein formation comprises SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged and comprise Al ₂O ₃As the layer of the flat crystal of principal ingredient, and outmost surface has the surface of difform shape, thereby reduces the reflection of light on each optical surface.

Because these routine optical clear parts 3 are configured to comprise inorganic constituents such as silicon dioxide or aluminium oxide as principal ingredient, it has high heat impedance, even and be placed on so and make optical clear parts 3 be exposed to the position 13a that height is pined near light source 12, descended by performance.

Example 18

The example that optics of the present invention is used for scanning optics (laser beam printer) illustrates as example 18 of the present invention.Figure 15 illustrates the xsect of scanning optics.

In this figure, reference number 12 expression light sources, reference number 21 expression collimator lens, reference number 11 expression diaphragms, reference number 22 expression cylindrical lenses, reference number 23 expression light deflectors, reference number 24a and 24b represent f θ lens, and reference number 7 expression mirror surface.In the drawings, reference number 3 (indicating scheming) the expression optical clear parts relevant with the present invention, wherein formation comprises SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and arranged and comprise Al ₂O ₃As the layer of the flat crystal of principal ingredient, and outmost surface has the surface of difform shape, thereby reduces the reflection of light on each optical surface, to realize the formation of high quality graphic.

Claims (11)

1. optical clear parts, it includes in substrate and comprises SiO ₂As the layer of principal ingredient, comprise Al ₂O ₃As the layer of principal ingredient and by comprising Al ₂O ₃As the flat crystal layer that the flat crystal of principal ingredient forms, these layers pile up with above-mentioned order, and wherein the surface of flat crystal layer comprises difform shape.

2. optical clear parts according to claim 1 wherein comprise Al ₂O ₃As the flat crystal of the flat crystal layer of principal ingredient by with respect to comprising Al ₂O ₃Be equal to or greater than 45 ° and be equal to or less than 90 ° direction and arrange as the layer of principal ingredient.

3. optical clear parts according to claim 2, wherein the thickness of flat crystal layer is equal to or greater than 20nm and is equal to or less than 1000nm.

4. optical clear parts according to claim 1, wherein for the difform shape on the surface of flat crystal layer, two dimension by the mean roughness on the center line with difform surface is extended the average surface roughness Ra ' that obtains for being equal to or greater than 5nm and being equal to or less than 100nm, and surface area ratio S _r=S/S ₀For being equal to or greater than 1.1 and be equal to or less than 3.5, S wherein ₀The expression surface measurements is desirably the area when smooth, and S represents the surface area on actual measurement surface.

5. optical clear parts according to claim 1, the wherein refractive index n of substrate _b, comprise SiO ₂As principal ingredient the layer refractive index n _s, and comprise Al ₂O ₃As principal ingredient the layer refractive index n _aSatisfy following relation: n _b〉=n _s〉=n _a

6. optical clear parts according to claim 1 wherein comprise SiO ₂For being equal to or greater than 5nm and being equal to or less than 100nm, and comprise Al as the thickness of the layer of principal ingredient ₂O ₃As principal ingredient the layer thickness for being equal to or greater than 10nm and being equal to or less than 120nm.

7. the optical system that comprises optical clear parts according to claim 1.

8. optical system according to claim 7, wherein this optical system is an image-pickup optical system.

9. optical system according to claim 7, wherein this optical system is the observation optical system.

10. optical system according to claim 7, wherein this optical system is a projection optical system.

11. optical system according to claim 7, wherein this optical system is a scanning optics.

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