201109451 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種爲形成具有光學薄 膜時的薄膜形成用組成物、及使用該薄膜 形成的光學薄膜。 【先前技術】 以往，於很多的產業中，廣泛利用由 保護層等之氧化物所形成的薄膜。例如， 或照相機透鏡、望眼鏡透鏡、顯示裝置等 光碟裝置之透鏡或拾取器透鏡及二向色稜 之過濾器或鏡子等很多的技術領域中，利 成的薄膜。 一般而言，此等氧化物之薄膜係藉由 射法等成膜、製得，惟就成膜速度或成本 真空蒸鍍法。真空蒸鍍法係在約1〇_4〜1< 使蒸鍍材料加熱且蒸發•昇華，在基板表 ，形成薄膜的方法。提案有各種可藉由選 得高折射率至低折射率之薄膜，在基板上 用組成物。 —般而言，利用二氧化砂或二氧化石夕 物作爲低折射率氧化物，利用氧化鋁、氧 化合物、氧化鋁與氧化鑭之化合物等作爲 射率的氧化物。另外，利用氧化鈦、氧化 膜等之功能性薄 形成用組成物所 作爲光學功能或 在製造眼鏡鏡片 之防止反射膜、 鏡、彩色影印機 用由氧化物所形 真空蒸鍍法或濺 而言大多數選擇 「2Pa之真空中， 面上衝突•堆積 擇蒸鍍材料，製 蒸鍍的真空蒸鍍 與氧化鋁之化合 化鋁與氧化锆之 具有中程度之折 銀、氧化鉬、氧 201109451 化锆、氧化鈦與氧化鉻之化合物、氧化鈦與氧化鑭之化合 物等作爲具有高折射率之氧化物。 其中，於具有高折射率之氧化物薄膜中，就機械強度 較高、資源豐富之成本而言，廣泛利用以有利的氧化鈦、 且具有高透明性與附著性之氧化鑭等兩種爲主成分之蒸鍍 材料。而且，於具有中程度之折射率的氧化物薄膜中，廣 泛利用可製得在含有近紫外線範圍之較廣波長範圍內幾乎 沒有吸收、折射率約爲1 . 6〜1.9之薄膜的氧化鑭與氧化鋁 之化合物。有關該含有氧化鑭之蒸鍍材料的技術，已知有 下述之技術。 例如，於專利文獻1中，爲製得具有高折射率之光學 薄膜時，揭示 La2Ti2〇7-y(y=〇.3 〜0.7)。 而且，於專利文獻2中揭示，LaTi(l+Y)0(3.z) ( 〇<y$〇.2 ' 0.3^2^0.7 )，於專利文獻 3 中揭示，TiOx+ ZLa203 ( x =1.5〜1.8、z以混合物之合計重量爲基準時爲1〇〜65% ) 〇 另外’爲製得具有中程度之折射率的光學薄膜時之蒸 鍍材料，有專利文獻4之Lai.xAli+xO3(x=0〜0.84)或專 利文獻 5 之 La203 + Si02 ( La203:Si02 = 70:30〜5:95)。 〔習知技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本專利第27209 59號公報 〔專利文獻2〕日本特開平n_264〇68號公報 〔專利文獻3〕日本特開2002-226967號公報 201109451 〔專利文獻4〕日本專利第3 723 5 80號公報 〔專利文獻5〕日本專利第3 723 62〇號公報 【發明內容】 一般而言，如專利文獻5中揭示的含有2種以上氧化物 之蒸鍍材料，蒸氣壓高的氧化物優先蒸發，蒸氣壓低的氧 化物大多數殘留於蒸鍍源中。因此，在真空蒸鍍後之蒸鍍 材料殘渣中補足未使用的蒸鍍材料使用時，會有所形成的 薄膜及蒸鍍源之元素組成產生變化的問題。所以’無法在 使用後之蒸鍍殘渣中補足新的蒸鍍材料使用，就成本或資 源保護而言不利。 另外，如專利文獻1〜4中揭示的由氧化鑭與氧化鈦或 氧化鑭與氧化鋁所形成的蒸鍍材料’與由2種氧化物所形 成的複合組成物無關，可在蒸鑛後之蒸鍍材料殘渣中補足 新的蒸鍍材料使用。無論如何’氧化鑭及氧化欽、氧化鋁 之蒸發特性較爲接近，故不會因進行調和、蒸發而導致蒸 鍍薄膜或蒸鍍殘渣之組成改變。 此處，由於如眼鏡鏡片之防止反射膜’在藉由擦拭污 垢等之摩擦、或藉由超音波洗淨 '酸性洗劑或鹼性洗淨之 洗淨、長時間利用等、在嚴苛的環境下使用時’不僅企求 光學薄膜具有光學功能且企求具有更高的耐久性。 專利文獻1〜專利文獻5中具有鑭之氧化物薄膜及蒸鍍 材料，會有在大氣中安定性的問題。藉由本發明人等之見 解，使成膜的薄膜在大氣中放置特定時間後’不僅膜特性 201109451 會有變化且會產生白濁、裂紋、膜剝離等情形，就安定性 而言會形成大問題。而且，使蒸鍍材料在大氣中放置特定 時間後，會有膨脹且崩壞成粉末狀的問題，不僅有濺射情 形增加、且不可能使用於真空蒸鍍。此等係因於光學薄膜 中或蒸鍍材料中存在有經游離的氧化鑭時，使氧化鑭與空 氣中之水分或二氧化碳進行反應，自氧化物變化成氫氧化 物等之故。而且，藉由使前述含有氧化鑭之薄膜在浴室或 雨天時等濕度高的環境中使用，或在含有洗淨洗淨或超音 波洗淨等含水之液體中進行洗淨時，基於與上述相同的理 由，會有產生薄膜之白濁或裂紋、膜剝離等情形。 專利文獻2及專利文獻3中由氧化鑭與氧化鈦所形成的 薄膜，與專利文獻1之薄膜相比時，鈦的組成比例多。因 此，不能說不易產生經游離的氧化鑭，大氣中之安定性經 充分改善，與專利文獻1之薄膜相同地，會有膜之特性產 生變化或膜剝離、白濁的情形。而且，由於氧化鈦之含率 高，故於真空蒸鍍時很少會有濺射情形產生。 因此，本發明之目的係提供一種高耐濕性、低濺射性 且可補足並利用的光學薄膜形成用組成物，此外，提供一 種兼具高的耐濕性、附著性、耐酸性、耐鹼性之光學薄膜 〇 本發明之薄膜形成用組成物，其特徵爲組成式 LawTixAlyOz(w + x + y=l〇〇 時，w=19 〜54、x + y=81 〜46 (x:y=l :99 〜99: 1 ) 、1.5w+1.5x+1.5y^z^l.5w + 2x + 1.5y )所表示。 -8 - 201109451 另外，本發明之光學薄膜，其特徵爲使上述本發明之 薄膜形成用組成物進行真空蒸鍍所形成。 〔發明效果〕 本發明之薄膜形成用組成物，對大氣中之水分而言的 安定性高，於真空蒸鍍時很少會產生濺射情形，可再補足 利用。 此外，本發明之光學薄膜，可同時滿足高的耐濕性、 附著性、透明性、耐酸性、耐鹼性。因此，藉由使用該光 學薄膜，可提高光學零件等之薄膜在大氣中的安定性，且 可減低白濁或膜剝離等之不良情形。而且，亦可提高兼具 高的耐濕性、耐酸性、耐鹼性、透明性之光學零件。 〔爲實施發明之形態〕 於下述中，詳細說明本發明。 本發明之薄膜形成用組成物，係以組成式LawTixAlyOz (w+x+y=l〇〇時，w=19〜54、 x+y=81~ 46 (x:y=l:99 〜99:1 ) 、1.5w+1.5x + 1.5y^z^ 1.5w + 2x + 1.5y )所表示。[Technical Field] The present invention relates to a film forming composition for forming an optical film and an optical film formed using the film. [Prior Art] Conventionally, a film formed of an oxide such as a protective layer has been widely used in many industries. For example, a lens formed by a lens or a pickup lens of a disc device such as a camera lens, a spectacle lens, a display device, or the like, and a filter or mirror of a dichroic prism. In general, films of such oxides are formed by film formation or the like, but at a film formation rate or a cost vacuum deposition method. The vacuum evaporation method is a method in which a vapor deposition material is heated and evaporated and sublimated to form a thin film on a substrate surface. There are various proposals for selecting a film having a high refractive index to a low refractive index and using a composition on a substrate. Generally, silica sand dioxide or a dioxide dioxide is used as a low-refractive-index oxide, and an oxide of alumina, an oxygen compound, a compound of alumina and cerium oxide, or the like is used. Further, the functional thin-forming composition such as titanium oxide or an oxide film is used as an optical function, or an anti-reflection film for producing an eyeglass lens, a vacuum vapor deposition method for a mirror or a color photocopier, or a splash. Most of the choices are "2Pa vacuum, surface conflicts, stacking of vapor deposition materials, vacuum evaporation of vapor deposition and aluminum oxide and aluminum oxide with a moderate degree of silver, molybdenum oxide, oxygen 201109451 A compound having a high refractive index, such as a compound of zirconium, titanium oxide and chromium oxide, a compound of titanium oxide and cerium oxide, etc., wherein the oxide film having a high refractive index has a high mechanical strength and a resource-rich cost. In addition, a vapor deposition material containing two types of titanium oxide and cerium oxide having high transparency and adhesion as a main component is widely used, and an oxide film having a moderate refractive index is widely used. It is possible to obtain a combination of cerium oxide and aluminum oxide in a film having a refractive index of about 1.6 to 1.9 in a wide wavelength range containing a near ultraviolet range. Regarding the technique of the vapor-deposited material containing cerium oxide, the following technique is known. For example, in Patent Document 1, when an optical film having a high refractive index is obtained, La2Ti2〇7-y (y= 〇.3 to 0.7). Further, as disclosed in Patent Document 2, LaTi(l+Y)0(3.z) (〇<y$〇.2 '0.3^2^0.7) is disclosed in Patent Document 3 It is disclosed that TiOx+ZLa203 (x=1.5~1.8, z is 1〇~65% based on the total weight of the mixture) 〇In addition, the vapor deposition material is a patent for producing an optical film having a medium refractive index. Lai.xAli+xO3 (x=0 to 0.84) of Document 4 or La203 + Si02 (La203:SiO2 = 70:30 to 5:95) of Patent Document 5. [Practical Technical Literature] [Patent Literature] [Patent Literature Japanese Patent Publication No. 2720959 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei. No. 2002-226967 (Patent Document 3) Japanese Patent Publication No. Hei. [Patent Document 5] Japanese Patent No. 3 723 62 【 SUMMARY OF THE INVENTION Generally, as disclosed in Patent Document 5, two types are included. In the vapor deposition material of oxide, the oxide having a high vapor pressure is preferentially evaporated, and most of the oxide having a low vapor pressure remains in the vapor deposition source. Therefore, the vapor deposition material residue after vacuum vapor deposition is used to make up the unused vapor deposition material. When it is used, there is a problem that the elemental composition of the formed film and the vapor deposition source changes. Therefore, it is not advantageous in terms of cost or resource protection to make it impossible to use a new vapor deposition material in the vapor deposition residue after use. The vapor deposition material formed by cerium oxide and titanium oxide or cerium oxide and aluminum oxide as disclosed in Patent Documents 1 to 4 can be steamed after steaming regardless of the composite composition composed of two kinds of oxides. The plating material residue is used to make up the new vapor deposition material. In any case, the evaporation characteristics of yttrium oxide, oxidized osmium and alumina are relatively close, so