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

Optical transparent member and optical system using the same Download PDF

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CN1834693A
CN1834693A CN 200610009415 CN200610009415A CN1834693A CN 1834693 A CN1834693 A CN 1834693A CN 200610009415 CN200610009415 CN 200610009415 CN 200610009415 A CN200610009415 A CN 200610009415A CN 1834693 A CN1834693 A CN 1834693A
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main component
equal
surface
al2o3
film
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CN100414321C (en )
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山田雅之
小谷佳范
田中博幸
奥野丈晴
南努
辰巳砂昌弘
忠永清治
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佳能株式会社
大阪府立大学
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Abstract

本发明的一个目的是提供一种能够长时间为基底保持高性能的抗反射效果的光学透明部件,以及使用该光学透明部件的光学系统,特别是在基底上包括包含SiO An object of the present invention is to provide a high-performance antireflection effect for a long time holding of an optically transparent base member, and an optical system using the optical transparent member, particularly comprising on a substrate comprising SiO

Description

光学透明部件和使用该光学透明部件的光学系统 An optically transparent member and a transparent member using the optical system of the optical

技术领域 FIELD

本发明涉及一种具有抗反射性能的光学透明部件和使用该光学透明部件的光学系统,更具体地,涉及一种适合于长时间获得从可见区域到近红外区域的高抗反射性能的光学透明部件,以及使用该光学透明部件的光学系统。 Relates to an optically transparent member having an antireflection performance and using the optical system of the optical transparent member of the present invention, more particularly, to a time suitable for obtaining a high antireflection performance from a visible region to near infrared region is optically transparent member, and an optical system using the optical transparent member.

特别地,本发明的光学透明部件可以适应于具有任何折射率的透明基底,对可见光显示出极好的抗反射效果,并且具有长期的抗侵蚀能力,因此可以用于文字处理器、计算机、电视、等离子显示板等的各种显示器的光学部件;液晶设备的极化板;太阳眼镜、渐变眼镜镜片、用于照相机的取景器透镜、棱镜、蝇眼透镜、复曲面透镜、以及由各种光学玻璃材料和透明塑料组成的各种滤光器和传感器等;进一步地,使用这些光学部件的图像拾取光学系统的各种光学透镜的光学部件、诸如双筒望远镜的观测光学系统、在液晶投影机中使用的投影光学系统、在激光打印机等中使用的扫描光学系统、各种仪器的表面、以及汽车、电气列车等的窗玻璃。 Particularly, the optical transparent member of the present invention can be adapted to any of a transparent substrate having a refractive index of visible light exhibits excellent antireflection effect, and long-term erosion resistance, and therefore can be used for word processor, computer, TV the optical member of various displays such as plasma display panel; polarizing plate of the liquid crystal device; sunglasses, progressive ophthalmic lenses, finder lenses for cameras, prisms, fly-eye lenses, toric lenses, and various optical various filters and sensors and transparent glass materials consisting of plastic; various optical lenses of the optical component further, the use of these optical members image pickup optical system, observation optical systems such as binoculars, in the liquid crystal projector a projection optical system used in the scanning optical system in the window glass and the like used in a laser printer, the surfaces of various equipment, and automobiles, electric trains and the like.

背景技术 Background technique

已经公知,使用具有可见光区域波长或较短波长的精细周期性结构的抗反射结构形成具有适当倾斜度和高度的精细周期性结构,从而在宽波长区域中示出了优秀的抗反射性能。 It is well known that an antireflection structure using a finely periodic structure having a wavelength or shorter wavelength visible light region is formed having a suitable inclination and height of the fine periodic structure, so that a wide wavelength region shown excellent antireflective properties. 作为用于形成精细周期性结构的方法,公知涂覆一种其中散布着微粒直径等于或小于波长的精细微粒的膜(日本专利申请No.03135944)等的方法。 As a method for film forming method of the fine periodic structure, coated with a known interspersed with particle diameter less than or equal to the wavelength of fine particles (Japanese Patent Application No.03135944) and the like.

已经公知,通过由精细处理设备(电子束压印设备、激光干涉曝光设备、半导体曝光设备、蚀刻设备等)形成图案而形成精细周期性构造的方法允许要被控制的倾斜度和高度,并且使得可能形成具有优秀抗反射特性的精细周期性结构(日本专利申请公开No.S50-70040)是可能的。 It is known, is formed by the fine pattern processing apparatus (imprint apparatus an electron beam, laser interference exposure apparatus, a semiconductor exposure apparatus, etching apparatus, etc.) to form a fine periodic structure allows a method to be controlled the height and inclination, and such that may form a fine periodic structure having excellent anti-reflection characteristics (Japanese Patent application Laid-Open No.S50-70040) are possible.

对于与上述方法不同的方法,在基底上生长水软铝石即铝的氢氧化物以获得抗反射效果的方法是公知的。 For the different methods of the above-described method, growing boehmite on a substrate, ie an aluminum hydroxide to obtain an antireflection effect are known. 在这些方法中,由真空膜形成工艺(日本专利公开No.S61-48124)或液相工艺(溶胶工艺)(日本专利申请公开No.H9-202649)形成的铝(氧化铝)层经受水蒸气处理或热水浸泡处理,以将表面层形成为水软铝石,以形成精细周期性结构,并从而获得抗反射膜。 In these processes, a film is formed by a vacuum process (Japanese Patent Publication No.S61-48124) or a liquid phase process (sol process) (Japanese Patent Application Publication No.H9-202649) aluminum (aluminum oxide) layer is subjected to water vapor hot water treatment or soaking treatment, the surface layer is formed to boehmite to form a fine periodic structure, and thereby obtaining the antireflection film.

然而,在使用精细微粒的技术中,很难控制精细周期性结构的倾斜度和高度,并且如果要获得用于获得足够抗反射效果的高度,倾斜度增加以引起散射,相反,光透射率降低。 However, in the technique using fine particles, it is difficult to control the inclination and height of the fine periodic structure, and if the height to be obtained for obtaining a sufficient antireflection effect, the inclination is increased to cause scattering, on the contrary, the light transmittance is lowered .

通过精细处理设备形成精细图案的方法具有这样的缺点:这种形成图案的方法不仅需要非常大规模的设备,因而需要非常高的资本支出,而且虽然该方法适合于在平坦表面上形成图案,但是很难在诸如曲线表面的复杂形状上形成图案。 The method of forming a fine pattern by fine processing apparatus has a drawback: not only the method of forming a pattern of this requires very large-scale equipment, thus requiring a very high capital expenditure, but also although the method is suitable for forming a pattern on a flat surface, but difficult to form a pattern on a complicated shape such as a curved surface. 此外,该方法不适合对通用光学部件的应用,因为吞吐量低并且在大区域上的处理很困难。 In addition, this method is not suitable for general use optical members because of the low throughput and the process over a large area is difficult.

在基底上生长水软铝石的方法很便利,并且具有很高的生产率,但是氧化铝和水软铝石是两性化合物,因而容易由酸和碱分解。 The method of growing boehmite on a substrate is very convenient, and has high productivity, but alumina and boehmite are amphoteric compounds, which can easily decomposed by the acid and base. 因此,当基底的碱性离子等迁移到表面,并且由于与空气中的水进行交换作用而使表面成为碱性环境时,由于表面的分解,保持不规则形的形状变得困难,因而性能降低。 Thus, when the alkali ions migrate to the surface of the substrate, and the like, and the surface becomes alkaline environment due to the effect of exchange with water in the air due to the decomposition of the surface, an irregular shape retention becomes difficult, thereby reducing performance . 对于折射率与氧化铝显著不同的基底,基底和铝之间的界面处的折射率的差异如此之大,以至于没有充分表现出抗反射性能。 For a refractive index significantly different from the alumina substrate, the difference in refractive index at the interface between the substrate and the aluminum so large that the antireflection performance is not fully demonstrated.

发明内容 SUMMARY

考虑到上述相关技术而做出本发明,且本发明的目的是提供一种对于任何基底能够长时期保持高性能抗反射效果的光学透明部件,以及使用该光学透明部件的光学系统。 Considering the above-described related art of the present invention has been made, and an object of the present invention is to provide a long period of time to maintain a high-performance antireflection effect for any optically transparent base member, and an optical system using the optical transparent member.

本发明提供了一种以下面所述方式配置的用于实现上述目的的光学透明部件。 The present invention provides an optical transparent member for achieving the above object in a manner following the configuration.

即,本发明提供了一种光学透明部件,其在基底上具有:包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及由包含Al2O3作为主要成分的片状晶体形成的片状晶体层,其中该片状晶体层的表面由不规则形状构成。 That is, the present invention provides an optical transparent member having on a substrate: layer containing SiO2 as a main component, the layer containing Al2O3 as a main component, and a sheet-like crystals containing Al2O3 as a main component is formed plate-like crystals of layer, wherein the surface of the sheet-shaped crystal layer formed of irregular shape.

按照包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及由包含Al2O3作为主要成分的片状晶体形成的片状晶体层的次序在基底上堆叠是优选的。 According to the order contains SiO2 as a main component, containing Al2O3 as a main component, and a plate crystal layer containing Al2O3 as a main component of the plate-like crystals formed in a stack on a substrate are preferred.

包含Al2O3作为主要成分的片状晶体层的片状晶体按相对于包含Al2O3作为主要成分的层大于或等于45°且小于或等于90°的方向设置是优选的。 Containing Al2O3 as a main component of the plate crystal layer by the plate-like crystals containing Al2O3 as a layer with respect to the main component is equal to or greater than 45 ° and less than or equal to a direction 90 ° setting is preferred.

片状晶体层的表面的不规则形状的厚度为大于或等于20nm且小于或等于1000nm是优选的。 The thickness of the sheet-like irregular surface of the crystal layer is equal to or greater than 20nm and less than or equal to 1000nm is preferable.

对于片状晶体层的表面的不规则形状,通过具有不规则形的表面的中心线平均粗糙度的二维延伸而获得的平均表面粗糙度Ra′值为大于或等于5nm且小于或等于100nm,并且表面面积比Sr=S/S0(其中S0表示当测量表面为理想平坦时的面积,且S表示实际测量表面的表面积)为大于或等于1.1且小于或等于3.5是优选的。 For the irregular shape of the surface of the sheet-shaped crystal layer, the average surface roughness Ra obtained by extending the two-dimensional shape having an irregular surface roughness of center line average 'value is greater than or equal to 5nm and less than or equal to 100 nm or, and the surface area ratio Sr = S / S0 (where S0 represents an area when a measurement surface when over flat and S represents the surface area of ​​an actual measurement surface) is greater than or equal to 1.1 and less than or equal to 3.5 are preferred.

基底的折射率nb、包含SiO2作为主要成分的层的折射率ns、以及包含Al2O3作为主要成分的层的折射率na满足如下关系:nb≥ns≥na是优选的。 The refractive index of the substrate nb, containing SiO2 as a main component of the refractive index ns, and the refractive index of the layer containing Al2O3 as a main component of the na satisfies the following relationship: nb≥ns≥na are preferred.

包含SiO2作为主要成分的层的厚度大于或等于5nm且小于或等于100nm,并且包含Al2O3作为主要成分的层的厚度大于或等于10nm且小于或等于120nm是优选的。 The thickness of layer containing SiO2 as a main component is equal to or greater than a thickness of less than or equal to 5nm and 100nm, and the layer containing Al2O3 as a main component is greater than or equal to 10nm and less than or equal to 120nm is preferable.

此外,本发明提供了一种具有上述光学透明部件的光学系统。 Further, the present invention provides an optical system having the optical transparent member.

该光学系统是图像拾取光学系统、观测光学系统、投影光学系统或扫描光学系统是优选的。 The optical system is an image pickup optical system, observation optical system, a projection optical system or the scanning optical system is preferred.

本发明的光学透明部件具有包含SiO2作为主要成分的层,该层设置在基底上,且在包含Al2O3作为主要成分的层之下,并且基底的折射率nb、包含SiO2作为主要成分的层的折射率ns、以及包含Al2O3作为主要成分的层的折射率na满足如下关系:nb≥ns≥na,因而使得可能进一步改进由包含氧化铝作为主要成分的片状晶体形成的片状晶体层的低反射性质。 The optical transparent member according to the present invention has a layer containing SiO2 as a main component, the layer disposed on the substrate and below the layer containing Al2O3 as a main component, and the refractive index nb of the base, containing SiO2 as a main component of the refractive ratio ns, and the refractive index of the layer containing Al2O3 as a main component of the na satisfies the following relationship: nb≥ns≥na, thus making it possible to further improve the low-reflection layer composed of plate crystals containing alumina as a main component formed of plate-like crystals nature.

此外,包含SiO2作为主要成分的层抑制碱成分等从基底到表面的迁移,并且可以长期保持抗反射性能。 Further, containing SiO2 as a main component from the substrate to inhibit migration of the surface of the base component and the like, and may be maintained for a long antireflective properties.