that the composition of the vapor deposition film or the vapor deposition residue is not changed by the adjustment and evaporation. Here, since the antireflection film of the spectacle lens is rubbed by wiping off dirt or the like, or washed by ultrasonic cleaning, cleaning with an acidic lotion or alkaline washing, long-term use, etc., is severe. When used in an environment, it is not only required to have an optical function of an optical film but also to have higher durability. In Patent Document 1 to Patent Document 5, there is a problem that the oxide film of tantalum and the vapor deposition material have stability in the atmosphere. According to the findings of the inventors of the present invention, after the film formed film is left in the air for a certain period of time, not only the film property 201109451 changes, but also white turbidity, cracks, film peeling, and the like occur, and a large problem is formed in terms of stability. Further, after the vapor deposition material is left in the atmosphere for a certain period of time, there is a problem that it expands and collapses into a powder form, and not only the sputtering condition is increased, but also it is impossible to use it for vacuum vapor deposition. These are caused by the reaction of cerium oxide with water or carbon dioxide in the air, and the conversion of oxides into hydroxides or the like due to the presence of free cerium oxide in the optical film or in the vapor deposition material. Further, when the cerium oxide-containing film is used in an environment having a high humidity such as a bathroom or a rainy day, or when it is washed in a liquid containing water such as washing or ultrasonic cleaning, it is the same as above. For the reason, there may be cases where the film is turbid or cracked, and the film is peeled off. In Patent Document 2 and Patent Document 3, a film formed of cerium oxide and titanium oxide has a larger composition ratio of titanium than the film of Patent Document 1. Therefore, it cannot be said that the free cerium oxide is less likely to be generated, and the stability in the atmosphere is sufficiently improved. Similarly to the film of Patent Document 1, the film characteristics are changed, or the film is peeled off or clouded. Further, since the content of titanium oxide is high, sputtering is rarely generated during vacuum evaporation. Accordingly, an object of the present invention is to provide a composition for forming an optical film which is highly resistant to moisture and has low sputterability and which can be complemented and utilized, and further provides a composition which has high moisture resistance, adhesion, acid resistance and resistance. Basic optical film 〇 The film forming composition of the present invention is characterized by the composition formula LawTixAlyOz (w + x + y = l〇〇, w = 19 ～ 54, x + y = 81 ～ 46 (x: y =l :99 ~99: 1 ) , 1.5w+1.5x+1.5y^z^l.5w + 2x + 1.5y ). -8 - 201109451 Further, the optical film of the present invention is characterized in that the film forming composition of the present invention is subjected to vacuum deposition. [Effect of the Invention] The film-forming composition of the present invention has high stability to moisture in the atmosphere, and is rarely sputtered during vacuum vapor deposition, and can be reused. Further, the optical film of the present invention can simultaneously satisfy high moisture resistance, adhesion, transparency, acid resistance, and alkali resistance. Therefore, by using the optical film, the stability of the film of an optical component or the like in the atmosphere can be improved, and problems such as white turbidity and film peeling can be reduced. Further, it is possible to improve optical parts having high moisture resistance, acid resistance, alkali resistance, and transparency. [Formation for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The composition for forming a film of the present invention is of the composition formula LawTixAlyOz (w+x+y=l〇〇, w=19 to 54, x+y=81 to 46 (x:y=l:99 to 99: 1), 1.5w+1.5x + 1.5y^z^ 1.5w + 2x + 1.5y).
第1圖係表示本發明之薄膜形成用組成物的鑭、鈦及 鋁元素之組成範圍。此處，使用第3圖說明第1圖所示之三 角圖的讀取方法。於第3圖中，粗線係表示Ti與A1 ( X與y )之比例不同，惟L a ( w ) = 6 0 m ο 1 %之組成。粗虛線係表 Tf；La(w)比例不同，惟 Ti:Al(x:y) = 40:60。藉此，點 P 201109451 係表示（w，x，y) = ( 60:16:24)之組成。 如第1圖所示，本發明之薄膜形成用組成物之鑭、飲 及鋁元素的組成，係在使下述A、B、C、D各點（單位爲 m ο 1 % )以在該順序連結的直線所圍成的範圍內及各直線上 〇 A ( w,x,y ) = (19,0.81,80.19) B(w,x,y) = (19, 80.19, 0.81) C ( w,x,y ) = ( 54, 45.54, 0.46) D ( w, x, y ) = ( 54, 0.46, 45.54) w超過54時，就容易變成具有氧化鑭之特性，所得的 薄膜或蒸鍍材料容易與酸、鹼及水分反應而言不爲企求。 另外，w未達1 9時，就容易變得具有氧化鋁或氧化鈦特有 的容易吸收特性且附著性惡化而言不爲企求。 此外，超過x:y = 1:99〜99:1之範圍、任何一方過大時 ，就不易具有藉由鑭、鈦及鋁同時存在的效果，即提高耐 酸性或耐鹼性、耐濕性等之效果而言不爲企求。 而且，z未達K5w+1.5x+1.5y時，由於所得的薄膜容 易形成低級氧化物，就薄膜容易產生吸收情形而言不佳。 本發明之組成物，以使y $ 1 〇，即於第1圖中下述B ’、 B、C、C’之各點（單位爲mol% )以在該順序連結的直線 所圍成的範圍內及各直線上較佳。爲該範圍時，可藉由真 空蒸鍍處理，製得特別是具有高耐擦傷性之高折射率的光 學薄膜。 B，（ w，x，y) = ( 19, 71，10) -10- 201109451 B ( w,x,y ) = (19,80.19,0.81) C ( w,x，y ) = ( 54, 45.54, 0.46 ) C5 ( w,x,y) = ( 54, 36, 10) 本發明之組成物，較僅由鑭與鈦之氧化物所形成的化 合物、或僅由鑭與鋁之氧化物所形成的化合物在大氣中更 具有安定性。理由係藉由氧化鑭及氧化鈦、氧化鋁等3種 物質同時存在，爲於燒成或合成等時促進結晶格子之緩和 作用或擴散時，相鄰的分子變得容易結合，故氧化鑭不易 產生游離或凝聚而存在之故。 本發明之組成物，以使X S 1 〇，即於第1圖中下述A、 A’、D’、D之各點（單位爲m〇l% )以在該順序連結的直線 所圍成的範圍內及各直線上較佳。爲該範圍時，可藉由真 空蒸鍍處理，製得特別是直至近紫外線範圍具有高透明性 之中折射率的光學薄膜。 A ( w，x，y ) = ( 19，0_ 8 1，80.19 ) A’（ w，x，y ) = ( 19, 10, 71 ) D，（ w，x，y ) = ( 54，1 0，36 ) D ( w，x，y ) = ( 54，0.46，45.5 4 ) 本發明之組成物，可爲化合物或混合物中之任一形態 ，惟以化合物之形態較佳。此處’本發明之化合物係指各 元素化學鍵結形成安定的狀態者，混合物係指2種以上元 素或含有該元素之化合物僅單純地混合，沒有化學鍵結的 狀態。 爲化合物時’由於氧化鑭與氧化鈦或氧化鋁形成安定 -11 - 201109451 的化合物，故氧化鑭幾乎完全沒有單獨存在。因此，幾乎 完全沒有水分或二氧化碳之吸收，可抑制成膜時有害氣體 產生，且由於蒸鍍時很少有濺射的情形’故可得安定的薄 膜。另外，爲混合物的形態時，由於氧化鑭會吸收大氣中 之水分或二氧化碳，故會有於真空蒸鍍時產生有害的氣體 或濺射等缺點。 此外，本發明之組成物，以燒結物或熔融物更佳。 燒結壓力·溫度係視元素組成或粉體之比表面積而不 同，於真空中以1350°C以上較佳。在l〇_2Pa以下之真空中 進行燒結或熔融時，可更爲減少蒸鍍時之濺射或氧氣等氣 體產生情形。而且，若未達3 50°C，可能會有燒結反應變 得不充分的情形，亦可能會引起未反應的氧化鑭殘留，或 所得的燒結物變成低強度且低密度等之缺點。燒結時間係 藉由燒結溫度適當選擇，通常爲1小時以上。未達1小時時 ，會有燒結反應變得不充分的情形。 於本發明之組成物進行燒結或熔融時，除使用低級氧 化鈦或金屬鈦、氫化鈦、金屬鋁等外，亦可使用經還原的 低級氧化物之組成物。藉由使用低級氧化物，可於蒸鍍時 減低游離的氧氣產生。 本發明之組成物的形狀，可爲粒料狀、片錠狀、顆粒 狀等任何一種，於蒸鍍前以電子束溶解後使用較佳，此時 ，特別是利用顆粒狀較爲容易。 於本發明之組成物中，在不會影響本發明之範圍內， 亦可含有其他的元素。換言之，於本發明之組成物中不僅 -12- 201109451 有不可避免的雜質元素存在，亦可在不會影響本發明之範 圍內視其所需添加其他元素。 其次，說明有關本發明之光學薄膜。 本發明之光學薄膜，藉由使本發明之組成物進行真空 蒸鍍處理，在玻璃或合成樹脂製等之基板上形成，具有約 1·7〜2.2之折射率。蒸鍍處理可以使用電子束之一般方法 進行。 藉由本發明人等之見解，氧化鋁、氧化鑭及氧化鈦係 作爲光學薄膜充分的透明物質，皆具有相近的蒸發特性。 而且，藉由使鑭、鈦、鋁之氧化物同時存在，於成膜 時引起蒸鍍物質之格子間的緩和作用、或促進基板上之移 動作用，相鄰的分子間變得容易鍵結之故。因此，由於薄 膜中之氧化鑭等在不易游離或凝聚下存在，可提高耐濕性 ’且可提高薄膜之附著性或耐酸性、耐鹼性等之物理、化 學安定性。該效果係在僅由氧化鑭與氧化鋁所形成的薄膜 中沒有發現，且在僅由氧化鑭與氧化鈦所成的薄膜中亦沒 有發現。 本發明之光學薄膜，可使用作爲防止反射膜或光學濾 光片、光學鏡、光學稜鏡等之多層薄膜形成用薄膜。 【實施方式】 於下述中’藉由實施例更詳細地說明本發明，惟本發 明不受此等實施例所限制。 201109451 〔實施例〕 <組成物之製造> 以表1所示之組成式（計算値）、以表1所示之重量比 分取氧化鑭粉末（La203、純度99.99%、平均粒徑2μηι )、 氧化鈦粉末（Ti02、純度99.99%、平均粒徑1 μιη )、金屬 鈦粉末（Ti、純度99%、平均粒徑7μιη )、氧化鋁粉末（ Al2〇3、純度 99.99%、平均粒徑 0·6μιη )。 使分取的各粉末以球磨進行混合48小時後，在混合粉 中加入'分散材料，再以球磨進行混合8小時。使所得的混 合物以98066.5kPa( 1000kg f /cm2)之壓力進行冷間成型且 粉碎，予以顆粒狀化。然後，使用附有脫脂功能之真空加 熱裝置，在1 X 10·2Pa以下之真空中、以表1所示之溫度加熱 24小時，製得顆粒狀燒結物。 -14- 201109451 【表1 組成式(計算値） L&2〇3 wt(« TiOz wt〇i) Ti wt(« A1A wt(X) 真空燒結 溫度CC) 實施例1 乙347.5〜7.^15〇173.75 65.65 32.19 0.00 2.16 1490 實施例2 64.11 31.43 0.00 4.46 1490 實施例3 ^33.33^ ^33.33^1-33.33〇167.67 55.46 27.19 0.00 17.35 1490 實施例4 47.25 23.17 0.00 29.58 1490 實施例5 La3〇Tie〇AIi〇〇i5〇 50.34 37.02 7.40 5.24 1720 實施例6 La4〇Ti]〇Alii〇〇i5〇 66.60 8.12 1.22 26.06 1650 實施例7 La54Tio.4RAl45.wO160 23 78.86 0.33 0.00 20.81 1600 比較例7 LaMAl460lwl 78.95 0.00 0.00 21.05 1600 實施例8 ^a5〇Ti〇.