本发明的光学部件的基底表面依次涂覆有包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及由包含Al2O3作为主要成分的片状晶体形成的片状晶体层,并且片状晶体层的最外表面具有不规则形状。 The base surface of the optical member of the present invention is sequentially coated with a layer containing SiO2 as a main component, containing Al2O3 as a main component, and a plate crystal layer containing Al2O3 as a main component is formed plate-like crystals, and flake crystals the outermost surface layer has an irregular shape. 由于按相对于包含Al2O3作为主要成分的层大于或等于45°且小于或等于90°的方向的设置、层中的板表面之间的间隔、板表面的方向性的无规则、和片状晶体的大小的无规则,由片状晶体形成的片状晶体层形成不规则形状,并且层的厚度大于或等于20nm且小于或等于1000nm。 Since the press with respect to contain Al2O3 as a non-directional regular intervals, the plate surface is provided between the plate surface of the primary component is greater than or equal to 45 ° and less than or equal to 90 ° in the direction of the layer, and plate-like crystals the irregular, plate-like crystals formed layer is formed of a plate-like crystals of irregular shape, and the thickness of the layer is greater than or equal to 20nm and less than or equal to the size of 1000nm. 对于片状晶体的密度,通过涂层的中心线平均粗糙度的二维延伸而获得的平均表面粗糙度值Ra′为大于或等于5nm,并且表面面积比Sr=S/S0(其中S0表示当测量表面为理想平坦时的表面积,且S表示实际测量表面的表面积)为大于或等于1.1。 For the density of the plate crystals, an average surface by two-dimensionally extending centerline average roughness of the coating obtained roughness value Ra 'is greater than or equal to 5 nm, and the surface area ratio Sr = S / S0 (where S0 represents when surface area when the measurement surface is perfectly flat and S represents the surface area of ​​an actual measurement surface) is greater than or equal to 1.1. 布置了片状晶体的层的厚度大于或等于20nm且小于或等于1000nm。 Lamellar crystal is disposed a thickness greater than or equal to 20nm and less than or equal to 1000nm.

基底的折射率nb、包含SiO2作为主要成分的层的折射率ns、以及包含Al2O3作为主要成分的层的折射率na满足如下关系:nb≥ns≥na,包含SiO2作为主要成分的层的厚度大于或等于5nm且小于或等于100nm,并且包含Al2O3作为主要成分的层的厚度大于或等于10nm且小于或等于120nm,从而折射率从基底到由片状晶体形成的片状晶体层的表面的不规则形状逐渐降低,并且片状晶体层的抗反射效果得到显著改善。 The refractive index of the substrate nb, containing SiO2 as a main component of the refractive index ns, and the refractive index of the layer containing Al2O3 as a main component of the na satisfies the following relationship: nb≥ns≥na, the thickness of the layer containing SiO2 as a main component is greater than and less than or equal to 5nm or equal to 100nm, and the layer containing Al2O3 as a main component of a thickness greater than or equal to 10nm and less than or equal to 120nm, so that the refractive index of the irregular surface of the sheet from the substrate to the crystal layer formed from plate crystals shape gradually reduced, and the sheet-like crystal layer antireflection effect is significantly improved.

包含SiO2作为主要成分的层将包含各种成分的基底和具有高反应性且包含Al2O3作为主要成分的层彼此隔离开,并且抑制诸如碱的反应成分从基底迁移到包含Al2O3作为主要成分的层,因而使得可能长期稳定地显示出抗反射效果。 Layer containing SiO2 as a main component comprising a substrate having various components and high reactivity and containing Al2O3 as a main component is isolated from each other, and inhibit the reaction such as a base ingredient to migrate from the substrate layer containing Al2O3 as a main component, thus making possible long-term stability exhibit anti-reflection effect.

如上所述,本发明的光学透明部件可以长期稳定地显示出高的抗反射效果。 As described above, the optical transparent member of the present invention can exhibit long-term stability of a high antireflection effect.

从如下结合附图的描述中,本发明的其他特征和优势将变得明显。 From the following description in conjunction with the accompanying drawings Other features and advantages of the invention will become apparent.

附图说明 BRIEF DESCRIPTION

图1是示出了本发明的光学透明部件的一个实施例的示意图;图2是示出了第一例中通过FE-SEM从顶表面拍摄的在玻璃基底上形成的且在表面上具有精细不规则形的层的观测结果的照片(比例因子:X100000);图3是示出了第一例中通过FE-SEM拍摄的在玻璃基底上形成的且具有精细不规则形的层的横截面的观测结果的照片(比例因子:X150000);图4是本发明的第六例的前视图;图5是本发明的第六例的剖视图;图6是本发明的第七例的前视图;图7是本发明的第七例的剖视图;图8是本发明的第八例的前视图;图9是本发明的第八例的剖视图;图10是本发明的第九例的前视图;图11是本发明的第九例的剖视图;图12是本发明的第十例的剖视图;图13是本发明的第十一例的剖视图;图14是本发明的第十二例的剖视图;以及图15是本发明的第十三例的剖视图。 FIG 1 is a schematic diagram showing an embodiment of an optically transparent member of the present invention; FIG. 2 is a diagram showing a fine on a surface and having a first embodiment taken from the top surface by FE-SEM formed on a glass substrate observation photograph of irregularly shaped layers (scale factor: X100000); FIG. 3 is a diagram illustrating a layer having a fine irregular shape and in a first embodiment taken by FE-SEM formed on a glass substrate in a cross-section photo observations (the scaling factor: X150000); FIG. 4 is a front view of a sixth embodiment of the present invention; FIG. 5 is a sectional view of a sixth embodiment of the present invention; FIG. 6 is a front view of a seventh embodiment of the present invention; 7 is a sectional view of a seventh embodiment of the present invention; FIG. 8 is a front view of an eighth embodiment of the present invention; FIG. 9 is a cross-sectional view of an eighth embodiment of the present invention; FIG. 10 is a front view of a ninth embodiment of the present invention; FIG 11 is a sectional view of a ninth embodiment of the present invention; FIG. 12 is a sectional view of a tenth embodiment of the present invention; FIG. 13 is a sectional view of an eleventh embodiment of the present invention; FIG. 14 is a sectional view of a twelfth embodiment of the present invention; and FIG. 15 is a sectional view of a thirteenth embodiment of the present invention.

具体实施方式 detailed description

下面将详细描述本发明。 The present invention will be described in detail below.

图1是示出了本发明的光学透明部件的一个实施例的示意图。 FIG 1 is a schematic diagram showing an embodiment of an optical transparent member of the present invention. 在图1中,本发明的光学透明部件在基底21上具有:包含SiO2作为主要成分的层22、包含Al2O3作为主要成分的层23、以及由包含Al2O3作为主要成分的片状晶体形成的片状晶体层24,并且该片状晶体层24的表面具有不规则形状25。 In FIG 1, the optical transparent member of the present invention on a substrate 21: a layer containing SiO2 as a main component 22, layer 23 containing Al2O3 as a main component, and a sheet-like plate crystals containing Al2O3 as a main component formed crystal layer 24, and the surface of the plate crystal layer 24 has an irregular shape 25.

包含Al2O3(氧化铝)作为主要成分的片状晶体是通过使用铝的氧化物或氢氧化物或其水合物作为主要成分而形成的。 Containing Al2O3 (alumina) as a main component is a sheet-like crystal by using aluminum oxide or hydroxide or a hydrate thereof as a main component is formed. 特别优选的晶体是水软铝石。 Especially preferred are boehmite crystals. 通过布置这些片状晶体,它们的端部形成精细不规则形,因此片状晶体选择性地按相对于层表面大于或等于45°且小于或等于90°的方向设置是优选的,用于增加精细不规则形的高度以及降低其间的间隔。 These tabular crystals are arranged, their ends to form a fine irregular shape, so the sheet-like crystal by selectively provided with respect to the surface layer is preferably greater than or equal to 45 ° and less than or equal to 90 ° direction for increasing fine irregular shape and reduced height intervals therebetween.

由片状晶体形成的晶体层的厚度优选地为大于或等于20nm且小于或等于1000nm,更优选地为大于或等于50nm且小于或等于1000nm。 Thickness of the crystal layer formed from plate crystals is preferably greater than or equal to 20nm and less than or equal to 1000nm, more preferably greater than or equal to 50nm and less than or equal to 1000nm. 如果形成不规则形的层的厚度大于或等于20nm且小于或等于1000nm,通过精细不规则形结构的抗反射性能是有效的,消除了破坏不规则形的机械强度的可能性,并且精细不规则形的结构在制造成本方面变得有优势。 If the thickness of the layer formed irregular than or equal to 20nm and less than or equal to the fine irregularities 1000nm, the antireflection performance by a fine irregular structure is effective, eliminates the possibility of damage to the mechanical strength of the irregularly shaped, and shaped structure becomes advantageous in terms of manufacturing costs. 更优选地,厚度为大于或等于50nm且小于或等于1000nm,从而进一步改善抗反射性能。 More preferably, the thickness is greater than or equal to 50nm and less than or equal to 1000nm, thereby further improving the antireflection property.

本发明的精细不规则形的表面密度也是重要的,并且通过中心线平均粗糙度的二维延伸而获得的相应平均表面粗糙度Ra′值为大于或等于5nm,更优选地为大于或等于10nm,进一步更优选地为大于或等于15nm且小于或等于100nm,并且表面面积比Sr为1.1,更优选地为大于或等于1.15,进一步优选地为大于或等于1.2且小于或等于3.5。 Fine irregular surface density of the present invention is also important, and the respective two-dimensional extension of an average surface roughness of center line average roughness obtained by Ra 'value is greater than or equal to 5 nm, more preferably greater than or equal to 10nm , even more preferably greater than or equal to 15nm and less than or equal to 100 nm or, and the surface area ratio Sr is 1.1, more preferably greater than or equal to 1.15, more preferably greater than or equal to 1.2 and less than or equal to 3.5.

用于评估所获得的精细不规则形结构的方法之一是通过扫描探测显微镜来观察精细不规则形结构的表面,并且通过观察,确定了通过层的中心线平均粗糙度Ra的二维延伸而获得的平均表面粗糙度Ra′值和表面积比Sr。 One of the methods for assessing the fine irregular structure is obtained by observing the surface of a fine irregular structure by scanning probe microscope, and by observation, determined by two-dimensionally extending centerline average roughness Ra of the layer and obtaining an average surface roughness Ra 'value and the surface area ratio Sr. 即,平均表面粗糙度Ra′值(nm)是使得JIS B0601中定义的中心线平均粗糙度Ra应用于测量表面并且被三维延伸的值,并且Ra′值表达为“通过对从参考表面到指定表面的偏差的绝对值取平均而获得的值”,并且由下式(1)给出。 That is, the average surface roughness Ra 'value (nm) is such that center line average roughness Ra JIS B0601 defined value is applied to measure the three-dimensional surface and extended, and the Ra' value is expressed as "by the reference surface to a specified absolute value of the deviation of the surface obtained by averaging ", and is given by the following formula (1).

Ra′=1S0∫YBYT∫XLXR|F(X,Y)-Z0|dXdY---(1)]]>Ra′:平均表面粗糙度值(nm),S0:当测量表面为理想平坦时的面积,|XR-XL|×|YT-YB|,F(X,Y):测量点(X,Y)的高度,其中X是X坐标,且Y是Y坐标,XL-XR:测量表面上的X坐标范围,YB-YT:测量表面上的Y坐标范围,Z0:在测量表面内的平均高度。 Ra & prime; = 1S0 & Integral; YBYT & Integral; XLXR | F (X, Y) -Z0 | dXdY --- (1)]]> Ra ': average surface roughness value (nm), S0: when the measuring surface is perfectly flat , the area |, F (X, Y) XR-XL | × | | YT-YB: measuring surface: measurement point (X, Y) of the height, wherein X is the X coordinate and Y is a Y coordinate, XL-XR X-coordinate range, YB-YT: Y coordinate range on the measurement surface, Z0: average height within the measurement surface.

通过Sr=S/S0来确定表面积比Sr(S0:当测量表面为理想平坦时的面积。S:实际测量表面的表面积)。 Is determined by Sr = S / S0 surface area ratio Sr (S0: area when the measurement surface is perfectly flat when .S: surface area of ​​an actual measurement surface). 实际测量表面的表面积确定如下。 The actual surface area of ​​the measurement surface is determined as follows. 测量表面被划分为由最接近的三个数据点(A、B、C)组成的非常小的三角形,接着使用向量积来确定每个非常小三角形的面积ΔS。 The measurement surface is divided into a very small triangle closest three data points (A, B, C) of the composition, then the vector product used to determine the area ΔS of each very small triangle. ΔS(ΔABC)等于[s(s-AB)(s-BC)(s-AC)]0.5(其中AB、BC和AC是各边的长度,并且S≡0.5(AB+BC+AC)保持),并且面积ΔS的总和是待确定的表面积S。 ΔS (ΔABC) equals [s (s-AB) (s-BC) (s-AC)] 0.5 (where AB, BC and AC are the lengths of the sides, and S≡0.5 (AB + BC + AC) holds) and the area ΔS is the sum of the surface area to be determined S. 如果作为精细不规则形的表面密度的Ra′值等于或大于5nm并且Sr等于或大于1.1,可以实现通过不规则形结构的抗反射。 If as a fine irregular surface density Ra 'value is equal to or larger than 5nm or more and Sr 1.1, may be achieved through the antireflection structure is irregular. 如果Ra′值等于或大于10nm并且Sr等于或大于1.15,则抗反射效果变得高于前述情况的抗反射效果。 If the Ra 'value is equal to or greater than 10nm and equal to or greater than 1.15 Sr, the antireflection effect becomes higher than the case where the antireflection effect. 如果Ra′等于或大于15nm并且Sr等于或大于1.2,不规则形的结构具有耐受实际使用的性能。 If Ra 'is equal to or more than 15nm and equal to or greater than 1.2 Sr, irregularly shaped structures having properties withstand practical use. 然而,如果Ra′值等于或大于100nm并且Sr等于或大于3.5,不规则形结构造成的散射效果与抗反射效果相比占优势,使得不能获得充分的抗反射效果。 However, if the Ra 'value is equal to or more than 100nm and is equal to or greater than 3.5 Sr, irregular structure caused by the scattering effect as compared with the antireflection effect predominates, making it impossible to obtain a sufficient antireflection effect.