&Al49.5〇150 76.09 0.28 0.06 23.57 1600 比較例8 La^AUnOicin (LaAI0s) 76.16 0.00 0.00 23.84 1600 實施例9 La<〇Ti〇 fiAL59.4〇iB〇.3 67,93 0.50 0.00 31.57 1600 比較例9 La4〇ALen〇i so 68.05 0.00 0.00 31.95 1600 實施例10 La3〇Ti〇7Ale93〇i &〇 57.70 0.49 0.10 41.71 1600 比較例10 La3〇Al7n〇i¥ifl 57.80 0.00 0.00 42.20 1600 實施例11 La^Tio diAleo i9〇iso.4i 42.71 0.89 0.00 56.40 1600 比較例11 42.84 0.00 0.00 57.16 1600 實施例12 LaiflTi；nAlfi〇〇i5〇 40.39 16.41 3.28 39.92 1720 比較例12 Lai8Tl22AlR〇〇i5〇 38.72 17.40 3.48 40.40 1720 實施例13 ^3ΐ9^ΰΐΑΐ40〇170.5 36.81 38.94 0.00 24.25 1490 比較例13 LaigTi42AUo〇i7i 35.22 40.29 0.00 24.49 1490 實施例14 LaigTL6iAl20〇i50 36.42 42.99 8.59 12.00 1720 比較例14 Lai8Ti62Al70〇1F10 34.88 44.17 8.82 12.13 1720 實施例15 LaigTigo 1qA1〇.81〇190.1 32.44 67.13 0.00 0.43 1490 比較例15 LaiaTiR1〇iQn a 32.36 67.64 0.00 0.00 1490 實施例16 La3〇Ti69.3AL〇.7〇l50 49.35 41.92 8.37 0.36 1720 比較例16 La3〇Ti7n〇iii〇 49.28 42.28 8.44 0.00 1720 實施例17 La4〇T“9 aAL〇.B〇179.7 57.71 42.02 0.00 0,27 1490 比較例17 La4〇T ΐβηΟίβο 57.62 42.38 0.00 0.00 1490 實施例18 La50Ti496Al〇.5〇i5〇 69.45 25.28 5.05 0.22 1720 比較例18 La&〇Ti5n〇iw) (LaTi03) 69.39 25.51 5.10 0.00 1720 實施例19 La54X145 wAl〇 4B〇i72.77 70.61 29.20 0.00 0.19 1490 比較例19 LawTi^Om 70.54 29.46 0.00 0.00 1490 實施例20 La^Ti^AlToO^o 73.96 18.13 3.62 4.29 1700 比較例20 La55Ti35All〇〇15〇 74.78 17.49 3.50 4.25 1700 實施例21 73.97 17.46 0.00 8.57 1490 比較例21 La65Ti^Al^〇〇i62.B 74.82 16.67 0.00 8.51 1490 實施例22 La54Ti16Al3〇〇i5〇 76.65 8.35 1.67 13.33 1650 比較例22 ^a55^il5Ala〇〇i5〇 77.46 7.77 1.55 13.22 1650 比較例23 La7〇Tii〇Alj：0〇i55 86.25 6.04 0.00 7.71 1490 比較例24 La7〇Tij>〇ALi〇〇i6〇 84.40 11.82 0.00 3.78 1490 比較例25 La8〇^M〇Ali〇〇i55 90.88 5.57 0.00 3.55 1490 比較例26 Lai〇TiinAlfl〇〇i55 25.04 12.27 0.00 62.69 1490 比較例27 La10Ti^M4s〇m s 21.67 47.81 0.00 30.52 1490 比較例28 Lai〇Ti8nAli〇〇ii)〇 19.10 74.92 0.00 5.98 1490 比較例29 TistlAUo〇,7<;(ALTi03) 0.00 48.70 9.74 41.50 1720 比較例30 Lai〇〇〇i&n (La^Og) 100.00 0.00 0.00 0.00 1500 比較例31 Ali〇〇〇i ^(AL^Os) 0.00 0.00 0.00 100.00 1580 比較例32 Til00〇20D(ri〇2) 0.00 100.00 0.00 0.00 1450 比較例33 ^a33.33^1-33 33AI33 33^133.33 58.65 14.38 8.62 18.35 1720 比較例34 La^TUoM^oO]^ 67.14 4.12 2.47 26.27 1720 比較例35 ^47.5^147 f,Al5〇i2G.25 70.18 17.20 10.31 2.31 1720 -15- 201109451 <蒸鍍薄膜之形成> 將所得的組成物塡充配置於真空蒸鍍裝置（蒸鍍距離 1100mm)之電子束蒸鍍用Hearth Liner中，且使裝置內排 氣至lxl 0_3Pa之壓力。然後，藉由電子束以蒸發組成物， 在裝置內預先設置的清潔玻璃基板（BK7或合成石英）上 ，直至以光學膜厚爲1/4入〜4人（波長人=54〇11111)之範圍內 、直至目的之膜厚爲止，以約5A/秒之蒸鍍速度進行蒸鍍 處理。 <組成物之評估> 使所作成的組成物以下述所示之試驗方法進行評估。 結果如表2所示。 (1 )組成分析 在瑪瑙乳缽中使組成物粉碎成粉末狀，藉由鹼熔融法 予以溶液化後’加入硝酸釔溶液作爲內部標準物質，作成 試料液。然後，使所得的溶液導入ICP發光分光分析裝置 中’藉由內部標準法進行La、Ti及A1元素之定量分析。 JCP發光分光分析裝置，係使用BALIAN公司製 VISTA PRO ΑΧ，藉由觀察軸方向觀測發光強度。 另外’使組成物藉由惰性氣體溶解-紅外線吸收法， 進行氧之定量。裝置係使用堀場製作所製E M G A · 6 5 0，測 定方法係以JIS-Z2613金屬材料之氧定量方法通則之紅外 線吸收法爲基準進行。 -16- 201109451 藉由所得的分析結果，計算組成物之化學組成式。如 表2所示’於全部實施例及比較例中，可確認與表1所示之 計算値幾乎同等的元素組成。 各組成物中之鑭、鈦及鋁元素之組成比例，如第2圖 所示。 (2 )耐濕性 將組成物於溫度35°C、相對濕度95%RH之恆溫恆濕槽 中保'存3 0日，觀察外觀變化，且測定重量變化。重量變化 之測定係使用電子天秤。 所得的結果以下述基準進行評估。 ◎ : 3 0日內外觀沒有變化，因吸濕之重量增加亦未達 + 1 w t % 〇：3 0日內外觀沒有變化，惟因吸濕之重量增加+ 1 w t %以上 △ : 1日以上、3 0日以內有組成物崩壞或膨漲的情形 X :未達1日有組成物崩壞的情形 如表2所示，可確認本發明之組成物皆對大氣中之濕 度具有充分的安定性。 此外，比較例2 3〜比較例2 5及比較例3 0，會有較實施 例及其他比較例之耐濕性更爲不佳的結果。此等係因鑭之 含率過高，吸收大氣中之水分之故。 (3 )補足利用性 -17- 201109451 在玻璃基板（合成石英）上形成蒸鏟薄膜（光學膜厚 1/4λ)後，補足經減少的部分之組成物。重複該操作20次 時觀察蒸鍍薄膜之折射率變化與組成物殘渣之元素組成的 變化。 反射 折射率係以下述式1、藉由薄膜之反射率計算 率之測定係使用PERKINELMER公司製Lambda900。 【數1】 折射率= (基板折射率）x{l+ (反射率)1/2} {1—(反射率）1/2} ， 1/2 組成物之殘渣的元素組成分析，係與前述（1 )組成 分析相同地，使用ICP發光分光分析裝置進行。 使所得的結果以下述基準進行評估。 〔薄膜之折射率變動〕 ◎:第1次成膜與第20次成膜之折射率的差未達0.01 〇：第1次成膜與第20次成膜之折射率的差爲0_01以 上、未達0.02 △:第1次成膜與第20次成膜之折射率的差爲0.02以上 、未達0.05 X:第1次成膜與第20次成膜之折射率的差爲0.05以上 〔組成物殘渣之組成變動〕 ◎:成膜前與第20次成膜後組成物中之La含率的差未 達± 1 % 〇：成膜前與第20次成膜後組成物中之La含率的差爲 -18- 201109451 ±1%以上、未達±2% △:成膜前與第20次成膜後之組成物中之La含率的差 爲±2%以上、未達±3% x :成膜前與第20次成膜後組成物中之La含率的差爲 ±3 %以上 如表2所示，鑭、鈦及鋁之氧化物、不含鋁之氧化物 、不含鈦之氧化物，皆爲元素組成物之變動少的結果。 另外，爲薄膜之折射率幾乎完全沒有變化的結果。而 且，部分比較例中折射率變動的理由，係因薄膜中缺氧， 在薄膜中產生吸收，無法求得正確的折射率。 由此等結果可確認，可補足利用本發明之組成物體。 (4 )濺射情形 於蒸鍍薄膜時，觀察於組成物上照射電子束時產生濺 射的情形，以下述基準進行評估。 ◎:幾乎完全沒有濺射情形 〇：稍微產生濺射情形 △:頻繁地產生濺射情形 X : —直產生濺射情形 如表2所示，於本發明之組成物中，沒有觀察到濺射 情形產生。 另外’部分比較例中產生很多濺射情形。比較例2 3〜 25及比較例3〇，由於鑭之含率高，吸收大氣中之水分，且 變成產生濺射情形的原因。而且，可確認比較例3 2爲濺射 -19- 201109451 情形很多的氧化鈦之特性。 由此等結果可確認，本發明之組成物爲濺射情形少的 組成物。 (5 )微細粒子對基板之附著情形 以光學顯微鏡觀察因濺射情形等附著於藍板玻璃基板 (80φ )上之微細粒子的個數’以下述基準進行評估。 ◎:附著處〇 〇：附著處1〜2 ' △:附著處 3〜4 X :附著處 5以上 如表2所示’爲本發明之組成物時，於基板上沒有觀 察到微細粒子。此外，部分比較例中有觀察到很多微細粒 子。有觀察到微細粒子之比較例’係因容易附著微細粒子 之氧化鈦及氧化鋁的特性。 由此等之結果可確認’本發明之組成物可製得附著很 少微細粒子之薄膜。 -20- 201109451 【表2】 組成分析 耐濕性 補足利用性 濺射 情形 微細粒子 附著於基板 之狀態 薄膜之 折射率變動 組成物殘渣 之組成變動 實施例1 La47.sT“7.5Al5.1〇172 Θ ® Θ 0 © 實施例2 La4sTi^ nAlin ι〇ΐ7ΐ Θ Θ 0 0 © 實施例3 La 33.33*^ i 33 λ AI33.4〇ι 66 @ @ Θ 0 © 實施例4 La^Ti^ 1AI4C1 .qOifii © ® Θ 0 © 實施例5 La3〇Ti6〇 iAl10 !〇u9 0 Θ 0 Θ 實施例6 LawTiioAUnOufi @ © Θ 0 0 實施例7 La54Ti〇 4f}Al4(； ii〇uii 〇 Θ © ® 0 ® 比較例7 La^Al^ Λ ® 〇 0 實施例8 La(i〇Ti〇.5iAl4g.5〇i49 〇 Θ © 0 比較例8 LasoAL^o 2〇uft Θ ® ® 0 實施例9 La^oTio.eAlsfl sOur ® Θ Θ Θ 0 © 比較例9 La^oAleo i〇us Θ ® Θ Θ 0 實施例10 La30Ti。72Α1Μ 3O咖 ® Θ Θ @ 0 ® 比較例10 La3〇Al7〇 2〇im Θ ® ® 0 Θ 實施例11 La1flTin mAIm ：Am © 0 Θ 比較例11 La19Al80 80151 Θ 0 ® 實施例12 LajgTiz! gAleig 8〇!49 ® Θ 0 Θ 比較例12 La18TL22.lAl6〇.]〇u8 Θ @ © 0 ® 實施例13 La19Ti41 ^Al^o 2〇i ® ® ® 0 Θ 比較例13 Lai8Ti42 2AI40 4〇17〇 <s> Θ Θ 1 Ο 實施例14 LaigTig! ^Aljo TOug ® Θ ® 0 ® 比較例14 LaigTi62Al2〇〇u9 Θ @ ® 〇 實施例15 Θ © ® Θ 〇 比較例15 Lai9Ti81 〇0] 89 © 〇 3 Δ 實施例16 La3〇Tie9.3Al〇.72〇i5〇 Θ Θ 1 〇 比較例16 La30ri7〇 办以 © 〇 〇 3 Δ 實施例17 La4〇Ti5g 4AL0 Ri〇t7fi ® ® 〇 比較例17 LaioTisg fi〇i7ft ® ® Θ Ο 1 〇 實施例18 La5〇Ti49.4Al〇.52〇149 Θ @ Θ Θ 0 比較例18 La&〇Ti5〇.3〇u8 〇 0 @ ® 0 ® 實施例19 La54Ti45.7Aln 49O170 ® @ Θ 0 比較例19 La54^i-46.0〇171 〇 © 0 Θ 0 ® 實施例20 iAl10jOim Θ Θ Θ ® 0 @ 比較例20 Lac^Ti^e； iAlon n〇us 〇 @ 〇 0 Θ 實施例21 Las4Ti26 ?Μί!Π 0〇1fil Θ ® 0 ® 比較例21 La5sTi25 3AI20 2〇im 〇 0 實施例22 La64Til6.lAL30.2〇]48 Θ Θ 0 比較例22 La&sTiu.gAUo.iOuf} 〇 ® 0 ® 比較例23 La7〇Tii〇.2Al7〇 2〇1&4 X ® Θ . Δ Ο 比較例24 La7〇Ti2〇 X Θ © Δ 〇 比較例25 La8〇Tii〇.iAlin X Θ Δ Ο 比較例26 La]〇Tii〇.2Al8〇.3〇i 54 Θ ® © ® 3 Δ 比較例27 Lai〇Ti^ ιΑΙ^ς i〇i7〇 ® © Θ Θ 3 Δ 比較例28 Lai〇Ti8〇.2Ali〇.2〇l 89 Θ 〇 0 Δ 4 Δ 比較例29 ΤΪ50Α149.7Ο174 ® Θ — Ο 3 Δ 比較例30 Lai〇〇〇is〇 (La2〇3) X © △ 4 Δ 比較例31 All00〇lS0 (Al?,〇3) ® 〇 - 3 Δ 比較例32 Ti】00〇19S - - Δ 6 X 比較例33 ^333.3^^33 aAl33 3〇1；i3 〇 〇 2 〇 比較例34 La‘f)Tii〇Al&〇〇us ® Θ ® 〇 2 〇 比較例35 La47 sTi47 sAI&0咖 Θ Ο Θ 〇 2 〇 -21 - 201109451 <蒸鍍薄膜之評估> 藉由下述所示之試驗方法評估所形成的薄膜。結果如 表3所示。 (6 )耐濕性 使薄膜（玻璃基板：BK7、光學膜厚：4λ )於溫度35°C 、相對濕度 95%RH之恆溫恆濕槽中保存30日，觀察薄膜 外觀之變化，且測定折射率之變動。折射率係與前述（3 )補足利用性相同地求得。 所得的結果以下述基準進行評估。 ◎:外觀沒有變化，折射率之變動値未達〇.〇3 〇：外觀沒有變化，惟折射率變化0.03以上 △:外觀產生白濁情形 X :外觀產生膜剝離或裂紋情形 如表3所示，可確認於本發明之組成物中皆具有對大 氣中之水分而言高的安定性。 此外，鑭之含率多的比較例2 0〜2 5、或不含鋁之比較 例1 5〜1 9、不含鑭之比較例7〜1 1，與實施例相比時，可 確認耐濕性不佳。 (7)吸收率（可見光範圍） 薄膜（玻璃基板：合成石英、光學膜厚：3/4λ)之分光 透過率及藉由分光反射率之可見光範圍的吸收率，以「吸 收率=1〇〇 %—透過率—反射率」求取。透過率及反射率之 -22- 201109451 測定，係使用PERKINELMER公司製Lambda900。 使所求得的吸收率’以下述基準進行評估。 ◎:吸收率 未達0.5% 〇：吸收率 0 · 5 %〜0.7 % △: 吸收率 0.7 %〜1 . 5 % X :吸收率 1 · 5 %以上 如表3所示，於本發明之組成物中會有薄膜之吸收少 的結果。 另外’於部分比較例中會有薄膜之吸收多的結果。比 較例3 3〜3 5 ’由於組成物之氧含量少，所得的薄膜爲低級 氧化物，產生吸收之故。有關其他吸收較多的比較例，係 因容易產生薄膜吸收的氧化鈦與氧化鋁之特性。 由該結果可確認，本發明之組成物可製得透明性高的 薄膜。 (8 )折射率 與前述（3 )補足利用性相同地，求取薄膜（玻璃基 板：合成石英、光學膜厚：3/4λ )之折射率。 如表3所示可確認，本發明之組成物可形成折射率約 〜2.2之寬度廣的薄膜 (9)近紫外線範圍之透明性（紫外線側之吸收端） 藉由薄膜（玻璃基板：合成石英、光學膜厚：3/4λ)在 近肩外線範圍（ 3 00〜400nm)之分光透過率及分光反射率 -23- 201109451 ，以「吸收率=1〇〇%-透過率—反射率」求取吸收率。在 近紫外線範圍之透過率及反射率的測定，係使用 卩£111^1犯1^£11公司製之1^1^£1&900。 此處，以所求得的吸收率爲3 %以上之波長作爲紫外線 側之吸收端，且以下述基準進行評估。 ◎:吸收端 未達3 3 0nm 〇：吸收端 3 3 0nm以上 如表3所示，Ti之含率低的實施例6〜1 1及比較例7〜 1 1等，於近紫外線範圍內具有特別優異的透明性。 (10)耐酸性（JIS-K5400 8.22) 使薄膜（玻璃基板：BK7、光學膜厚：4λ )於5w/v%之 稀硫酸（液溫3 5 °C )中浸漬1 6 8小時，每經過24小時後觀 察薄膜之變化，以下述基準進行評估。 ◎:沒有變化 〇：直至24小時以內沒有變化，惟繼後會產生白濁等 之除膜剝離以外之變化 △:於24小時以內會產生除白濁、裂紋等之膜剝離以 外的變化 X :於24小時以內會產生膜剝離的情形 如表3所示，可確認本發明之組成物對酸而言皆安定 〇 另外，鑭之含率多的比較例2 0〜2 5，與本發明之組成 物相比時’可確認耐酸性不佳。係耐酸性或耐水性低的氧 -24- 201109451 化鑭之特性。而且，本發明之組成物與不含鋁之比較例1 5 〜1 9 '不含鈦之比較例7〜Π相比時，可確認耐酸性不佳 (11)耐鹼性（JIS-K5400 8.21) 使薄膜（玻璃基板：BK7、光學膜厚：4λ )於5w/v%之 碳酸鈉水溶液（液溫35°C )中浸漬168小時，每經過24小 時後觀察薄膜之變化，以下述基準進行評估。 ◎:沒有變化 〇：直至24小時以內沒有變化，惟繼後會產生白濁等 除膜剝離以外之變化 △:於2 4小時以內會產生除白濁、裂紋等除膜剝離以 外的變化 X :於24小時以內會產生膜剝離的情形 如表3所示，可確認本發明之組成物對鹼而言皆安定 〇 另外，鑭之含率多的比較例2 0〜2 5，與本發明之組成 物相比時，可確認耐驗性不佳。係耐鹼性或耐水性低的氧 化鑭之特性。 (12 )附著性（JIS-R3 25 5 ) 對薄膜（玻璃基板：合成石英、光學膜犀：4λ)而言， 以微擦傷試驗進行評估附著性。試驗機係使用RHESC Α公 司製CSR-02F。而且，測定條件係鑽石壓子之半徑5μιη、 -25- 201109451 段速度ΙΟμιη/s、段角度3DEG、增量爲1 000、激振級數 9 0 μηι 0 藉由微擦傷試驗所得的臨界荷重感應器出力之値’以 下述基準進行評估。Fig. 1 is a view showing a composition range of bismuth, titanium and aluminum elements of the film-forming composition of the present invention. Here, the reading method of the triangular diagram shown in Fig. 1 will be described using Fig. 3 . In Fig. 3, the thick line indicates the ratio of Ti to A1 (X and y), but the composition of L a ( w ) = 6 0 m ο 1 %. The thick dashed line is Tf; the ratio of La(w) is different, but Ti:Al(x:y) = 40:60. Thus, point P 201109451 represents the composition of (w, x, y) = (60:16:24). As shown in Fig. 1, the composition of the enamel, the drink, and the aluminum element of the film-forming composition of the present invention is such that each of the following points A, B, C, and D (unit: m ο 1 %)范围A ( w,x,y ) = (19,0.81,80.19) B(w,x,y) = (19, 80.19, 0.81) C ( w ) in the range enclosed by the straight lines connected to the sequence , x, y ) = ( 54, 45.54, 0.46) D ( w, x, y ) = ( 54, 0.46, 45.54) When w exceeds 54, it is easy to become a characteristic of cerium oxide, and the obtained film or vapor-deposited material It is not easy to react with acid, alkali and water. Further, when w is less than 19, it is easy to have an easy absorption property characteristic of alumina or titanium oxide, and the adhesion is not deteriorated. In addition, when the range of x:y = 1:99 to 99:1 is exceeded, when either one is too large, it is difficult to have the effect of simultaneously coexisting with yttrium, titanium, and aluminum, that is, improving acid resistance, alkali resistance, moisture resistance, and the like. The effect is not in demand. Further, when z is less than K5w + 1.5x + 1.5y, since the obtained film is liable to form a lower oxide, the film is less likely to be absorbed. The composition of the present invention is such that y $ 1 〇, that is, each of the following points B', B, C, and C' (in mol%) in Fig. 1 is surrounded by straight lines connected in the order It is better in the range and on the straight lines. When it is in this range, an optical film having a high refractive index, particularly high scratch resistance, can be obtained by vacuum evaporation treatment. B,( w,x,y) = ( 19, 71,10) -10- 201109451 B ( w,x,y ) = (19,80.19,0.81) C ( w,x,y ) = ( 54, 45.54 , 0.46 ) C5 ( w, x, y) = ( 54, 36, 10) The composition of the present invention is formed only by a compound formed of an oxide of cerium and titanium, or only an oxide of cerium and aluminum. The compounds are more stable in the atmosphere. The reason is that three kinds of substances such as cerium oxide, titanium oxide, and aluminum oxide are simultaneously present, and when the crystallization is promoted or synthesized, the crystallization of the lattice is promoted or diffused, and adjacent molecules are easily bonded. Produces free or agglomerated and exists. The composition of the present invention is such that XS 1 〇, that is, the points (unit: m〇l%) of the following A, A', D', and D in the first drawing are surrounded by straight lines connected in this order. It is better in the range and on the straight line. When it is in this range, an optical film having a refractive index particularly high in the near ultraviolet range can be obtained by vacuum evaporation treatment. A ( w,x,y ) = ( 19,0_ 8 1,80.19 ) A'( w,x,y ) = ( 19, 10, 71 ) D,( w,x,y ) = ( 54,1 0 , 36 ) D ( w, x, y ) = ( 54, 0.46, 45.5 4 ) The composition of the present invention may be in any form of a compound or a mixture, but is preferably in the form of a compound. Here, the compound of the present invention means a state in which each element is chemically bonded to form a stable state, and the mixture means a state in which two or more elements or a compound containing the element is simply mixed and has no chemical bond. In the case of a compound, since cerium oxide forms a compound of diazepam-11-201109451 with cerium oxide or aluminum oxide, cerium oxide is almost completely absent alone. Therefore, there is almost no absorption of moisture or carbon dioxide, and generation of harmful gas during film formation can be suppressed, and since there is little sputtering during vapor deposition, a stable film can be obtained. Further, in the form of a mixture, since cerium oxide absorbs moisture or carbon dioxide in the atmosphere, there are disadvantages such as generation of harmful gas or sputtering during vacuum vapor deposition. Further, the composition of the present invention is more preferably a sintered product or a molten material. The sintering pressure and temperature are different depending on the elemental composition or the specific surface area of the powder, and it is preferably 1350 ° C or more in a vacuum. When sintering or melting is performed in a vacuum of 1 〇 2 Pa or less, the generation of gas such as sputtering or oxygen at the time of vapor deposition can be further reduced. Further, if it is less than 3 50 ° C, the sintering reaction may become insufficient, and unreacted cerium oxide may remain, or the obtained sintered product may have disadvantages such as low strength and low density. The sintering time is appropriately selected by the sintering temperature, and is usually 1 hour or longer. When it is less than 1 hour, the sintering reaction may become insufficient. When the composition of the present invention is sintered or melted, a composition of a reduced low-order oxide may be used in addition to low-grade titanium oxide or titanium metal, titanium hydride, metal aluminum or the like. By using a lower oxide, free oxygen generation can be reduced during vapor deposition. The shape of the composition of the present invention may be any of a pellet shape, a tablet shape, a pellet shape, and the like, and is preferably used after being dissolved by an electron beam before vapor deposition. In this case, it is particularly easy to use a pellet. The composition of the present invention may contain other elements as long as it does not impair the invention. In other words, in the composition of the present invention, not only -12-201109451 has an unavoidable impurity element, but also other elements may be added as needed within the scope of the present invention. Next, an optical film relating to the present invention will be described. The optical film of the present invention is formed on a substrate made of glass or synthetic resin by vacuum evaporation treatment of the composition of the present invention, and has a refractive index of about 1. 