包含Al2O3作为主要成分的层可以是包含Al2O3作为主要成分的任何非晶氧化物涂层,并且作为不同种类的成分,可以单独添加诸如TiO2、ZrO2、SiO2、ZnO或MgO的氧化物,或可以选择、组合和添加这些氧化物的两种或更多种。 Containing Al2O3 as a main component may be any amorphous oxide containing Al2O3 as a main component of the coating, and as a different kind of component, oxides may be added, such as TiO2, ZrO2, SiO2, ZnO or MgO alone, or may choose , and adding a combination of two or more of these oxides. 具体地,选择层使得此膜的折射率na与包含SiO2作为主要成分的层的折射率ns之间的关系是ns≥na,作为控制成分含量的结果。 In particular, the selection layer such that the refractive index na of this film comprising SiO2 as the relationship between the refractive index ns of the layer is a main component ns≥na, as a result of the control component content. 在这种情况下,与Al2O3膜的优选mol%比为等于或大于50%且等于或小于100%,更优选地,等于或大于70%且等于或小于100%。 In this case, the preferred ratio of% mol Al2O3 film is equal to or greater than 50% and equal to or less than 100%, more preferably, equal to or greater than 70% and equal to or less than 100%. 因此,在从基底到与空气的界面的范围内,折射率连续降低,并且随着已经布置了包含氧化铝作为主要成分的片状晶体的层的效应,可以实现高的抗反射性能。 Thus, the range of the interface with the air, the refractive index continuously decreases from the substrate to, and as have been arranged effect layer containing alumina as a main component of the plate-like crystals, can achieve high antireflection performance.

本发明的包含SiO2作为主要成分的层可以是包含SiO2作为主要成分的任何非晶氧化物涂层,并且作为不同种类的成分,可以单独或组合地添加诸如TiO2和ZrO2的氧化物。 The present invention contains SiO2 as a main component may be any amorphous oxide containing SiO2 as a main component of the coating, and as a different kind of component, may be added alone or in combination of oxides such as TiO2 and ZrO2. 具体地,选择层以使得可抑制碱等向包含Al2O3作为主要成分的层的迁移,且此膜的折射率ns与基底的折射率nb之间的关系是nb≥ns,作为控制成分含量的结果。 In particular, the selection layer is suppressed so that the base or the like to the transport layer comprising Al2O3 as a main component, and the relationship between the refractive index nb and the refractive index ns of the substrate of the film is nb≥ns, as a result of the control component content . 在这种情况下,与SiO2膜的优选mol%比为等于或大于40%且等于或小于100%,更优选地,等于或大于60%且等于或小于100%。 In this case, it is preferable mol% ratio of the SiO2 film to be equal to or greater than 40% and equal to or less than 100%, more preferably equal to or greater than 60% and equal to or less than 100%. 因此,在从基底到与空气的界面的范围内,折射率连续降低,并且随着由包含Al2O3作为主要成分的片状晶体形成的片状晶体层以及包含Al2O3作为主要成分的层的效应,可以实现高的抗反射性能。 Thus, the range of the interface with the air, the refractive index continuously decreases from the substrate to, and as a plate crystal layer containing Al2O3 as a main component and formed by plate-like crystals containing Al2O3 as a main component of the layer effect may be high anti-reflection performance. 进一步地,通过除了上述氧化物以外添加诸如磷酸的酸成分,可以改进抑制碱等从基底向包含Al2O3作为主要成分的层的迁移效应的性能。 Further, by adding an acid component such as phosphoric acid addition to the above oxides, alkali and other properties can be improved to suppress the migration effect from the substrate to the layer containing Al2O3 as a main component.

本发明的光学透明部件可以由公知的诸如CVD或PVD的气相工艺、诸如溶胶-凝胶工艺的液相工艺、使用无机盐的热液合成等形成。 The optical transparent member according to the present invention can, by a known sol such as CVD or PVD process vapor - liquid-phase process of gel process, hydrothermal synthesis using an inorganic salt formed. 通过这种方法,可以在包含由SiO2作为主要成分的层之后直接设置由包含氧化铝作为主要成分的片状晶体组成的片状晶体,并且依次形成包含Al2O3作为主要成分的层。 By this method, may be provided by a plate-like crystals composed of plate-like crystals containing aluminum oxide as a main component directly after the layer containing SiO2 as a main component, a layer containing Al2O3 and sequentially as a main component. 可替换地,在各层的这两层上形成只有金属Al的层,或包含金属Al、以及金属Zn和金属Mg中的任何金属的金属层之后,该层的表面可以通过浸泡在50℃或更热的热水中或暴露在水蒸气中而被溶解或沉淀,以提供氧化铝的片状晶体。 Alternatively, after forming only the Al metal layer on the two layers each layer comprising a metal or Al, and any metal layer of the metal Zn and metal Mg and metal, the surface of the layer may be 50 deg.] C or by immersion in more in hot water or exposure to water vapor and is dissolved or precipitated to provide plate crystals of alumina. 可替换地,在包含SiO2作为主要成分的层上形成只有Al2O3的层,或包含Al2O3、以及ZrO2、SiO2、TiO2、ZnO和MgO中任何成分的一个或多个氧化物层之后,层的表面会选择性地溶解或沉淀,以提供氧化铝的片状晶体。 Alternatively, after the layer containing SiO2 as the only layer of Al2O3 is formed on a main component, or comprising Al2O3, and ZrO2, SiO2, TiO2, ZnO and MgO, an oxide of one or more layers of any component, the surface layer may selectively dissolved or precipitated to provide plate crystals of alumina. 其中,优选的是这样一种方法,其中用热水处理通过依次涂覆包含SiO2的溶胶涂渍溶液和包含Al2O3的溶胶涂渍溶液而形成的凝胶膜,以生长氧化铝片状晶体。 Among them, preferred is a method wherein the treatment with hot water are sequentially coated by gel film containing SiO2 sol coating solution and the coating solution containing Al2O3 sol is formed, to grow alumina plate crystals.

对于从包含Al2O3的溶胶涂渍溶液获得的凝胶膜的原材料,使用Al化合物,或者Zr、Si、Ti、Zn和Mg的化合物中的至少一种与Al化合物共同使用。 For the raw material of the gel film obtained from a coating solution comprising a sol of Al2O3, an Al compound, or Zr, Si, Ti, Al and at least one compound of Zn and Mg compound used in common. 对于Al2O3、ZrO2、SiO2、TiO2、ZnO和MgO的原材料,可以使用各金属的烷氧基化合物和诸如氯化物和硝酸盐的盐化合物。 For Al2O3, ZrO2, SiO2, TiO2, ZnO and MgO in the raw materials may be used each metal alkoxide compound and salts of compounds such as chlorides and nitrates. 从制膜能力的观点来看,优选地使用金属烷氧基化合物,尤其是对于ZrO2、SiO2和TiO2原材料。 From the viewpoint of film formation ability, it is preferable to use a metal alkoxide, particularly for ZrO2, SiO2 and TiO2 raw materials.

铝化合物例如包括:乙醇铝、异丙醇铝、正丁醇铝、仲丁醇铝、叔丁醇铝、乙酰乙酸铝或这些化合物的低聚物,硝酸铝、氯化铝、醋酸铝、磷酸铝、硫酸铝和氢氧化铝。 Aluminum compounds include, for example: ethanol, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, aluminum tert-butoxide oligomers, acetoacetate aluminum or combinations of these compounds, aluminum nitrate, aluminum chloride, aluminum acetate, phosphate aluminum, aluminum sulfate and aluminum hydroxide.

烷氧基锆的具体例子包括四甲醇锆、四乙醇锆、四正丙醇锆、四异丙醇锆、四正丁醇锆以及四叔丁醇锆。 Specific examples of zirconium alkoxide include zirconium tetramethoxide, zirconium tetraethoxide, zirconium propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide and zirconium tetra-t-butoxide.

对于烷氧基硅,可以使用由通式Si(OR)4表达的各种化合物。 For the silicon alkoxide, a variety of compounds expressed by the general formula Si (OR) 4. R是相同或不同的较低烃基,例如甲基、乙基、丙基、异丙基、丁基或异丁基。 R is the same or different lower hydrocarbyl group such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl.

烷氧基钛例如包括:四甲氧基钛、四乙氧基钛、四正丙氧基钛、四异丙氧基钛、四正丁氧基钛、和四异丁氧基钛。 Titanium alkoxide include, for example: tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, and tetraisobutoxy titanium.

锌化合物例如包括:醋酸锌、氯化锌、硝酸锌、硬脂酸锌、油酸锌以及水杨酸锌,并且特别优选的是醋酸锌和氯化锌。 Zinc compounds include, for example: zinc acetate, zinc chloride, zinc nitrate, zinc stearate, zinc oleate and zinc salicylate, and especially preferable are zinc acetate and zinc chloride.

镁化合物包括:例如诸如二甲氧基镁、二乙氧基镁、二丙氧基镁以及二丁氧基镁的烷氧基镁、乙酰乙酸镁和氯化镁。 Magnesium compounds include: for example, as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, alkoxy magnesium and dibutoxy magnesium, magnesium acetate and acetyl chloride.

有机溶剂可以是不导致诸如上述烷氧基化合物的原材料凝胶化的任何有机溶剂,该有机溶剂例如包括:诸如甲醇、乙醇、2-丙醇、丁醇、乙二醇或乙二醇单正丙醚的醇;诸如正乙烷、正辛烷、环己烷、环戊烷以及环辛烷的各种脂肪族烃或脂环烃;诸如甲苯、二甲苯以及乙苯的各种芳族烃;诸如甲酸乙酯、乙酸乙酯、乙酸正丁酯、乙二醇甲醚乙酸酯、乙二醇乙醚乙酸酯和乙二醇丁醚乙酸酯的各种酯;诸如丙酮、甲基乙酮、甲基异丁酮、以及环己酮的各种酮;诸如二甲氧基乙烷、四氢呋喃、二氧杂环乙烷、以及二异丙醚的各种醚;诸如氯仿、二氯甲烷、四氯化碳以及四氯乙烷的各种氯化碳氢化合物;以及诸如N-甲基喀酮(N-methyl pyrolidone)、二甲基甲酰胺、二甲基乙酰胺以及碳酸乙二酯的非质子极性溶剂。 The organic solvent may not result in the raw materials such as alkoxide gelled any organic solvent, the organic solvents include: such as methanol, ethanol, 2-propanol, butanol, ethylene glycol or ethylene glycol mono-n ether alcohols; such as n-hexane, n-octane, cyclohexane, cyclopentane and cyclooctane various aliphatic hydrocarbon or alicyclic hydrocarbon; various aromatic hydrocarbons such as toluene, xylene and ethylbenzene ; such as ethyl formate, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate and ethylene glycol monobutyl ether acetate various esters; such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and various ketones; such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether and the various ethers; such as chloroform, dichloro methane, carbon tetrachloride and tetrachloroethane various chlorinated hydrocarbons; and Ji Ka ketone such as methyl N- (N-methyl pyrolidone), dimethyl formamide, dimethyl acetamide and ethylene carbonate aprotic polar solvents esters. 在上述的各种溶剂中,在溶液的稳定性方面,醇是优选使用的。 In various solvents described above, in terms of stability of the solution, alcohols are preferably used.

如果使用烷氧基化合物原材料,特别是铝、锆和钛的烷氧基化合物与水高度反应,并且通过添加空气的水分或水而急剧水解,导致浑浊和沉淀。 If alkoxide raw materials, in particular water and aluminum alkoxide, zirconium and titanium are highly reactive, moisture or by the addition of water and air rapidly hydrolyzed, resulting in turbidity and sedimentation. 氯化铝化合物、氯化锌化合物和氯化镁化合物很难仅在有机溶剂中溶解,并且它们的溶液的稳定性低。 Aluminum chloride compounds, zinc chloride compounds and magnesium chloride compounds only difficult to dissolve in organic solvents and their low stability in solution. 为了防止这种状况,优选地添加稳定剂来稳定溶液。 In order to prevent such a situation, a stabilizer is preferably added to stabilize the solution.

稳定剂例如可以包括:诸如乙酰丙酮、三氟乙酰丙酮、六氟乙酰丙酮、苯甲酰丙酮以及二苯甲酰甲烷的β二酮化合物;诸如乙酰乙酸甲酯、乙酰乙酸乙酯、丙酮酸烯丙酯(allyl ketoacetate)、乙酰乙酸苯甲酯、乙酰乙酸异丙酯、乙酰乙酸叔丁酯、乙酰乙酸异丙酯、乙酰乙酸根-2-甲氧基乙基(acetoacetate-2-methoxyethyl)以及3-酮基-正甲基戊酸酯(3-keto-n-methyl-valeriate)的β酮酯化合物;以及诸如单乙醇胺、二乙醇胺以及三乙醇胺的烷醇氨。 Stabilizers may include, for example: such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone and β-diketone compound is dibenzoylmethane; such as methyl acetoacetate, ethyl acetoacetate, alkenyl pyruvate propyl (allyl ketoacetate), benzyl acetoacetate, methyl acetoacetate, isopropyl, t-butyl acetoacetate, isopropyl acetoacetate, acetoacetate-2-methoxyethyl (acetoacetate-2-methoxyethyl), and 3-keto group - n-methyl pentanoate (3-keto-n-methyl-valeriate) a β-ketoester compound; and such as monoethanolamine, diethanolamine and triethanolamine, ammonia alkanol. 所添加的稳定剂的量按照与烷氧基化合物或盐化合物的摩尔比优选地为1。 The amount of stabilizer added is in accordance with the alkoxide or salt compound molar ratio is preferably 1. 添加稳定剂之后,优选地添加催化剂用于促进部分反应,以形成适当的前驱体。 After the stabilizer is added, the catalyst is preferably added for promoting the reaction section, to form an appropriate precursor. 催化剂例如可以包括硝酸、盐酸、硫酸、磷酸、醋酸和氨水。 The catalyst may comprise, for example, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid and ammonia.

对于从包含SiO2的溶胶涂渍溶液获得的凝胶膜的原材料,使用Si化合物,或者Ti和Zr的化合物中的至少一种与Si化合物共同使用。 For the raw material of the gel film obtained from a coating solution comprising a sol of SiO2, a Si compound, or at least one co-compound using the Si compound of Ti and Zr. 对于SiO2、TiO2和ZrO2的原材料,可以使用各金属的烷氧基化合物和诸如氯化物和硝酸盐的盐化合物,但是从制膜能力的观点来看,优选地使用金属烷氧基化合物。 For SiO2, TiO2 and ZrO2 raw materials may be used each metal alkoxide compound and salts of compounds such as chlorides and nitrates, but from the viewpoint of film-forming ability, it is preferable to use the metal alkoxide compound. 对于金属的烷氧基化合物、溶剂、稳定剂等,可以使用前述化合物。 For the metal alkoxide, the solvent, stabilizer and the like, the compound can be used. 作为促进部分反应的催化剂,优选地使用诸如磷酸的酸,用于捕捉在膜中迁移的碱。 As a catalyst for the reaction part, preferably using an acid such as phosphoric acid, for capturing an alkali migrating in the film. 使用SiO2(本身的n=1.45)、TiO2(本身的n=2.20)和ZrO2(本身的n=1.90),适当选择每种成分的组成比,使得折射率ns与基底的折射率nb和包含Al2O3作为主要成分的层的折射率na之间的关系是nb≥ns≥na。 Use of SiO2 (itself n = 1.45), TiO2 (itself n = 2.20) and ZrO2 (itself n = 1.90), the composition ratio of each component is appropriately selected such that the refractive index ns of the substrate and comprising Al2O3 nb as the relationship between the refractive index na of the layer is a main component nb≥ns≥na. 已知TiO2具有高的折射率,并且提高膜的折射系数的控制范围,然而TiO2通过沉浸在热水中或暴露在水蒸汽中的处理会导致从非晶体改变为锐钛矿晶体。 It is known that TiO2 has a high refractive index and improving control of the refractive index of the film, however, TiO2 by immersion in hot water or exposure to water vapor in the process lead to a change from amorphous to anatase crystals. 从维持涂层同质性以及抑制碱迁移的效果等角度来看,优选地减小膜中的TiO2部分以抑制晶体化为锐钛矿晶体,并且膜中的TiO2的mol%比优选地小于40%。 Of maintaining homogeneity of the coating and inhibit the migration of alkali viewpoint of effects, preferably partially reduced TiO2 film to inhibit crystal into anatase crystals, and the mol% of TiO2 in the film is preferably less than 40 %. 更优选地为30%或更少。 More preferably 30% or less.

作为使用上述溶胶涂渍溶液形成层的方法,例如可以适当使用诸如浸渍方法、旋涂方法、喷涂方法、印刷方法、流涂(flow coating)方法、及其组合的公知涂覆方法。 As a method of using the sol-forming layer coating solution, for example, can be suitably used such as dipping method, a spin coating method, spray coating method, a printing method, a flow coating (flow coating) method, a known coating method and combinations thereof. 膜厚度可以通过改变浸渍方法中的提升速度、旋涂方法中的基底旋转速度等,以及改变涂覆溶液的浓度来控制。 The film thickness by changing the lifting speed in a dipping method, a substrate rotation speed in the spin coating method, and varying the concentration of the coating solution is controlled. 其中,可以根据所需膜厚度来适当选择浸渍方法中的提升速度,但是优选的是,在浸泡之后以缓和均匀的速度提起膜,该缓和均匀的速度例如为大约0.1到3.0mm/秒。 Wherein the lifting speed may be suitably selected in accordance with the desired method of immersing the film thickness, but preferably, after soaking in a uniform speed to ease lifting film, relaxing the uniform velocity, for example about 0.1 to 3.0mm / sec. 涂覆该层之后,可以在室温下使之干燥大约30分钟。 After coating the layer, and dried for about 30 minutes at room temperature. 该膜也可以在更高温度下进行干燥或热处理,并且热处理温度越高,该膜就越容易高密度化。 The membrane may be performed at a higher temperature drying or heat treatment, and the higher the heat treatment temperature, the more easily the film is high density. 在包含Al2O3作为主要成分的凝胶膜的情况下,可以通过增高热处理温度而形成较大不规则形的结构。 In the case of a gel film containing Al2O3 as a main component, and may be formed by a large irregularly shaped configuration increasing heat treatment temperature. 在包含SiO2作为主要成分的凝胶膜的情况下,可以通过增加热处理温度来改善抑制碱等迁移的能力。 In the case of a gel film containing SiO2 as a main component, it is possible to improve the ability to inhibit migration of alkali, by increasing the heat treatment temperature.

接着,在热水中浸泡通过依次涂覆包含SiO2作为主要成分的溶胶涂渍溶液和包含Al2O3作为主要成分的溶胶涂渍溶液而形成的凝胶膜,从而沉淀包含Al2O3作为主要成分的片状晶体,以形成最外表面的不规则形的形状。 Then, soak the gel film is formed by sequentially coating a sol containing SiO2 as a main component of the coating solution containing Al2O3 as a main component of a sol of the coating solution in hot water to precipitate plate crystals containing Al2O3 as a main component to form the outermost surface of an irregular shape. 通过在热水中浸泡,通过依次涂覆包含Al2O3的溶胶涂渍溶液而形成的凝胶膜的表面层承受胶溶作用等,并且一些成分被洗提,但是由于各种氢氧化物在热水中的溶解度的差异,包含Al2O3作为主要成分的片状晶体沉淀在凝胶膜的表面层,并且生长。 The surface layer of the gel film formed by immersion in hot water by sequentially coating a sol coating solution containing Al2O3 and the like subjected to peptization, and some components are eluted, but due to various hydroxides in hot water differences in solubility, plate crystals containing Al2O3 as a main component is precipitated in the surface layer of the gel film, and grow. 热水的温度优选地为40℃到100℃。 Temperature of hot water is preferably 40 ℃ to 100 ℃. 热水处理时间为大约5分钟到大约24小时。 The hot water treatment time is about 5 minutes to about 24 hours.

对于具有作为添加到包含Al2O3作为主要成分的膜的不同种类的成分的诸如TiO2、ZrO2、SiO2、ZnO和MgO的氧化物的凝胶膜的热水处理,使用各成分在热水中的溶解度的差异来执行结晶,因此与Al2O3的单独成分膜的热水处理不同,可以通过改变无机成分的组成而在宽范围内控制片状晶体的大小。 For a component to be added to a different kind of film containing Al2O3 as a main component of the hot water treatment of the gel film of the oxide TiO2, ZrO2, SiO2, ZnO and MgO, such as the solubility of each component used in hot water differences crystallization is performed, and thus the hot water treatment of the single component film of Al2O3 different, can control the size of plate crystals over a wide range by changing the composition of inorganic components. 结果,可以在宽范围内控制通过片状晶体形成的不规则形的形状。 As a result, control of irregular shape formed by the plate-like crystals over a wide range. 此外,如果ZnO用作子成分,与Al2O3一起沉淀成为可能,从而可以在更宽的范围内控制折射率,因而使得可能实现极好的抗反射性能。 Moreover, if ZnO is used as the sub-component, and Al2O3 with the precipitate becomes possible, the refractive index can be controlled in a wider range, thus making it possible to realize an excellent antireflection performance.

包含SiO2作为主要成分的本发明的层的厚度等于或大于5nm并且等于或小于100nm,更优选地为等于或大于5nm并且等于或小于80nm。 Thickness of the layer of the present invention contains SiO2 as a main component is equal to or greater than 5nm and less than or equal to 100nm, more preferably equal to or greater than 5nm and less than or equal to 80nm. 如果厚度小于5nm,则不能获得抑制碱迁移的充分效果。 If the thickness is less than 5nm, it is not obtained a sufficient effect of suppressing migration of the alkali. 如果厚度大于100nm,由于干扰等原因而对反射降低效果的贡献降低。 If the thickness is greater than 100nm, while the contribution due to interference reflection reducing effect is reduced. 包含Al2O3作为主要成分的层的厚度为等于或大于10nm并且等于或小于120nm,更优选地为等于或大于10nm并且等于或小于100nm。 Thickness of the layer containing Al2O3 as a main component is greater than or equal to 10nm and equal to or less than 120nm, more preferably greater than or equal to 10nm and equal to or less than 100nm. 如果厚度小于10nm,片状晶体的粘着特性降低,并且包含SiO2作为主要成分的层和片状晶体层之间折射率的差的梯度变得过大,以至于光学性能受到损害。 If the thickness is less than 10 nm, the sheet-like crystal is reduced adhesive properties, and comprising SiO2 as a gradient refractive index difference between the layer and the plate crystal layer is a main component becomes too large, so that the optical performance is impaired. 如果厚度大于120nm,由于干扰等原因而对反射降低效果的贡献降低。 If the thickness is greater than 120nm, while the contribution due to interference reflection reducing effect is reduced.

在本发明中使用的基底包括玻璃、树脂、玻璃反射镜、和由树脂制成的反射镜。 The substrate used in the present invention include glass, resins, glass mirrors and mirrors made of resin. 树脂基底的典型例子包括诸如聚酯、三乙酰纤维素、乙酸纤维素、聚对苯二甲酸乙二醇酯、聚丙烯、聚苯乙烯、聚碳酸酯、聚甲基丙烯酸甲酯、ABS树脂、聚苯醚、聚氨酯、聚乙烯以及聚氯乙烯的热塑树脂的膜和模制产品;从诸如不饱和聚酯树脂、苯酚树脂、交联聚氨酯、交联压克力树脂以及交联饱和聚酯树脂的各种热固性树脂获得的交联膜和交联模制产品。 Typical examples of substrates include resin such as polyester, triacetyl cellulose, cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene, polycarbonate, polymethyl methacrylate, ABS resins, polyphenylene oxide, polyurethane, polyethylene, and polyvinyl chloride film and the thermoplastic resin molded product; from such unsaturated polyester resins, phenol resins, crosslinked polyurethane, crosslinked acrylic resin, and a crosslinking saturated polyester various thermosetting resins crosslinked film obtained resins and crosslinked molded product. 玻璃的具体例子可以包括无碱玻璃和硅酸铝玻璃。 Specific examples of glass may include alkali-free glass, and aluminosilicate glass. 在本发明中使用的基底可以用能够最终形成适合于使用目的的形状的任何材料制成,该形状包括平板、膜和片,并且可以具有二维或三维曲面。 The substrate used in the present invention may be any material capable of forming the final shape suitable for the purpose of use is made, which comprises a flat plate shape, films and sheets, and may have a two-dimensional or three-dimensional surface. 可以适当地确定厚度,并且厚度大约为等于或小于5mm,但是不限于此。 The thickness can be appropriately determined, and a thickness of about equal to or less than 5mm, but is not limited thereto.

除了上述层之外,本发明的光学透明部件可以进一步设置有用于赋予各种功能的层。 In addition to the above layers, the optically transparent member of the present invention may further be provided with a layer for imparting various functions. 例如,可以在片状晶体层上设置硬涂覆层用于改进膜的硬度,或者可以设置氟代烷基硅烷(fluoroalkyl silane)或烷基硅烷的防水层用于赋予防水性。 For example, a hard coat layer may be provided for improving the hardness of the film, or may be provided fluoroalkyl silane (fluoroalkyl silane) or alkylsilane waterproofing layer for imparting water repellency crystal layer on the sheet. 为了防止污染物的堆积等,可以设置折射率低于包含Al2O3作为主要成分的片状晶体的折射率的材料的层,或者由两性化合物组成的层。 In order to prevent the accumulation of contaminants and the like, it may be disposed lower than the refractive index of the layer containing Al2O3 as a main component of the refractive index of the plate-like crystals of the material, or a layer of amphoteric compounds. 为了改进基底和包含SiO2作为主要成分的层之间的粘着性,可以使用粘着层或底漆层。 To improve substrate containing SiO2 as an adhesive layer between the main component, may be used an adhesive layer or a primer layer. 在基底和包含SiO2作为主要成分的层之间设置的其他层的折射率优选地是基底的折射率和包含SiO2作为主要成分的层的折射率之间的中间值。 And comprising SiO2 as the substrate refractive index layer is preferably disposed between the other layer is a main component of the refractive index of the substrate containing SiO2 as an intermediate value between the refractive index layer is a main component.

将结合例子具体描述本发明。 The present invention is specifically described with examples. 然而,本发明不限于这种例子。 However, the present invention is not limited to such an example. 通过下述的方法评估从各例和比较例获得的、并且在表面上具有精细不规则形的透明膜。 Evaluation obtained by the following method from the respective examples and comparative examples and having fine irregular shape on the surface of the transparent film.