7 to 2.2. The vapor deposition treatment can be carried out by a general method using an electron beam. According to the findings of the present inventors, alumina, cerium oxide, and titanium oxide are all transparent materials which are sufficiently transparent as optical films, and have similar evaporation characteristics. Further, by simultaneously forming oxides of lanthanum, titanium, and aluminum, the effect of the relaxation between the lattices of the vapor deposition material or the movement of the substrate is promoted at the time of film formation, and the adjacent molecules become easily bonded. Therefore. Therefore, since cerium oxide or the like in the film is not easily released or aggregated, the moisture resistance can be improved, and the physical and chemical stability of the film adhesion, acid resistance, and alkali resistance can be improved. This effect was not found in a film formed only of cerium oxide and aluminum oxide, and was not found in a film formed only of cerium oxide and titanium oxide. As the optical film of the present invention, a film for forming a multilayer film which is an antireflection film, an optical filter, an optical mirror, an optical iridium or the like can be used. [Embodiment] The present invention is described in more detail by way of the following examples, but the invention is not limited by the examples. 201109451 [Examples] <Production of Composition> The cerium oxide powder (La203, purity 99.99%, average particle diameter 2μηι) was obtained by the composition formula (calculated 値) shown in Table 1 and weight ratio shown in Table 1. , titanium oxide powder (Ti02, purity 99.99%, average particle size 1 μιη), metal titanium powder (Ti, purity 99%, average particle size 7μιη), alumina powder (Al2〇3, purity 99.99%, average particle size 0 · 6μιη). Each of the separated powders was mixed by ball milling for 48 hours, and then a 'dispersion material' was added to the mixed powder, followed by ball milling for 8 hours. The resulting mixture was cold-formed and pulverized at a pressure of 9,8066.5 kPa (1000 kgf / cm2) to be granulated. Then, using a vacuum heating apparatus equipped with a degreasing function, the mixture was heated in a vacuum of 1 × 10 · 2 Pa or less at a temperature shown in Table 1 for 24 hours to obtain a particulate sintered product. -14- 201109451 [Table 1 Composition formula (calculation 値) L&2〇3 wt(« TiOz wt〇i) Ti wt (« A1A wt(X) vacuum sintering temperature CC) Example 1 B 347.5~7.^15 〇173.75 65.65 32.19 0.00 2.16 1490 Example 2 64.11 31.43 0.00 4.46 1490 Example 3 ^33.33^^33.33^1-33.33〇167.67 55.46 27.19 0.00 17.35 1490 Example 4 47.25 23.17 0.00 29.58 1490 Example 5 La3〇Tie〇AIi 〇〇i5〇50.34 37.02 7.40 5.24 1720 Example 6 La4〇Ti]〇Alii〇〇i5〇66.60 8.12 1.22 26.06 1650 Example 7 La54Tio.4RAl45.wO160 23 78.86 0.33 0.00 20.81 1600 Comparative Example 7 LaMAl460lwl 78.95 0.00 0.00 21.05 1600 Example 8 ^a5〇Ti〇.&Al49.5〇150 76.09 0.28 0.06 23.57 1600 Comparative Example 8 La^AUnOicin (LaAI0s) 76.16 0.00 0.00 23.84 1600 Example 9 La<〇Ti〇fiAL59.4〇iB〇. 3 67,93 0.50 0.00 31.57 1600 Comparative Example 9 La4〇ALen〇i so 68.05 0.00 0.00 31.95 1600 Example 10 La3〇Ti〇7Ale93〇i &〇57.70 0.49 0.10 41.71 1600 Comparative Example 10 La3〇Al7n〇i¥ifl 57.80 0.00 0.00 42.20 1600 Example 11 La^Tio diAleo I9〇iso.4i 42.71 0.89 0.00 56.40 1600 Comparative Example 11 42.84 0.00 0.00 57.16 1600 Example 12 LaiflTi; nAlfi〇〇i5〇40.39 16.41 3.28 39.92 1720 Comparative Example 12 Lai8Tl22AlR〇〇i5〇38.72 17.40 3.48 40.40 1720 Example 13 ^ 3ΐ9^ΰΐΑΐ40〇170.5 36.81 38.94 0.00 24.25 1490 Comparative Example 13 LaigTi42AUo〇i7i 35.22 40.29 0.00 24.49 1490 Example 14 LaigTL6iAl20〇i50 36.42 42.99 8.59 12.00 1720 Comparative Example 14 Lai8Ti62Al70〇1F10 34.88 44.17 8.82 12.13 1720 Example 15 LaigTigo 1qA1〇. 81〇190.1 32.44 67.13 0.00 0.43 1490 Comparative Example 15 LaiaTiR1〇iQn a 32.36 67.64 0.00 0.00 1490 Example 16 La3〇Ti69.3AL〇.7〇l50 49.35 41.92 8.37 0.36 1720 Comparative Example 16 La3〇Ti7n〇iii〇49.28 42.28 8.44 0.00 1720 Example 17 La4〇T “9 aAL〇.B〇179.7 57.71 42.02 0.00 0,27 1490 Comparative Example 17 La4〇T ΐβηΟίβο 57.62 42.38 0.00 0.00 1490 Example 18 La50Ti496Al〇.5〇i5〇69.45 25.28 5.05 0.22 1720 Comparative Example 18 La&Ti5n〇iw) (LaTi03) 69.39 25.51 5.10 0.00 1720 Example 19 La54X145 w Al〇4B〇i72.77 70.61 29.20 0.00 0.19 1490 Comparative Example 19 LawTi^Om 70.54 29.46 0.00 0.00 1490 Example 20 La^Ti^AlToO^o 73.96 18.13 3.62 4.29 1700 Comparative Example 20 La55Ti35All〇〇15〇74.78 17.49 3.50 4.25 1700 Example 21 73.97 17.46 0.00 8.57 1490 Comparative Example 21 La65Ti^Al^〇〇i62.B 74.82 16.67 0.00 8.51 1490 Example 22 La54Ti16Al3〇〇i5〇76.65 8.35 1.67 13.33 1650 Comparative Example 22 ^a55^il5Ala〇〇i5〇 77.46 7.77 1.55 13.22 1650 Comparative Example 23 La7〇Tii〇Alj:0〇i55 86.25 6.04 0.00 7.71 1490 Comparative Example 24 La7〇Tij>〇ALi〇〇i6〇84.40 11.82 0.00 3.78 1490 Comparative Example 25 La8〇^M〇Ali〇 〇i55 90.88 5.57 0.00 3.55 1490 Comparative Example 26 Lai〇TiinAlfl〇〇i55 25.04 12.27 0.00 62.69 1490 Comparative Example 27 La10Ti^M4s〇ms 21.67 47.81 0.00 30.52 1490 Comparative Example 28 Lai〇Ti8nAli〇〇ii)〇19.10 74.92 0.00 5.98 1490 Comparative Example 29 TistlAUo〇,7<;(ALTi03) 0.00 48.70 9.74 41.50 1720 Comparative Example 30 Lai〇〇〇i&n (La^Og) 100.00 0.00 0.00 0.00 1500 Comparative Example 31 Ali〇〇〇i ^(AL^Os ) 0 .00 0.00 0.00 100.00 1580 Comparative Example 32 Til00〇20D(ri〇2) 0.00 100.00 0.00 0.00 1450 Comparative Example 33 ^a33.33^1-33 33AI33 33^133.33 58.65 14.38 8.62 18.35 1720 Comparative Example 34 La^TUoM^oO ]^ 67.14 4.12 2.47 26.27 1720 Comparative Example 35 ^47.5^147 f, Al5〇i2G.25 70.18 17.20 10.31 2.31 1720 -15- 201109451 <Formation of vapor deposited film> The obtained composition was subjected to vacuum distillation. The plating apparatus (vapor deposition distance: 1100 mm) was used in the Hearth Liner for electron beam evaporation, and the inside of the apparatus was evacuated to a pressure of lxl 0_3 Pa. Then, by evaporating the composition by electron beam, on a clean glass substrate (BK7 or synthetic quartz) set in advance in the apparatus, until the optical film thickness is 1/4 into 4 people (wavelength person = 54 〇 11111) The vapor deposition treatment was carried out at a vapor deposition rate of about 5 A/sec up to the desired film thickness. <Evaluation of Composition> The composition thus obtained was evaluated by the test method shown below. The results are shown in Table 2. (1) Composition analysis The composition was pulverized into a powder in an agate mortar, and after solutionization by an alkali fusion method, a cerium nitrate solution was added as an internal standard material to prepare a sample liquid. Then, the obtained solution was introduced into an ICP emission spectroscopic analyzer. Quantitative analysis of elements of La, Ti and A1 was carried out by an internal standard method. The JCP luminescence spectroscopic analysis apparatus uses the VISTA PRO 制 manufactured by BALIAN Co., Ltd. to observe the luminescence