(1)观察涂层的形状使用扫描电子显微镜(日立制作所生产的FE-SEM,S4500)通过摄影方式观察涂层的表面层的表面(加速电压;10.0kV,缩放因子;30000)。 (1) was observed using a scanning electron microscope, the shape of the coating layer (produced by Hitachi FE-SEM, S4500) the surface of the surface coating layer was observed by a photographic mode (acceleration voltage; 10.0 kV, scaling factor; 30000). 使用扫描探测显微镜(SPM,DFM型,由Seiko电子工业公司生产的SPI3800),确定了通过在JIS B 0601中定义的中心线平均粗糙度的二维延伸而获得的平均表面粗糙度Ra′值和表面积比Sr。 Using a scanning probe microscope (SPM, DFM type, manufactured by Seiko Electronics Industry Co., Ltd. of SPI3800), the average surface roughness Ra is determined by the two-dimensional extension of the center line average roughness defined in JIS B 0601 obtained 'value and surface area ratio Sr.

(2)透射率的测量使用自动光学部件测量设备(JASCO生产的ART-25GD),在从可见区域到近红外区域的范围内测量透射率。 (2) measuring the transmittance of an optical component using an automatic measuring apparatus (produced by a JASCO ART-25GD), measuring the transmittance in the range from the visible region to near infrared region. 使用盘状玻璃板。 Discotic glass. 在透射率和反射率测量中的光入射角分别是0°和10°。 Angle of incidence of the light transmittance and reflectance measurements are 0 ° and 10 °.

(3)膜折射率的测量通过日本JAWoollam株式会社生产的Ellipsometer VASE,在380nm到800nm的波长范围内进行测量。 (3) Measurement of refractive index film produced by Japan Co. JAWoollam Ellipsometer VASE, measurements performed in a wavelength range of 380nm to 800nm.

例1尺寸为大约100mm×100mm且厚度为大约2mm的浮法玻璃(clear-float glass)基片(组分:钠钙硅酸盐类型,折射率ng=1.52)由异丙醇进行超声波清洗,干燥,并且用作用于涂覆的玻璃基片。 Example 1 a size of about 100mm × 100mm and a thickness of float glass (clear-float glass) substrate of about 2mm (composition: soda lime silicate type, refractive index ng = 1.52) was subjected to ultrasonic cleaning with isopropyl alcohol, dried and used as a glass substrate for coating.

四乙氧基硅烷(TEOS)溶解在乙醇(EtOH)中,0.01M的磷酸水溶液被添加到所得的溶液中作为催化剂,并且将所得混合物搅拌6小时。 Tetraethoxysilane (TEOS) dissolved in ethanol (EtOH), a 0.01M aqueous solution of phosphoric acid is added to the resultant solution as a catalyst, and the resulting mixture was stirred for 6 hours. 此时各成分的摩尔比为TEOS∶EtOH∶H3PO4aq=1∶40∶2。 At this time, the molar ratio of each component is TEOS:EtOH:H3PO4aq = 1:40:2. 正丁醇钛(TBOT)溶解在乙醇中,接着将乙酰乙酸乙酯(EAcAc)添加到所得溶液中作为稳定剂,并且所得混合物在室温下搅拌3小时。 Titanium n-butoxide (TBOT) was dissolved in ethanol, followed by ethyl acetoacetate (EAcAc) was added to the resultant solution as a stabilizer, and the resulting mixture was stirred at room temperature for 3 hours. 各成分的摩尔比为TBOT∶EtOH∶EAcAc=1∶20∶1。 Molar ratio of each component is TBOT:EtOH:EAcAc = 1:20:1. TiO2溶胶溶液添加到前述SiO2溶胶溶液中,使得获得SiO2∶TiO2=95∶5的摩尔比,并且所得混合物在室温下搅拌2小时,并且接着用作SiO2-TiO2涂渍溶液。 TiO2 sol solution was added to the aforementioned SiO2 sol solution so that the molar ratio of SiO2:TiO2 = 95:5 obtained, and the resulting mixture was stirred at room temperature for 2 hours, and then used as a SiO2-TiO2 coating solution. 接着,前述涂层玻璃基片浸泡在此涂渍溶液中,涂层膜通过浸渍方法(以0.5mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Next, the coated glass substrate was immersed in this coating solution, the coating film by a dipping method (lifting speed at 0.5mm / sec, and 20 ℃ and 56% RH) is formed on the surface of the glass substrate. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形SiO2/TiO2膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking one hour to 400 deg.] C, and the non-transparent amorphous SiO2 / TiO2 film coated thereon.

测量所得膜的厚度和折射率,且测量结果示出厚度ds是ds=20nm,且折射率是ns=1.48。 Measuring the resulting film thickness and refractive index, and the measurement shows the thickness ds was ds = 20nm, and the refractive index was ns = 1.48.

接着,仲丁醇铝(Al(O-sec-Bu)3)溶解在IPA中,EAcAc添加到所得溶液中作为稳定剂,并且所得的混合物在室温下搅拌大约3小时。 Next, aluminum sec-butoxide (Al (O-sec-Bu) 3) was dissolved in IPA, EAcAc was added to the resultant solution as a stabilizer, and the resulting mixture was stirred at room temperature for about 3 hours. 在这之后,0.01M[HCl aq.]添加到所得溶液中,并且所得混合物在室温下搅拌大约3小时,以准备Al2O3溶胶溶液。 After that, 0.01M [HCl aq.] Was added to the resulting solution, and the resulting mixture was stirred at room temperature for about 3 hours to prepare Al2O3 sol solution. 在此,溶液的摩尔比为Al(O-sec-Bu)3∶IPA∶EAcAc∶HClaq.=1∶20∶1∶1。 Here, the molar ratio of the solution was Al (O-sec-Bu) 3:IPA:EAcAc:HClaq. = 1:20:1:1. 前述涂层基片浸泡在该涂渍溶液中,并且涂层膜通过浸渍方法(以2mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 The coated substrate was immersed in the coating solution and the coating film is formed on the surface of the glass substrate by a dipping method (lifting speed at 2mm / sec, and 20 ℃ and 56% RH). 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,透明无定形Al2O3膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking one hour to 400 deg.] C, a transparent amorphous Al2O3 film coated thereon. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如图2所示。 FE-SEM observation of the surface of the obtained films, shaped to find a structure of fine irregularities in which plate crystals containing Al2O3 as a main component and complexly intertwined randomly, as shown in FIG. 通过FE-SEM观察横截面,以观察如图3所示其中包含Al2O3作为主要成分的片状晶体选择性地在与层的表面垂直的方向上布置的图像。 By FE-SEM observation of the cross section, shown in Figure 3 to see an image in which plate crystals containing Al2O3 main component is selectively disposed in a direction perpendicular to the surface layer. 图3中的最下层是基底的玻璃横截面,中间层是由包含SiO2作为主要成分的层和包含Al2O3作为主要成分的层组成的层,并且最上层是由片状晶体组成的片状晶体层。 Lowermost in FIG. 3 is a cross section of a glass substrate, comprising the intermediate layer is made of SiO2 as a main component and the layer containing Al2O3 as a main component of the composition, and the top plate crystal layer is made of a sheet-like crystals . 通过SPM测量表面,并且测量结果示出平均表面粗糙度Ra′值(nm)是Ra′=28nm,并且表面积比Sr是Sr=1.9。 By SPM measuring surface, and measurement results are shown an average surface roughness Ra 'value (nm) was Ra' = 28nm, and the surface area ratio Sr was Sr = 1.9.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试作为加速测试,以检验光学性能的耐久性,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test as an accelerated test to verify the durability of the optical properties, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例2尺寸为大约50mm×50mm且厚度为大约1mm的S-TIH53玻璃基片(由OHARA公司生产,折射率n=1.84)由异丙醇进行超声波清洗,干燥,并且用作用于涂覆的玻璃基片。 Example 2 a size of about 50mm × 50mm and a thickness of about 1mm of S-TIH53 glass substrate (manufactured by OHARA INC., Refractive index n = 1.84) was subjected to ultrasonic cleaning with isopropyl alcohol, dried, and used as a coated glass substrate.

TiO2溶胶溶液添加到前述SiO2溶胶溶液中,使得获得SiO2∶TiO2=7∶3的摩尔比,并且所得混合物在室温下搅拌2小时,并且接着用作SiO2-TiO2涂渍溶液,如同例1中所述。 TiO2 sol solution was added to the aforementioned SiO2 sol solution so as to obtain the molar ratio SiO2:TiO2 = 7:3, and the resulting mixture was stirred at room temperature for 2 hours, and then used as a SiO2-TiO2 coating solution as in Example 1 as above. 接着,前述涂层玻璃基片浸泡在此涂渍溶液中,涂层膜通过浸渍方法(以0.5mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Next, the coated glass substrate was immersed in this coating solution, the coating film by a dipping method (lifting speed at 0.5mm / sec, and 20 ℃ and 56% RH) is formed on the surface of the glass substrate. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形SiO2/TiO2膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking one hour to 400 deg.] C, and the non-transparent amorphous SiO2 / TiO2 film coated thereon. 测量所获得的膜的厚度和折射率,并且测量结果示出,厚度为28nm且折射率为ns为1.67。 Thickness and refractive index of the obtained film was measured, and the measured results are shown, having a thickness of 28nm and a refractive index of 1.67 ns.

接着,前述涂层基片浸泡在如同例1的Al2O3涂渍溶液中,接着涂层膜通过浸渍方法(以2mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Next, the coated substrate was immersed in the Al2O3 coating solution as in Example 1, and then the coating film is formed on the surface of the glass substrate by a dipping method (lifting speed at 2mm / sec, and 20 ℃ and 56% RH) on. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking 400 ℃ one hour, and a transparent amorphous Al2O3 film without a coating thereon. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=27nm,并且表面积比Sr是Sr=1.9。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 27nm, and the surface area ratio Sr was Sr = 1.9.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例3使用与例2相同的S-TIH53玻璃基片(由OHARA公司生产,折射率n=1.84)用作用于涂覆的玻璃基片。 Example 3 Example 2 using the same S-TIH53 glass substrate (manufactured by OHARA INC., Refractive index n = 1.84) is used as a glass substrate for coating.

涂覆SiO2/TiO2(7/3),接着以与例2相同的方式形成透明无定形SiO2/TiO2膜。 Coated SiO2 / TiO2 (7/3), followed by the same manner as in Example 2 to form a transparent amorphous SiO2 / TiO2 film. 测量所获得的膜的厚度和折射率,并且测量结果示出,厚度为28nm且折射率ns为1.67。 Thickness and refractive index of the obtained film was measured, and the measured results are shown, having a thickness of 28nm and a refractive index of 1.67 ns.

仲丁醇铝[Al(O-sec-Bu)3]溶解在2丙醇[IPA]中,乙酰乙酸乙酯[EAcAc]添加到所得的溶液中作为稳定剂,并且所得的混合物在室温下搅拌大约3小时,以准备Al2O3溶胶溶液。 Aluminum sec-butoxide [Al (O-sec-Bu) 3] was dissolved in 2-propanol [of IPA] in ethyl acetoacetate [EAcAc] was added to the resultant solution as a stabilizer, and the resulting mixture was stirred at room temperature about 3 hours to prepare the Al2O3 sol solution. 在此,该溶液的摩尔比为Al(O-sec-Bu)3∶IPA∶EAcAc=1∶20∶1。 Here, the molar ratio of the solution was Al (O-sec-Bu) 3:IPA:EAcAc = 1:20:1. 正丁醇钛[Ti(On-Bu)4]也溶解在IPA中,EAcAc添加到所得溶液中,并且所得混合物搅拌大约3小时,以准备TiO2溶胶溶液。 Titanium n-butoxide [Ti (On-Bu) 4] is also dissolved in IPA, EAcAc was added to the resulting solution, and the resulting mixture was stirred for about 3 hours to prepare a TiO2 sol solution. 该溶液的摩尔比为Ti(On-Bu)4∶IPA∶EAcAc=1∶20∶1。 The molar ratio of the solution was Ti (On-Bu) 4:IPA:EAcAc = 1:20:1. 此TiO2溶胶溶液添加到前述Al2O3溶胶溶液中,使得获得Al2O3∶TiO2=8∶2的重量比,所得溶液搅拌大约30分钟,接着将0.01M[HCl aq.]添加到所得混合物中,并且所得混合物在室温下搅拌大约3小时。 This TiO2 sol solution was added to the aforementioned Al2O3 sol solution so that a weight ratio Al2O3:TiO2 = 8:2 obtained, and the resulting solution was stirred for about 30 minutes, then 0.01M [HCl aq.] Was added to the resulting mixture, and the resulting mixture It was stirred at room temperature for about 3 hours. 以这种方式,准备好了作为Al2O3/TiO2溶胶的涂渍溶液。 In this manner, a coating solution ready as Al2O3 / TiO2 sol. 在此,所添加的HCl aq.的量按照摩尔比是Al(O-sec-Bu)3和Ti(On-Bu)4的量的两倍。 Here, the added HCl aq. An amount twice the molar ratio of Al (O-sec-Bu) 3 and the amount of Ti (On-Bu) 4 is.

接着,如同例1,前述涂层基片浸泡在Al2O3/TiO2涂渍溶液中,并且涂层膜通过浸渍方法(以1mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Subsequently, as in Example 1, the coated substrate is immersed in the Al2O3 / TiO2 coating solution and the coating film is formed on a glass substrate by the dipping method (lifting speed to 1mm / sec, and 20 ℃ and 56% RH) on the surface. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3/TiO2膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking one hour to 400 deg.] C, and the non-transparent amorphous Al2O3 / TiO2 film coated thereon. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=18nm,并且表面积比Sr是Sr=1.5。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 18nm, and the surface area ratio Sr was Sr = 1.5.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例4使用与例2相同的S-TIH53玻璃基片(由OHARA公司生产,折射率nb=1.84)作为用于涂覆的玻璃基片。 Example 4 Example 2 using the same S-TIH53 glass substrate (manufactured by OHARA INC., Refractive index nb = 1.84) as a glass substrate for coating.

涂覆SiO2/TiO2(7/3),接着以与例2相同的方式形成无定形SiO2/TiO2膜。 Coated SiO2 / TiO2 (7/3), followed by the same manner as in Example 2 to form an amorphous SiO2 / TiO2 film. 测量所获得的膜的厚度和折射率,并且测量结果示出,厚度为28nm且折射率为ns为1.67。 Thickness and refractive index of the obtained film was measured, and the measured results are shown, having a thickness of 28nm and a refractive index of 1.67 ns.

仲丁醇铝[Al(O-sec-Bu)3]溶解在2丙醇[IPA]中,乙酰乙酸乙酯[EAcAc]添加到所得溶液中作为稳定剂,并且所得的混合物在室温下搅拌大约3小时,以准备Al2O3溶胶溶液。 Aluminum sec-butoxide [Al (O-sec-Bu) 3] was dissolved in 2-propanol [of IPA] in ethyl acetoacetate [EAcAc] was added to the resultant solution as a stabilizer, and the resulting mixture was stirred at room temperature for about for 3 hours to prepare Al2O3 sol solution. 在此,该溶液的摩尔比为Al(O-sec-Bu)3∶IPA∶EAcAc=1∶20∶0.5。2水合乙酸锌[Zn(CH3COO)2·2H2O]也溶解在[IPA]中,将单乙醇胺[MEA]添加到所得溶液中,并且所得混合物搅拌大约3小时,以准备ZnO溶胶溶液。 Here, the molar ratio of the solution was Al (O-sec-Bu) 3:IPA:EAcAc = 1:20:0.5.2 zinc acetate dihydrate [Zn (CH3COO) 2 · 2H2O] is also dissolved in [of IPA] in monoethanolamine [the MEA] was added to the resulting solution, and the resulting mixture was stirred for about 3 hours to prepare a ZnO sol solution. 该溶液的摩尔比为Zn(CH3COO)2·2H2O∶IPA∶MEA=1∶10∶1。 The molar ratio of the solution was Zn (CH3COO) 2 · 2H2O:IPA:MEA = 1:10:1. 此ZnO溶胶溶液添加到前述Al2O3溶胶溶液中,使得获得Al2O3∶ZnO=0.8∶0.2的重量比,并且所得混合物搅拌大约30分钟。 This ZnO sol solution was added to the aforementioned Al2O3 sol solution so that a weight ratio Al2O3:ZnO = 0.8:0.2 obtained, and the resulting mixture was stirred for approximately 30 minutes. 以这种方式,准备好了作为Al2O3-ZnO溶胶的涂渍溶液。 In this manner, a coating solution ready as Al2O3-ZnO sol.

接着,如同例1,前述涂层基片浸泡在Al2O3/ZnO涂渍溶液中,接着,涂层膜通过浸渍方法(以2mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Subsequently, as in Example 1, the coated substrate is immersed in the Al2O3 / ZnO coating solution, and then, the coating film formed on the glass substrate by the dipping method (lifting speed at 2mm / sec, and 20 ℃ and 56% RH) on the surface of the sheet. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3/ZnO膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking 400 ℃ one hour, and the transparent amorphous Al2O3 / ZnO film coated thereon. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=32nm,并且表面积比Sr是Sr=2.0。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 32nm, and the surface area ratio Sr was Sr = 2.0.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例5使用尺寸为大约50mm×50mm且厚度为大约1mm的S-TIH1玻璃基片(由OHARA公司生产,折射率nb=1.71)作为用于涂覆的玻璃基片。 Example 5 a size of about 50mm × 50mm and a thickness of about 1mm of S-TIH1 glass substrate (manufactured by OHARA INC., Refractive index nb = 1.71) as a glass substrate for coating.

正丁醇锆(ZBOT)溶解在乙醇中,乙酰乙酸乙酯(EAcAc)添加到所得溶液中作为稳定剂,并且所得的混合物在室温下搅拌大约3小时。 Zirconium n-butoxide (ZBOT,) was dissolved in ethanol, ethyl acetoacetate (EAcAc) was added to the resultant solution as a stabilizer, and the resulting mixture was stirred at room temperature for about 3 hours. 各成分的摩尔比为ZBOT∶EtOH∶EAcAc=1∶20∶1。 Molar ratio of each component is ZBOT:EtOH:EAcAc = 1:20:1. 如同例1,TiO2溶胶溶液接着是ZrO2溶胶溶液添加到SiO2溶胶溶液中,使得获得SiO2∶TiO2∶ZrO2=7∶1∶2的摩尔比,并且所得混合物在室温下搅拌2小时,并且接着用作SiO2-TiO2-ZrO2涂渍溶液。 As in Example 1, TiO2 sol solution followed ZrO2 sol solution was added to the SiO2 sol solution so that the molar ratio SiO2:TiO2:ZrO2 = 7:1:2 obtained, and the resulting mixture was stirred at room temperature for 2 hours, and then used SiO2-TiO2-ZrO2 coating solution. 接着,前述涂层玻璃基片浸泡在此涂渍溶液中,涂层膜通过浸渍方法(以0.5mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Next, the coated glass substrate was immersed in this coating solution, the coating film by a dipping method (lifting speed at 0.5mm / sec, and 20 ℃ and 56% RH) is formed on the surface of the glass substrate. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形SiO2/TiO2/ZrO2膜涂覆于其上。 The glass substrate was dried, and then baked by a heat treatment of 400 deg.] C for one hour, and a transparent amorphous SiO2 / TiO2 / ZrO2 film coated on thereon. 测量所获得的膜的厚度和折射率,并且测量结果示出,厚度为25nm且折射率为ns=1.62。 Thickness and refractive index of the obtained film was measured, and the measured results are shown, having a thickness of 25nm and a refractive index ns = 1.62.

仲丁醇铝[Al(O-sec-Bu)3]溶解在2丙醇[IPA]中,乙酰乙酸乙酯[EAcAc]添加到所得溶液中作为稳定剂,并且所得的混合物在室温下搅拌大约3小时,以准备Al2O3溶胶溶液。 Aluminum sec-butoxide [Al (O-sec-Bu) 3] was dissolved in 2-propanol [of IPA] in ethyl acetoacetate [EAcAc] was added to the resultant solution as a stabilizer, and the resulting mixture was stirred at room temperature for about for 3 hours to prepare Al2O3 sol solution. 在此,该溶液的摩尔比为Al(O-sec-Bu)3∶IPA∶EAcAc=1∶20∶0.5。2水合乙酸锌[Zn(CH3COO)2·2H2O]也溶解在[IPA]中,将单乙醇胺[MEA]添加到所得溶液中,并且所得混合物搅拌大约3小时,以准备ZnO溶胶溶液。 Here, the molar ratio of the solution was Al (O-sec-Bu) 3:IPA:EAcAc = 1:20:0.5.2 zinc acetate dihydrate [Zn (CH3COO) 2 · 2H2O] is also dissolved in [of IPA] in monoethanolamine [the MEA] was added to the resulting solution, and the resulting mixture was stirred for about 3 hours to prepare a ZnO sol solution. 该溶液的摩尔比为Zn(CH3COO)2·2H2O∶IPA∶MEA=1∶10∶1。 The molar ratio of the solution was Zn (CH3COO) 2 · 2H2O:IPA:MEA = 1:10:1. 此ZnO溶胶溶液添加到前述Al2O3溶胶溶液中,使得获得Al2O3∶ZnO=0.9∶0.1的重量比,并且所得混合物搅拌大约3小时。 This ZnO sol solution was added to the aforementioned Al2O3 sol solution so that a weight ratio Al2O3:ZnO = 0.9:0.1 obtained, and the resulting mixture was stirred for about 3 hours. 以这种方式,准备好了作为Al2O3-ZnO溶胶的涂渍溶液。 In this manner, a coating solution ready as Al2O3-ZnO sol.

接着,如同例1,前述涂层基片浸泡在Al2O3/ZnO涂渍溶液中,接着,涂层膜通过浸渍方法(以1mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Subsequently, as in Example 1, the coated substrate is immersed in the Al2O3 / ZnO coating solution, and then, the coating film formed on the glass substrate by the dipping method (lifting speed to 1mm / sec, and 20 ℃ and 56% RH) on the surface of the sheet. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3/ZnO膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking 400 ℃ one hour, and the transparent amorphous Al2O3 / ZnO film coated thereon. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=30nm,并且表面积比Sr是Sr=1.9。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 30 nm, and the surface area ratio Sr was Sr = 1.9.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例6对于与例5中相同的基片,使用由OHARA公司生产的S-TIH1玻璃基片(折射率n=1.71)作为用于涂覆的玻璃基片,涂覆例2中所使用的SiO2-TiO2涂渍溶液,并且接着形成透明无定形SiO2/TiO2膜。 Example 6 Example 5 as in the same substrate, using the S-TIH1 glass substrate manufactured by the OHARA INC. (Refractive index n = 1.71) as a glass substrate for coating, the coating used in Example 2 SiO2 -TiO2 coating solution, and then forming a transparent amorphous SiO2 / TiO2 film. 测量所获得的膜的厚度和折射率,并且测量结果示出,厚度为28nm,且折射率为n=1.67。 Thickness and refractive index of the obtained film was measured, and the measured results are shown, with a thickness of 28nm, and a refractive index n = 1.67.

接着,该玻璃基片浸泡在例4中使用的Al2O3/ZnO中,接着涂层膜以1mm/秒的提升速度形成在玻璃基片的表面上。 Next, the glass substrate used in Example 4 was immersed in the Al2O3 / ZnO, followed by the coating film to improve the speed of 1mm / sec is formed on the surface of the glass substrate. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3/ZnO膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking 400 ℃ one hour, and the transparent amorphous Al2O3 / ZnO film coated thereon. 接着,玻璃基片进一步浸泡在例1中使用的Al2O3涂渍溶液中,并且涂层膜以1mm/秒的提升速度形成。 Next, the glass substrate is further immersed in the Al2O3 coating solution used in Example 1, and the coating film formed to enhance the speed of 1mm / sec. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking 400 ℃ one hour, and a transparent amorphous Al2O3 film without a coating thereon. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=23nm,并且表面积比Sr是Sr=1.7。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 23nm, and the surface area ratio Sr was Sr = 1.7.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例7在例1中使用的浮法玻璃基片上,使用磁控溅射设备形成厚度为30nm的SiO2膜。 The float glass substrate in Example 7 used in Example 1, using a magnetron sputtering apparatus for forming an SiO2 film thickness of 30nm. 该膜的折射率为1.45。 The refractive index of the film was 1.45. 接着,玻璃基片浸泡在例1中使用的Al2O3涂渍溶液中,接着,涂层膜以2mm/秒的提升速度形成。 Next, the glass substrate is immersed in the Al2O3 coating solution used in Example 1, followed by coating to improve the film forming speed of 2mm / sec. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking 400 ℃ one hour, and a transparent amorphous Al2O3 film without a coating thereon. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=22nm,并且表面积比Sr是Sr=1.6。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 22nm, and the surface area ratio Sr was Sr = 1.6.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例8在例1中使用的浮法玻璃基片上,使用磁控溅射设备形成厚度为30nm的SiO2膜。 The float glass substrate in Example 8 used in Example 1, using a magnetron sputtering apparatus for forming an SiO2 film thickness of 30nm. 该膜的折射率为1.45。 The refractive index of the film was 1.45. 接着,通过磁控溅射设备涂覆厚度为35nm的Al金属膜。 Subsequently, the device is coated by magnetron sputtering an Al metal film thickness of 35nm. 接着,玻璃基片在100℃的热水中浸泡30分钟。 Next, the glass substrate was immersed in hot water of 100 deg.] C for 30 minutes. 在浸泡后的几分钟内,Al的金属光泽消失,并且在提升后,透明膜留在表面层上。 Within a few minutes after soaking, Al metallic luster disappeared, and after lifting, the transparent film remaining on the surface layer. 之后,该玻璃基片在100℃下干燥10分钟。 Thereafter, the glass substrate was dried at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=57nm,并且表面积比Sr是Sr=2.6。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 57nm, and the surface area ratio Sr was Sr = 2.6.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例9在例2中所使用的TIH53基片上,使用二重磁控溅射设备形成厚度为40nm的其中SiO2与ZrO2的组分比为7∶3的合成透明氧化物膜。 On 9 TIH53 substrate used in Example 2 embodiment, the use of dual magnetron sputtering apparatus wherein a thickness of the ZrO2 composition ratio of SiO2 to 40nm for the synthesis of a transparent oxide film 7:3. 膜的折射率为1.65。 Refractive index film was 1.65. 接着,通过二重溅射形成厚度为50nm的、Al2O3和ZnO的组分比为8∶2的膜。 Next, sputtering is formed by the double thickness of 50nm, the composition ratio of ZnO and Al2O3 in a film 8:2. 通过磁控溅射涂覆厚度为25nm的Al金属膜。 An Al metal film is formed by magnetron sputter coating thickness of 25nm. 接着,玻璃基片在100℃的热水中浸泡30分钟。 Next, the glass substrate was immersed in hot water of 100 deg.] C for 30 minutes. 在浸泡后的几分钟内,Al的金属光泽消失,并且在提升后,透明膜留在表面层上。 Within a few minutes after soaking, Al metallic luster disappeared, and after lifting, the transparent film remaining on the surface layer. 之后,该玻璃基片在100℃下干燥10分钟。 Thereafter, the glass substrate was dried at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=42nm,并且表面积比Sr是Sr=2.2。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 42nm, and the surface area ratio Sr was Sr = 2.2.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