intensity by observing the axial direction. Further, the composition was subjected to an inert gas dissolution-infrared absorption method to carry out the quantification of oxygen. The apparatus was E M G A · 65 0 manufactured by Horiba, Ltd., and the measurement method was carried out based on the infrared absorption method of the general method of oxygen quantification of the metal material of JIS-Z2613. -16- 201109451 Calculate the chemical composition of the composition by the analysis results obtained. As shown in Table 2, in all the examples and comparative examples, the elemental composition almost identical to the calculated enthalpy shown in Table 1 was confirmed. The composition ratio of bismuth, titanium and aluminum in each composition is shown in Fig. 2. (2) Moisture resistance The composition was kept in a constant temperature and humidity chamber at a temperature of 35 ° C and a relative humidity of 95% RH for 30 days, and the change in appearance was observed, and the change in weight was measured. The measurement of the weight change is performed using an electronic scale. The results obtained were evaluated on the basis of the following criteria. ◎ : The appearance did not change within 30 days, and the weight increase due to moisture absorption did not reach + 1 wt %. 〇: The appearance did not change within 30 days, but the weight due to moisture absorption increased by + 1 wt% or more △ : 1 day or more, 3 In the case where the composition collapses or swells within 0 days X: The case where the composition collapses on the 1st day is as shown in Table 2, and it can be confirmed that the compositions of the present invention have sufficient stability to the humidity in the atmosphere. . Further, in Comparative Example 23 to Comparative Example 2 5 and Comparative Example 30, the moisture resistance of the examples and the other comparative examples was more unsatisfactory. These are due to the high content of cockroaches and the absorption of moisture in the atmosphere. (3) Compensatory utilization -17- 201109451 After forming a steaming shovel film (optical film thickness 1/4λ) on a glass substrate (synthetic quartz), the composition of the reduced portion is complemented. When this operation was repeated 20 times, the change in the refractive index of the vapor-deposited film and the change in the elemental composition of the composition residue were observed. The reflectance refractive index was measured by the following formula 1, and the reflectance calculation rate of the film was carried out using Lambda 900 manufactured by PERKINELMER. [Number 1] Refractive index = (substrate refractive index) x {l + (reflectance) 1/2} {1 - (reflectance) 1/2} , 1/2 compositional composition analysis of the residue of the composition, (1) The composition analysis was carried out in the same manner using an ICP emission spectroscopic analyzer. The results obtained were evaluated on the basis of the following criteria. [Reflection of refractive index of film] ◎: The difference in refractive index between the first film formation and the 20th film formation is less than 0.01 〇: the difference between the refractive index of the first film formation and the 20th film formation is 0_01 or more. 0.02 △: The difference in refractive index between the first film formation and the 20th film formation is 0.02 or more and less than 0.05 X: the difference between the refractive index of the first film formation and the 20th film formation is 0.05 or more. Change in composition of the residue of the composition] ◎: The difference in La content between the film formation and the 20th film-forming composition is less than ± 1 %. 〇: La before and after the 20th film formation. The difference in the content ratio is -18-201109451 ±1% or more and less than ±2%. △: The difference in La content between the film formation and the 20th film formation is ±2% or more, which is less than ± 3% x : The difference in La content between the film formation and the 20th film-forming composition is ±3 % or more. As shown in Table 2, oxides of bismuth, titanium and aluminum, aluminum-free oxides, Titanium-free oxides are the result of less variation in the composition of the elements. In addition, there is almost no change in the refractive index of the film. Further, the reason why the refractive index fluctuates in some of the comparative examples is that the film is absorbed by the oxygen deficiency in the film, and the correct refractive index cannot be obtained. From these results, it was confirmed that the constituent objects using the present invention can be complemented. (4) Sputtering When the film was vapor-deposited, it was observed that sputtering occurred when the composition was irradiated with an electron beam, and evaluation was performed on the basis of the following criteria. ◎: almost no sputtering was observed 〇: sputtering was slightly generated Δ: sputtering was frequently generated X: - sputtering was generated as shown in Table 2, and no sputtering was observed in the composition of the present invention. The situation arises. In addition, many sputtering cases were produced in some of the comparative examples. In Comparative Examples 2 to 25 and Comparative Example 3, since the content of cerium was high, moisture in the atmosphere was absorbed and the sputtering was caused. Further, it was confirmed that Comparative Example 3 2 is a characteristic of titanium oxide in the case of sputtering -19-201109451. From these results, it was confirmed that the composition of the present invention is a composition having less sputtering. (5) Adhesion of fine particles to the substrate The number of fine particles adhering to the blue plate glass substrate (80?) due to sputtering or the like was observed by an optical microscope. ◎: adhesion 〇 〇: adhesion 1 to 2 ' △: adhesion 3 to 4 X : adhesion 5 or more As shown in Table 2, when the composition of the present invention was observed, fine particles were not observed on the substrate. In addition, many fine particles were observed in some of the comparative examples. In the comparative example in which fine particles were observed, the characteristics of titanium oxide and aluminum oxide which adhered to fine particles were easy to adhere. From the results of the above, it was confirmed that the composition of the present invention can produce a film in which very fine particles are attached. -20-201109451 [Table 2] Composition Analysis Humidity Resistant Usage Sputtering When fine particles adhere to the substrate, the refractive index of the film changes. Composition variation of the composition Example 1 La47.sT "7.5Al5.1〇172 Θ ® Θ 0 © Example 2 La4sTi^ nAlin ι〇ΐ7ΐ Θ Θ 0 0 © Example 3 La 33.33*^ i 33 λ AI33.4〇ι 66 @ @ Θ 0 © Example 4 La^Ti^ 1AI4C1 .qOifii © ® Θ 0 © Example 5 La3〇Ti6〇iAl10 !〇u9 0 Θ 0 Θ Example 6 LawTiioAUnOufi @ © Θ 0 0 Example 7 La54Ti〇4f}Al4(; ii〇uii 〇Θ © ® 0 ® Comparative Example 7 La^Al^ Λ ® 〇0 Example 8 La(i〇Ti〇.5iAl4g.5〇i49 〇Θ © 0 Comparative Example 8 LasoAL^o 2〇uft Θ ® ® 0 Example 9 La^oTio.eAlsfl sOur ® Θ Θ Θ 0 © Comparative Example 9 La^oAleo i〇us Θ ® Θ Θ 0 Example 10 La30Ti. 72Α1Μ 3O咖® Θ Θ @ 0 ® Comparative Example 10 La3〇Al7〇2〇im Θ ® ® 0 Θ Implementation Example 11 La1flTin mAIm : Am © 0 Θ Comparative Example 11 La19Al80 80151 Θ 0 ® Example 12 LajgTiz! gAleig 8〇!49 ® Θ 0 Θ Compare 12 La18TL22.lAl6〇.]〇u8 Θ @ © 0 ® Example 13 La19Ti41 ^Al^o 2〇i ® ® ® 0 Θ Comparative Example 13 Lai8Ti42 2AI40 4〇17〇<s> Θ Θ 1 实施 Example 14 LaigTig! ^Aljo TOug ® Θ ® 0 ® Comparative Example 14 LaigTi62Al2〇〇u9 Θ @ ® 〇Example 15 Θ © ® Θ 〇Comparative Example 15 Lai9Ti81 〇0] 89 © 〇3 Δ Example 16 La3〇Tie9.3Al〇 .72〇i5〇Θ Θ 1 〇Comparative Example 16 La30ri7〇© 〇〇3 Δ Example 17 La4〇Ti5g 4AL0 Ri〇t7fi ® ® 〇Comparative Example 17 LaioTisg fi〇i7ft ® ® Θ 〇 1 〇Example 18 La5〇Ti49.4Al〇.52〇149 Θ @ Θ Θ 0 Comparative Example 18 La&〇Ti5〇.3〇u8 〇0 @ ® 0 ® Example 19 La54Ti45.7Aln 49O170 ® @ Θ 0 Comparative Example 19 La54^i -46.0〇171 〇© 0 Θ 0 ® Example 20 iAl10jOim Θ Θ Θ ® 0 @ Comparative Example 20 Lac^Ti^e; iAlon n〇us 〇@ 〇0 Θ Example 21 Las4Ti26 ?Μί!Π 0〇1fil Θ ® 0 ® Comparative Example 21 La5sTi25 3AI20 2〇im 〇0 Example 22 La64Til6.lAL30.2〇]48 Θ Θ 0 Comparative Example 22 La&sTiu.gAUo.iO Uf} 〇® 0 ® Comparative Example 23 La7〇Tii〇.2Al7〇2〇1&4 X ® Θ . Δ Ο Comparative Example 24 La7〇Ti2〇X Θ © Δ 〇Comparative Example 25 La8〇Tii〇.iAlin X Θ Δ Ο Comparative Example 26 La]〇Tii〇.2Al8〇.3〇i 54 Θ ® © ® 3 Δ Comparative Example 27 Lai〇Ti^ ιΑΙ^ς i〇i7〇® © Θ Θ 3 Δ Comparative Example 28 Lai〇Ti8 〇.2Ali〇.2〇l 89 Θ 〇0 Δ 4 Δ Comparative Example 29 ΤΪ50Α149.7Ο174 ® Θ — Ο 3 Δ Comparative Example 30 Lai〇〇〇is〇(La2〇3) X © △ 4 Δ Comparative Example 31 All00 〇lS0 (Al?, 〇3) ® 〇 - 3 Δ Comparative Example 32 Ti] 00 〇 19S - - Δ 6 X Comparative Example 33 ^333.3^^33 aAl33 3〇1; i3 〇〇2 〇 Comparative Example 34 La' f)Tii〇Al&〇〇us ® Θ ® 〇2 〇Comparative Example 35 La47 sTi47 sAI&0Curry Ο Θ 〇2 〇-21 - 201109451 <Evaluation of vapor deposited film> The test method evaluates the formed film. The results are shown in Table 3. (6) Moisture resistance The film (glass substrate: BK7, optical film thickness: 4λ) was stored in a constant temperature and humidity chamber at a temperature of 35 ° C and a relative humidity of 95% RH for 30 days, and the change in the appearance of the film was observed, and the refractive index was measured. Change in rate. The refractive index system was obtained in the same manner as in the above (3). The results obtained were evaluated on the basis of the following criteria. ◎: The appearance did not change, and the change in refractive index did not reach 〇. 〇3 〇: the appearance did not change, but the refractive index changed by 0.03 or more Δ: the appearance of white turbidity X: appearance of film peeling or cracking as shown in Table 3, It was confirmed that the composition of the present invention has high stability to moisture in the atmosphere. Further, in Comparative Examples 20 to 25 in which the content of the crucible was high, or in Comparative Examples 1 to 5 in which no aluminum was contained, and in Comparative Examples 7 to 1 in which no antimony was contained, it was confirmed that the resistance was higher than in the examples. Poor wetness. (7) Absorption rate (visible range) The light transmittance of a film (glass substrate: synthetic quartz, optical film thickness: 3/4λ) and the absorption rate in the visible range by spectral reflectance, "absorption rate = 1〇〇 %—transmittance—reflectance” is obtained. Transmittance and reflectance -22- 201109451 The measurement was performed using Lambda900 manufactured by PERKINELMER. The obtained absorption rate was evaluated on the basis of the following criteria. ◎: Absorption rate is less than 0.5% 〇: Absorption rate 0 · 5 % 〜 0.7 % △: Absorption rate 0.7 % 〜1 . 5 % X : Absorption rate 1 · 5 % or more As shown in Table 3, the composition of the present invention There is a result of less absorption of the film. In addition, in some of the comparative examples, there was a result of a large absorption of the film. Comparative Example 3 3 to 3 5 ' Since the oxygen content of the composition was small, the obtained film was a low-level oxide and was absorbed. The comparative examples in which other absorption is more are characteristics of titanium oxide and aluminum oxide which are likely to cause film absorption. From the results, it was confirmed that the composition of the present invention can produce a film having high transparency. (8) Refractive index The refractive index of the film (glass substrate: synthetic quartz, optical film thickness: 3/4λ) was determined in the same manner as in the above (3). As shown in Table 3, it was confirmed that the composition of the present invention can form a film having a wide refractive index of about ～2.2 (9) transparency in the near ultraviolet range (absorption end on the ultraviolet side) by film (glass substrate: synthetic quartz) , optical film thickness: 3/4λ) in the near-shoulder outer line range (300 ~ 400nm), the light transmittance and the spectral reflectance -23-201109451, "absorption rate = 1% - transmittance - reflectivity" Take the absorption rate. The transmittance and reflectance in the near-ultraviolet range were measured using 1^1^£1&900 manufactured by the company. Here, the wavelength at which the obtained absorption rate is 3% or more is taken as the absorption end on the ultraviolet ray side, and the evaluation is performed based on the following criteria. ◎: the absorption end is less than 3 3 0 nm 〇: the absorption end is 3 3 0 nm or more. As shown in Table 3, Examples 6 to 1 1 and Comparative Examples 7 to 1 1 having a low Ti content have a near ultraviolet range. Particularly excellent transparency. (10) Acid resistance (JIS-K5400 8.22) The film (glass substrate: BK7, optical film thickness: 4λ) was immersed in 5w/v% dilute sulfuric acid (liquid temperature 3 5 °C) for 168 hours, each time passed. The change in the film was observed after 24 hours and evaluated on the basis of the following criteria. ◎: No change 〇: There is no change within 24 hours, but there is a change other than film peeling such as white turbidity. Δ: Change in film removal other than white turbidity, crack, etc. within 24 hours X: at 24 In the case where the film peeling occurred within the hour, as shown in Table 3, it was confirmed that the composition of the present invention was stable to the acid, and the comparative examples 20 to 2 5 having a large content of cerium, and the composition of the present invention When compared, it can be confirmed that the acid resistance is not good. It is an acid-resistant or water-resistant oxygen-24-201109451. Further, when the composition of the present invention is compared with the comparative example 7 to Π of the comparative example 15 to 19' which does not contain aluminum, it is confirmed that the acid resistance is poor (11) alkali resistance (JIS-K5400 8.21) The film (glass substrate: BK7, optical film thickness: 4λ) was immersed in a 5 w/v% sodium carbonate aqueous solution (liquid temperature: 35 ° C) for 168 hours, and the change of the film was observed every 24 hours, and the following criteria were used. Evaluation. ◎: No change 〇: There is no change within 24 hours, but there is a change other than peeling of the film, such as white turbidity. Δ: Change in addition to film peeling such as white turbidity and cracking within 24 hours X: at 24 In the case where the film peeling occurred within the hour, as shown in Table 3, it was confirmed that the composition of the present invention was stable to the alkali, and the comparative examples 20 to 2 5 having a large content of cerium, and the composition of the present invention When compared, it can be confirmed that the testability is not good. It is a characteristic of cerium oxide which is resistant to alkali or water. (12) Adhesion (JIS-R3 25 5 ) The film (glass substrate: synthetic quartz, optical film rhino: 4λ) was evaluated for adhesion by a micro-scratch test. The testing machine used the CSR-02F manufactured by RHESC Corporation. Moreover, the measurement conditions are the radius of the diamond press 5μιη, -25-201109451 speed ΙΟμιη/s, the segment angle 3DEG, the increment is 1 000, the excitation series 9 0 μηι 0 The critical load induction by the micro-scratch test The output of the device is evaluated on the basis of the following criteria.