例10在例5所使用的TIH01基片上,使用二重磁控溅射设备形成厚度为40nm的其中SiO2与ZrO2的组分比为8∶2的合成透明氧化物膜。 Example 10 On the TIH01 substrate used in Example 5, using a magnetron sputtering apparatus for forming a double thickness of 40nm wherein the composition ratio of SiO2 and ZrO2 is synthesized in a transparent oxide film 8:2. 膜的折射率为1.61。 Refractive index film was 1.61. 接着,通过二重溅射形成厚度为50nm的且Al2O3和ZnO的组分比为9∶1的膜。 Next, a thickness of 50nm and Al2O3 and ZnO components are formed by a sputtering ratio of 9 double film. 通过磁控溅射涂覆厚度为200nm的Al金属膜。 An Al metal film is formed by magnetron sputter coating thickness of 200nm. 接着,玻璃基片在100℃的热水中浸泡30分钟。 Next, the glass substrate was immersed in hot water of 100 deg.] C for 30 minutes. 在浸泡后的几分钟内,Al的金属光泽消失,并且在提升后,透明膜留在表面层上。 Within a few minutes after soaking, Al metallic luster disappeared, and after lifting, the transparent film remaining on the surface layer. 之后,该玻璃基片在100℃下干燥10分钟。 Thereafter, the glass substrate was dried at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=45nm,并且表面积比Sr是Sr=2.3。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 45nm, and the surface area ratio Sr was Sr = 2.3.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

比较例1在例1中使用的浮法玻璃基片浸泡在例1中使用的Al2O3溶胶溶液中,接着,涂层膜通过浸渍方法(以2mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Comparative Example 1 a float glass substrate used in Example 1 was immersed in the Al2O3 sol solution used in Example 1, and then, the coating film by a dipping method (lifting speed at 2mm / sec, and 56% RH and 20 ℃ ) is formed on the surface of the glass substrate. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,透明无定形Al2O3膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking one hour to 400 deg.] C, a transparent amorphous Al2O3 film coated thereon. 接着,该玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate is immersed in hot water at 100 deg.] C 30 minutes, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=28nm,并且表面积比Sr是Sr=1.9。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 28nm, and the surface area ratio Sr was Sr = 1.9.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

比较例2在例2中使用的S-TIH53基片(折射率n=1.84)浸泡在例3中使用的Al2O3/TiO2溶胶溶液中,并且涂层膜通过浸渍方法(以1mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基片的表面上。 Comparative Example 2 S-TIH53 substrate used in Example 2 (refractive index n = 1.84) was immersed in Example Al2O3 / TiO2 sol solution used in 3, and the coating film by a dipping method (at 1mm / sec speed lift and 20 ℃ and 56% RH) is formed on the surface of the glass substrate. 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且在其上涂覆透明无定形Al2O3/TiO2膜。 The glass substrate was dried, and then thermally treated by baking one hour to 400 deg.] C, and coated thereon a transparent amorphous Al2O3 / TiO2 film. 接着,玻璃基片在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=18nm,并且表面积比Sr是Sr=1.5。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 18nm, and the surface area ratio Sr was Sr = 1.5.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

比较例3例1中使用的浮法玻璃基片(组分:钠钙硅酸盐类型,折射率n=1.52)由异丙醇进行超声波清洗,干燥,并且用作用于涂覆的玻璃基片。 Comparative Example 3 Example 1 a float glass substrate used (composition: soda lime silicate type, refractive index n = 1.52) for ultrasonic cleaning with isopropyl alcohol, dried, and used as a glass substrate for coating .

将TiO2溶胶溶液添加到前述SiO2溶胶溶液中,以获得SiO2∶TiO2=3∶7的摩尔比,并且所得混合物在室温下搅拌2小时,接着用作SiO2-TiO2涂渍溶液,如同例1。 The TiO2 sol solution was added to the aforementioned SiO2 sol solution so as to obtain the molar ratio SiO2:TiO2 = 3:7, and the resulting mixture was stirred at room temperature for 2 hours, and then used as a SiO2-TiO2 coating solution as in Example 1. 接着,前述涂覆玻璃基片浸泡在此涂渍溶液中,涂层膜通过浸渍方法(以0.5mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基底的表面上。 Next, the coated glass substrate was immersed in this coating solution, the coating film by a dipping method (lifting speed at 0.5mm / sec, and 20 ℃ and 56% RH) is formed on the surface of the glass substrate. 使玻璃基底干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形SiO2/TiO2膜涂覆于其上。 The glass substrate was dried, and then baked by a heat treatment of 400 deg.] C for one hour and a transparent amorphous SiO2 / TiO2 film coated thereon.

测量所获得的膜的厚度和折射率,并且测量结果示出,厚度为28nm,且折射率为2.05。 Thickness and refractive index of the obtained film was measured, and the measured results are shown, with a thickness of 28nm, and a refractive index of 2.05.

接着,该玻璃基片浸泡在例1中使用的Al2O3溶胶溶液中,接着,涂层膜通过浸渍方法(以2mm/秒的提升速度,以及20℃和56%RH)形成在玻璃基底的表面上。 Next, the glass substrate was immersed in the Al2O3 sol solution used in Example 1, followed by coating the surface of the film formed on the glass substrate by the dipping method (lifting speed at 2mm / sec, and 20 ℃ and 56% RH) . 使玻璃基片干燥,并且接着通过400℃的烘烤热处理一小时,并且透明无定形Al2O3膜涂覆于其上。 The glass substrate was dried, and then thermally treated by baking 400 ℃ one hour, and a transparent amorphous Al2O3 film without a coating thereon. 接着,玻璃基底在100℃的热水中浸泡30分钟,接着在100℃下干燥10分钟。 Next, the glass substrate soak for 30 minutes in hot water of 100 deg.] C, followed by drying at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=28nm,并且表面积比Sr是Sr=1.9。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 28nm, and the surface area ratio Sr was Sr = 1.9.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

比较例4在例1中使用的浮法玻璃基片上,通过磁控溅射涂覆厚度为25nm的Al金属膜。 The float glass substrate in Comparative Example 4 used in Example 1, by magnetron sputter coating thickness of the Al metal film is 25nm. 接着,玻璃基片在100℃的热水中浸泡30分钟。 Next, the glass substrate was immersed in hot water of 100 deg.] C for 30 minutes. 在浸泡后的几分钟内,Al的金属光泽消失,并且在提升后,透明膜留在表面层上。 Within a few minutes after soaking, Al metallic luster disappeared, and after lifting, the transparent film remaining on the surface layer. 之后,该玻璃基片在100℃下干燥10分钟。 Thereafter, the glass substrate was dried at 100 ℃ 10 minutes.

通过FE-SEM观察所获得的膜的表面,以找到精细不规则形的结构,其中包含Al2O3作为主要成分的片状晶体随机且复杂地缠结,如同例1。 FE-SEM observation of the surface of the obtained film, to find a fine irregular structure, which contains Al2O3 as a main component and the plate crystal complexly intertwined randomly, as in Example 1. 对于通过FE-SEM对横截面进行的观察,观察到几乎和例1相同的结构。 For FE-SEM observation of cross sections observed almost the same structure as in Example 1. 通过SPM的测量结果示出,平均表面粗糙度Ra′值(nm)是Ra′=32nm,并且表面积比Sr是Sr=2.1。 SPM measurement results are shown, the average surface roughness Ra 'value (nm) was Ra' = 32nm, and the surface area ratio Sr was Sr = 2.1.

接着,对于所获得的膜,使用椭圆测量计测量膜厚度和折射率。 Next, for the obtained film, was measured using ellipsometry and the film thickness of the refractive index. 每个膜的厚度和折射率示于表1。 Thickness and refractive index of each film are shown in Table 1.

对于此基片,进行温度为60℃且湿度为90%的高温度和高湿度测试,并且在开始时刻、250小时之后和500小时之后测量透射率。 For this substrate, a temperature of 60 ℃ and a humidity of 90% high temperature and high humidity test, and the start time, after 250 hours and after 500 hours measured transmittance. 其结果示于表1。 The results are shown in Table 1.

[表1] [Table 1]

(注)片状晶体的晶体层的折射率示出了渐变折射率部分的开始点和结束点的值。 Refractive index (Note) crystal layer plate crystals shows values ​​of the start and end points of the graded-index portion. 例如,例1中的折射率1.42-1.0示出了折射率在230nm的厚度内从1.42到1.0连续降低。 For example, the refractive index 1.42-1.0 in Example 1 shows the refractive index decreases continuously from 1.42 to 1.0 in a thickness of 230nm.

[性能评估]如果比较550nm处所制成的透明部件的透射率,例1、7、和8中的初始性能以及比较例1和4几乎相同,并且示出了高的值。 [Performance evaluation] If the comparison 550nm spaces transmittance of the transparent member made of, 1,7, and initial performance of Example 8 and Comparative Examples 1 and 4 are almost the same, and shows a high value. 然而,对于高温度和高湿度的加速耐久性测试,具有包含SiO2作为主要成分的层的例1、7和8示出了恒定的高值,而在不具有这种层的比较例1和4中,性能随时间流逝而显著地下降。 However, for the accelerated durability test of high temperature and high humidity, with embodiments comprising SiO2 as a main component and Comparative Example 1, 7 8 shows a constant high value, while having no such layers 1 and 4 , the performance decreases significantly over time. 进一步地,对于具有高折射率的基底,例2、3、4、5、6、9和10在初始阶段和加速耐久性测试之后显示出了高的透射率,而在不具有包含SiO2作为主要成分的层的比较例2、以及在较低层中具有包含TiO2作为主要成分的层而不是包含SiO2作为主要成分的层且不满足nb≥ns≥na的关系的比较例3中,透射率从初始阶段就低,且性能随着加速测试的进行而显著地下降。 Further, for a substrate having a high refractive index, Examples 2,3,4,5,6,9 and 10 show the initial stage and after the accelerated durability test a high transmittance, while having no comprising SiO2 as a main Comparative Example 2 component layer, and a relationship between the comparative example comprises TiO2 as a main component and not containing SiO2 as a main component and met nb≥ns≥na 3, the transmittance of the lower layer from the initial stage is low, and the performance will be as the acceleration test significantly reduced.

例11图4是例11的光学部件的前视图。 Example 11 FIG. 4 is a diagram of the optical member 11 is a front view. 在此图中,光学部件1是凹透镜,并且基片2设置有光学透明部件3。 In this figure, the optical member 1 is a concave lens, and the substrate 2 is provided with an optical transparent member 3.

图5示出了例11的光学部件沿图4中的5-5剖面切割的横截面。 FIG. 5 shows a sectional view of cross section 5-5 4 Example 11 cut along an optical member of FIG. 包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了包含Al2O3作为主要成分的片状晶体的层形成在光学面上,并且具有不规则形的形状的光学透明部件3形成在最外表面上,从而降低该光学面上的光的反射。 Containing SiO2 as a main component, containing Al2O3 as a main component, and the layers have been arranged plate crystals containing Al2O3 as a main component is formed on the optical surface having an irregular shape and an optically transparent member 3 is formed the outermost surface, thereby reducing the reflected light of the optical surface.

在此例中,光学部件是凹透镜,但是本发明并不限制于此,且此透镜可以是凸透镜或者是半月形透镜。 In this embodiment, the optical member is a concave lens, but the present invention is not limited thereto, and this may be a convex lens or a meniscus lens.

例12图6是例12的光学部件的前视图。 Example 12 FIG. 6 is a diagram of the optical member 12 is a front view. 在此图中,光学部件1是棱镜,并且基片2设置有光学透明部件3。 In this figure, the optical member 1 is a prism, and the substrate 2 is provided with an optical transparent member 3.

图7示出了例12的光学部件沿图6中的7-7剖面切割的横截面。 FIG. 7 shows a sectional view of cross section 7-7 of the cutter 6 along the optical member 12 of the embodiment of FIG. 包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了包含Al2O3作为主要成分的片状晶体的层形成在光学面上,并且具有不规则形的形状的光学透明部件3形成在最外表面上,从而降低该光学面上的光的反射。 Containing SiO2 as a main component, containing Al2O3 as a main component, and the layers have been arranged plate crystals containing Al2O3 as a main component is formed on the optical surface having an irregular shape and an optically transparent member 3 is formed the outermost surface, thereby reducing the reflected light of the optical surface.

在此例中,棱镜的光学面形成的角度是90°和45°,但是本发明并不限制于此,并且棱镜的光学面可以形成任何角度。 In this embodiment, the angle formed by the optical surface of the prism is 90 ° and 45 °, but the present invention is not limited thereto, and the optical surface of the prism may form any angle.

例13图8是本发明的例13的光学部件的前视图。 Example 13 FIG. 8 is a front view of an optical member 13 of the embodiment of the present invention. 在此图中,光学部件1是蝇眼积分仪,并且基片2设置有光学透明部件3。 In this figure, the optical member 1 is a fly-eye integrator, and the substrate 2 is provided with an optical transparent member 3.

图9示出了例13的光学部件沿图8中的9-9剖面切割的横截面。 Figure 9 shows a cross-section of cross-section 9-9 of Example 8 cut along the optical member 13 of FIG. 包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了包含Al2O3作为主要成分的片状晶体的层形成在光学面上,并且具有不规则形的形状的光学透明部件3形成在最外表面上,从而降低该光学面上的光的反射。 Containing SiO2 as a main component, containing Al2O3 as a main component, and the layers have been arranged plate crystals containing Al2O3 as a main component is formed on the optical surface having an irregular shape and an optically transparent member 3 is formed the outermost surface, thereby reducing the reflected light of the optical surface.

例14图10是本发明的例14的光学部件的前视图。 Example 14 FIG. 10 is a front view of an optical member 14 of the embodiment of the present invention. 在此图中,光学部件1是fθ透镜,并且基片2设置有光学透明部件3。 In this figure, the optical member 1 is a fθ lens, and the substrate 2 is provided with an optical transparent member 3.

图11示出了例14的光学部件沿图10中的11-11剖面切割的横截面。 FIG. 11 shows an optical member of Example 14 cut along the cross-section of cross-section 11-11 in FIG. 10. 包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了Al2O3作为主要成分的片状晶体的层形成在光学面上,并且具有不规则形的形状的光学透明部件3形成在最外表面上,从而降低该光学面上的光的反射。 Containing SiO2 as a main component, containing Al2O3 as a main component, and Al2O3 layers have been arranged as a main component of the plate-like crystals formed in the optical surface having an irregular shape and an optically transparent member 3 is formed the outermost surface, thereby reducing the reflected light of the optical surface.

例15在观测光学系统中使用本发明的光学部件的例子示出为本发明的例15。 Examples of an optical member 15 according to the present invention in the observation optical system 15 embodiment illustrated embodiment of the present invention. 图12示出了双筒望远镜的一对光学系统之一的横截面。 FIG 12 shows a cross-section of one of the binocular optical system for each other.

在此图中,参考标号4表示物镜,参考标号5表示用于翻转图像的棱镜(以未折叠形式示出),参考标号7表示图像形成表面,且参考标号8表示光瞳面(评估面)。 In this figure, reference numeral 4 denotes an objective lens, reference numeral 5 denotes a prism (shown in an unfolded form) to flip the image, reference numeral 7 denotes an image formation surface, and reference numeral 8 denotes a pupil surface (evaluation surface) . 在此图中,参考标号3(以图标示出)表示关于本发明的光学透明部件,其中形成包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了包含Al2O3作为主要成分的片状晶体的层,并且最外表面具有不规则形的形状,从而降低该光学面上的光的反射。 In this figure, reference numeral 3 (in the drawing designate) denotes an optical transparent member on the present invention, wherein a layer containing SiO2 as a main component, containing Al2O3 as a main component, and have been arranged comprising Al2O3 as a main component the plate-like crystals of the layer, and the outermost surface has an irregular shape, thereby reducing the reflected light of the optical surface. 在此例中,由精细不规则形结构组成的光学透明部件3既不设置在距对象最近的物镜的光学面9上,也不设置在距评估面最近的目镜的光学面10上。 In this embodiment, the optically transparent member of a fine irregular structure 3 composed of either provided on the optical surface nearest the object from the objective lens 9, is not disposed on the optical surface closest to the surface of the eyepiece 10 assessment. 光学透明部件3不设置在这些表面上的原因是其性能将由于在使用时接触而降低,但是本发明不被限制于此,光学透明部件3可以被设置在光学面9和10上。 Cause optically transparent member 3 is not provided on these surfaces is that its performance will be due to the contact during use is reduced, but the present invention is not limited thereto, the optical transparent member 3 may be provided on the optical surfaces 9 and 10.

例16本发明的光学部件用于成像光学系统的例子示出作为本发明的例16。 Examples of the optical member 16 according to the present embodiment of the invention for the imaging optical system is shown as Example 16 of the present invention. 图13示出了照相机等的拍摄透镜(在此图中示出为摄远透镜)的横截面。 FIG 13 shows a photographing lens camera or the like (here shown as FIG telephoto lens) cross-section.

在此图中,参考标号7表示作为图像形成表面的膜,或者诸如CCD或CMOS的固态成像装置(光电转换元件),并且参考标号11表示光阑。 In this figure, reference numeral 7 denotes a film as an image forming surface, such as a CCD or a CMOS or a solid-state imaging device (photoelectric conversion element), and reference numeral 11 denotes a diaphragm. 在此图中,参考标号3(以图标示出)表示关于本发明的光学透明部件,其中形成包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了包含Al2O3作为主要成分的片状晶体的层,并且最外表面具有不规则形的形状,从而降低每个光学面上的光的反射。 In this figure, reference numeral 3 (in the drawing designate) denotes an optical transparent member on the present invention, wherein a layer containing SiO2 as a main component, containing Al2O3 as a main component, and have been arranged comprising Al2O3 as a main component the plate-like crystals of the layer, and the outermost surface has an irregular shape, thus reducing the reflected light in each optical surface. 在此例中,由精细不规则形结构组成的光学透明部件3不设置在距对象最近的物镜的光学面9上。 In this embodiment, the optically transparent member consisting of a fine irregular structure 3 is not provided on the optical surface nearest the object from the objective lens 9. 光学透明部件3不设置在该表面上的原因是其性能将由于在使用时接触而降低,但是本发明不被限制于此,光学透明部件3可以被设置在光学面9上。 Cause optically transparent member 3 is not provided on the surface due to the contact of its performance will be reduced during use, but the present invention is not limited thereto, the optical transparent member 3 may be provided on the optical surface 9.

例17本发明的光学部件用于投影光学系统(投影机)的例子示出作为本发明的例17。 Examples of the optical member of Example 17 of the present invention is used in a projection optical system (projector) is shown as Example 17 of the present invention. 图14示出了投影机光学系统的横截面。 FIG 14 shows a cross-section of a projector optical system.

在此图中,参考标号12表示光源,参考标号13a和13b表示蝇眼积分仪,参考标号14表示偏振转换元件,参考标号15表示会聚透镜,参考标号16表示反射镜,参考标号17表示场镜,参考标号18a、18b、18c和18d表示棱镜,参考标号19a、19b和19c表示光调制元件,并且参考标号20表示投影透镜。 In this figure, reference numeral 12 denotes a light source, reference numerals 13a and 13b represent the fly-eye integrator, reference numeral 14 denotes a polarizing conversion element, reference numeral 15 denotes a condenser lens, reference numeral 16 denotes a mirror, reference numeral 17 denotes a field lens , the reference numerals 18a, 18b, 18c, and 18d denotes a prism, reference numerals 19a, 19b and 19c denotes a light modulation element, and reference numeral 20 denotes a projection lens. 在该图中,参考标号3(以图标示出)表示与本发明有关的光学透明部件,其中形成包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了包含Al2O3作为主要成分的片状晶体的层,并且最外表面具有不规则形的形状的表面,从而降低每个光学面上的光的反射。 In the figure, reference numeral 3 (in the drawing designate) is related to the present invention, an optically transparent member, wherein a layer containing SiO2 as a main component, containing Al2O3 as a main component, and have been arranged comprising Al2O3 as a main plate-like crystals of component layers, and the outermost surface has an irregular surface shape, thereby reducing the reflected light in each optical surface.

由于此例的光学透明部件3配置成包含诸如二氧化硅或氧化铝的无机成分作为主要成分,它具有高的抗热性,并且即使放置在如此靠近光源12而使得光学透明部件3暴露在高热中的位置13a,也不会遭受性能下降。 Since the optical transparent member 3 of this embodiment is configured to contain an inorganic component such as silica or alumina as a main component, it has high heat resistance, and even in such a place near the light source 12 so that the optical transparent member 3 is exposed to heat the position 13a, and will not suffer performance degradation.

例18本发明的光学部件用于扫描光学系统(激光束打印机)的例子示出作为本发明的例18。 Examples of the optical member of Example 18 of the present invention is used in a scanning optical system (laser beam printer) is shown as Example 18 of the present invention. 图15示出扫描光学系统的横截面。 Figure 15 shows a cross-section of the scanning optical system.

在此图中,参考标号12表示光源,参考标号21表示准直器透镜,参考标号11表示光阑,参考标号22表示柱面透镜,参考标号23表示光偏转器,参考标号24a和24b表示fθ透镜,并且参考标号7表示反射镜表面。 In this figure, reference numeral 12 denotes a light source, reference numeral 21 denotes a collimator lens, reference numeral 11 denotes a diaphragm, reference numeral 22 denotes a cylindrical lens, reference numeral 23 denotes a light deflector, reference numerals 24a and 24b represent fθ lens, and reference numeral 7 denotes a mirror surface. 在图中,参考标号3(以图标示出)表示与本发明有关的光学透明部件,其中形成包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及已经布置了包含Al2O3作为主要成分的片状晶体的层,并且最外表面具有不规则形的形状的表面,从而降低每个光学面上的光的反射,以实现高质量图像的形成。 In the drawings, reference numeral 3 (in the drawing designate) denotes an optical transparent member of the present invention pertains, wherein a layer containing SiO2 as a main component, containing Al2O3 as a main component, and have been arranged comprising Al2O3 as a main component the plate-like crystals of the layer, and the outermost surface of the surface having an irregular shape, thereby reducing the reflected light in each optical surface to achieve a high quality image.

Claims (11)

  1. 1.一种光学透明部件,其在基底上包括有包含SiO2作为主要成分的层、包含Al2O3作为主要成分的层、以及由包含Al2O3作为主要成分的片状晶体形成的片状晶体层,这些层以上述次序堆叠,其中片状晶体层的表面包括不规则形的形状。 An optical transparent member, which comprises a layer containing SiO2 as a main component, the layer containing Al2O3 as a main component, and a plate crystal layer containing Al2O3 as a main component of the plate-like crystals formed on the substrate, the layers in the above-described stacking order, wherein the surface layer comprises a plate-like crystals of irregular shape.
  2. 2.根据权利要求1所述的光学透明部件,其中包含Al2O3作为主要成分的片状晶体层的片状晶体按相对于包含Al2O3作为主要成分的层等于或大于45°且等于或小于90°的方向布置。 The optical transparent member according to claim 1, wherein Al2O3 as a main component comprising a sheet-like flaky crystals with respect to the crystal layer by layer containing Al2O3 as a main component is equal to or greater than 45 ° and equal to or less than 90 ° arrangement direction.
  3. 3.根据权利要求2所述的光学透明部件,其中片状晶体层的厚度等于或大于20nm且等于或小于1000nm。 The optical transparent member according to claim 2, wherein a thickness of greater than or equal to 20nm and the sheet-like crystal layer is equal to or less than 1000nm.
  4. 4.根据权利要求1所述的光学透明部件,其中对于片状晶体层的表面的不规则形的形状,通过具有不规则形的表面的中心线上的平均粗糙度的二维延伸而获得的平均表面粗糙度Ra′为等于或大于5nm且等于或小于100nm,并且表面积比Sr=S/S0为等于或大于1.1且等于或小于3.5,其中S0表示测量表面理想地为平坦时的面积,且S表示实际测量表面的表面积。 The optical transparent member according to claim 1, wherein for the irregular shape of the surface of the sheet-shaped crystal layer, two-dimensional extension of the center line average roughness of the surface has an irregular shape obtained the average surface roughness Ra 'is equal to or greater than 100 nm or less than or equal to 5nm and, and the surface area ratio Sr = S / S0 is greater than or equal to 1.1 and less than or equal to 3.5, where S0 represents the measurement surface is ideally flat area, and S represents the surface area of ​​an actual measurement surface.
  5. 5.根据权利要求1所述的光学透明部件,其中基底的折射率nb、包含SiO2作为主要成分的层的折射率ns、以及包含Al2O3作为主要成分的层的折射率na满足如下关系:nb≥ns≥na。 The optical transparent member according to claim 1, wherein a refractive index nb of the substrate, the refractive index ns layer containing SiO2 as a main component, and a layer containing Al2O3 as a main component of the refractive index na satisfy the following relationship: nb≥ ns≥na.
  6. 6.根据权利要求1所述的光学透明部件,其中包含SiO2作为主要成分的层的厚度为等于或大于5nm且等于或小于100nm,并且包含Al2O3作为主要成分的层的厚度为等于或大于10nm且等于或小于120nm。 The optical transparent member according to claim 1, comprising SiO2 as a main component wherein the thickness of the layer is equal to or greater than 100 nm or less than or equal to 5nm and, and the thickness of the layer containing Al2O3 as a main component is greater than or equal to 10nm and It is equal to or less than 120nm.
  7. 7.包含根据权利要求1所述的光学透明部件的光学系统。 7. An optical system comprising an optical transparent member according to claim 1.
  8. 8.根据权利要求7所述的光学系统,其中该光学系统是图像拾取光学系统。 8. The optical system of claim 7, wherein the optical system is an image pickup optical system.
  9. 9.根据权利要求7所述的光学系统,其中该光学系统是观测光学系统。 9. The optical system of claim 7, wherein the optical system is an observation optical system.
  10. 10.根据权利要求7所述的光学系统,其中该光学系统是投影光学系统。 10. The optical system according to claim 7, wherein the optical system is a projection optical system.
  11. 11.根据权利要求7所述的光学系统,其中该光学系统是扫描光学系统。 11. The optical system of claim 7, wherein the optical system is a scanning optical system.
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