◎ : 50mN以上 〇：30mN以上、未達50mN △ : 20mN以上、未達30mN X : 未達20mN 如表3所示，可確認本發明之組成物，附著性皆較高 ，特別是實施例1〜2、5、1 5〜2 0之附著性高。 另外，鑭之含率多的比較例23〜25或比較例30、鑭之 含率少的比較例26〜29、不含鋁之比較例15〜19、不含鈦 之比較例7〜Π，皆有附著性不佳的結果。 (1 3 )組成分析 使用波長分散型螢光X光分析裝置（WD-XRF )，進 行薄膜（玻璃基板：合成石英、光學膜厚：4λ)中所含的 元素之定性分析。分析裝置係使用RIGAKU公司製RIX3000 〇 如表3所示’可確認組成物之元素與藉由真空蒸鍍處 理所得薄膜中之檢測元素一致，且本發明之光學薄膜含有 鑭、鈦、鋁元素。 <綜合評估> -26- 201109451 綜合前述（2)〜（7)及（9)〜（12)之評估，進 行評估。 ◎:評估爲〇之項目爲1個以下，△及χ之項目爲0 〇：評估爲〇之項目爲2個以上，△及x之項目爲0 △:評估爲△之項目爲1個以上’ x之項目爲0 X:評估爲χ之項目爲1個以上 如表3所示，本發明之組成物對大氣中之水分而言安 定’濺射情形及微細粒子附著於基板之情形少，即使補足 利用，仍爲組成變動少的組成物。 另外’藉由本發明之組成物所得的光學薄膜，係由同 時滿足高耐濕性、附著性、透明性、耐酸性、耐鹼性之鑭 、鈦、鋁，氧之元素所形成的光學薄膜。 -27- 201109451 【表3】◎ : 50 mN or more 〇: 30 mN or more, less than 50 mN Δ : 20 mN or more, less than 30 mN X : less than 20 mN As shown in Table 3, it was confirmed that the composition of the present invention has high adhesion, particularly Example 1 The adhesion of ~2, 5, 1 5~2 0 is high. Further, Comparative Examples 23 to 25 or Comparative Example 30 in which the content of ruthenium was high, Comparative Examples 26 to 29 in which the content of ruthenium was small, Comparative Examples 15 to 19 in which aluminum was not contained, and Comparative Examples 7 to 不含 in which titanium was not contained, All have poor adhesion results. (1 3 ) Composition analysis Qualitative analysis of elements contained in a film (glass substrate: synthetic quartz, optical film thickness: 4λ) was carried out using a wavelength dispersion type fluorescent X-ray analyzer (WD-XRF). As the analysis apparatus, RID3000 manufactured by RIGAKU Co., Ltd. was used. As shown in Table 3, it was confirmed that the elements of the composition were identical to those of the film obtained by the vacuum evaporation treatment, and the optical film of the present invention contained lanthanum, titanium, and aluminum. <Comprehensive evaluation> -26- 201109451 The evaluations of the above (2) to (7) and (9) to (12) are combined and evaluated. ◎: The number of items evaluated as 〇 is 1 or less, and the items of △ and χ are 0 〇: 2 items are evaluated as 〇, and 0 items of △ and x are △: 1 item or more is evaluated as △' The item of x is 0 X: the item evaluated as χ is one or more. As shown in Table 3, the composition of the present invention is stable to the moisture in the atmosphere, and the sputtering condition and the fine particles adhere to the substrate are small, even if To make up for the use, it is still a composition with little change. Further, the optical film obtained by the composition of the present invention is an optical film formed of an element which satisfies high moisture resistance, adhesion, transparency, acid resistance, alkali resistance, titanium, aluminum, and oxygen. -27- 201109451 [Table 3]
耐濕 試驗 吸收率(％) 折射 率 近紫外 線範圍 之透明 性 耐酸 性 耐鹼 性 附著 性 組成分析 綜合 評估 La Ti A1 實施例1 Θ 0.21 Θ 2.03 〇 Θ Θ ® 有檢測到 有檢測到 有檢測到 實施例2 ® 0.29 Θ 2.02 〇 ® ® Θ 有檢測到 有檢測到 有檢測到 © 實施例3 Θ 0.30 Θ 1.97 〇 Θ @ 〇 有檢測到 有檢測到 有檢測到 © 實施例4 © 0.31 ® 1.91 〇 Θ Θ 〇 有檢測到 有檢測到 有檢測到 0 實施例5 0.48 ® 1.91 〇 Θ Θ Θ 有檢測到 有檢測到 有檢測到 Θ 實施例6 ® 0.41 Θ 1.82 Θ Θ 〇 有檢測到 有檢測到 有檢測到 0 實施例7 Θ 0.34 Θ 1.82 Θ Θ Θ Ο 有檢測到 有檢測到 有檢測到 Θ 比較例7 Δ 0.36 © 1.82 Θ △ 〇 〇 有檢測到 沒有檢測到 有檢測到 △ 實施例8 © 0.40 0 1.82 0 ® 〇 有檢測到 有檢測到 有檢測到 0 比較例8 Δ 0.39 ® 1.S2 Θ Λ 〇 有檢測到 沒有檢測到 有檢測到 △ 實施例9 Θ 0.39 1.80 ® ® Θ . Ο 有檢測到 有檢測到 有檢測到 © 比較例9 Δ 0.39 1.79 Θ Λ ® 〇 有檢測到 沒有檢測到 有檢測到 △ 實施例10 Θ 0.40 Θ 1.72 0 Θ Θ 〇 有檢測到 有檢測到 有檢測到 © 比較例10 〇 0.S3 〇 1.71 Θ 〇 Λ 〇 有檢測到 沒有檢測到 有檢測到 △ 實施例11 Θ 0.47 ® 1.69 @ Θ Θ 〇 有檢測到 有檢測到 有檢測到 © 比較例11 〇 0.72 Δ 1.70 ® . Θ Δ 有檢測到 沒有檢測到 有檢測到 Δ 實施例12 Θ 0.61 〇 1.74 〇 ® 〇 有檢測到 有檢測到 有檢測到 〇 比較例12 © 0.88 Λ 1.72 〇 <2> Δ 有檢測到 有檢測到 有檢測到 Δ 實施例13 Θ 0.40 ® 2.01 〇 Θ Θ 〇 有檢測到 有檢測到 有檢測到 Θ 比較例13 0 0.67 〇 2.00 Ο © Θ Λ 有檢測到 有檢測到 有檢測到 △ 實施例14 Θ 0.68 〇 1.90 〇 Θ Θ 〇 有檢測到 有檢測到 有檢測到 〇 比較例14 ® 1.11 Δ 1.90 〇 〇 Δ 有檢測到 有檢測到 有檢測到 △ 實施例15 Θ 0.45 ® 2.21 〇 ® Θ 有檢測到 有檢測到 有檢測到 〇 比較例15 〇 0.77 Δ 2.21 〇 Θ 〇 Δ 有檢測到 有檢測到 沒有檢測到 △ 實施例16 ® 0.36 1.93 〇 Θ ® 有檢測到 有檢測到 有檢測到 〇 比較例16 Δ 0.38 1.93 〇 Θ 〇 Δ 有檢測到 有檢測到 沒有檢測到 △ 實施例17 Θ 0.33 2.08 Ο © © ® 有檢測到 有檢測到 有檢測到 〇 比較例17 Δ 0.38 Θ 2.0Θ 〇 Θ 〇 〇 有檢測到 有檢測到 沒有檢測到 △ 實施例18 ® 0.36 © 1.91 〇 Θ Θ Θ 有檢測到 有檢測到 有檢測到 比較例18 △ 0.40 @ 1.91 Ο 〇 〇 Ο 有檢測到 有檢測到 沒有檢測到 △ 實施例19 Θ 0.37 Θ 2.02 〇 @ Θ 有檢測到 有檢測到 有檢測到 ® 比較例19 X 0.37 ® 2.02 〇 Δ △ 〇 有檢測到 有檢測到 沒有檢測到 X 實施例20 Θ 0.61 〇 1.89 〇 © Θ 有檢測到 有檢測到 有檢測到 〇 比較例20 〇 0.58 〇 1.89 〇 Λ Δ 〇 有檢測到 有檢測到 有檢測到 Δ 實施例21 ® 0.29 Θ 1.94 〇 Θ Θ 〇 有檢測到 有檢測到 有檢測到 Θ 比較例21 Ο 0.29 ® 1.94 〇 △ Δ 〇 有檢測到 有檢測到 有檢測到 Δ 實施例22 Θ 0.44 @ 1.85 〇 0 ® Ο 有檢測到 有檢測到 有檢測到 Θ 比較例22 〇 0.47 Θ 1.85 〇 Δ Δ Ο 有檢測到 有檢測到 有檢測到 Δ 比較例23 X 1.10 △ 1.89. 〇 X X X 有檢測到 有檢測到 有檢測到 X 比較例24 X 1.08 Δ 1.93 〇 X X X 有檢測到 有檢測到 有檢測到 X 比較例25 X 1.31 Δ 1.89 0 X X X 有檢測到 有檢測到 有檢測到 X 比較例26 @ 0.71 Δ 1.78 Θ ® ® Δ 有檢測到 有檢測到 有檢測到 Δ 比較例27 ® 0.72 Δ 2.03 〇 Δ Δ 有檢測到 有檢測到 有檢測到 Λ 比較例28 0.80 Δ 2.23 〇 Λ Δ 有檢測到 有檢測到 有檢測到 Δ 比較例29 ® 2.41 X 1.83 〇 @ ® Δ 沒有檢測到 有檢測到 有檢測到 Δ 比較例30 X - 一 - - X X - 有檢測到 沒有檢測到 沒有檢測到 X 比較例31 ® 1.12 Λ 1.62 Θ ® Δ 沒有檢測到 沒有檢測到 有檢測到 Δ 比較例32 ® 1.59 X 2.37 〇 Θ A Δ 沒有檢測到 有檢測到 沒有檢測到 X 比較例33 Θ 5.11 X 1.98 〇 © Θ 〇 有檢測到 有檢測到 有檢測到 X 比較例34 © 3.81 X 1.83 Θ ® Θ Ο 有檢測到 有檢測到 有檢測到 X 比較例35 7.02 X 2.04 〇 Θ © Θ 有檢測到 有檢測到 有檢測到 X -28- 201109451 【圖式簡單說明】 〔第1圖〕係表示本發明之薄膜形成用組成物的鑭（ La )、鈦（Ti )及鋁（A1 )元素之組成範圍的三角圖。 〔第2圖〕係表示實施例之組成物中的鑭（La )、鈦 (Ti )及鋁（A1 )元素之組成比例的三角圖。 〔第3圖〕係說明第1圖、第2圖之三角圖的讀取方法 圖。 -29-Moisture resistance test Absorption rate (%) Refractive index Near ultraviolet range Transparency Acid resistance Alkaline adhesion Composition analysis Comprehensive evaluation La Ti A1 Example 1 Θ 0.21 Θ 2.03 〇Θ Θ ® Detected detected detected Example 2 ® 0.29 Θ 2.02 〇® ® Θ Detected detected detected © Example 3 Θ 0.30 Θ 1.97 〇Θ @ 〇 Detected detected detected © Example 4 © 0.31 ® 1.91 〇 Θ Θ 检测 Detected that there is detection detected 0 Example 5 0.48 ® 1.91 〇Θ Θ Θ Detected detected Θ detected Example 6 ® 0.41 Θ 1.82 Θ Θ 检测 Detected detected Detected 0 Example 7 Θ 0.34 Θ 1.82 Θ Θ Θ Ο Detected detection detected Θ Comparative Example 7 Δ 0.36 © 1.82 Θ △ 〇〇 Detected that no detected △ was detected Example 8 © 0.40 0 1.82 0 ® 〇 Detected detected 0 detected. Comparative Example 8 Δ 0.39 ® 1.S2 Θ 〇 检测 No detected △ detected 实施 Example 9 Θ 0.39 1.80 ® ® Θ . Ο It is detected that it has been detected. © Comparative Example 9 Δ 0.39 1.79 Θ Λ ® 检测 No detected △ detected 实施 Example 10 Θ 0.40 Θ 1.72 0 Θ Θ 检测 Detected detected Detected © Comparative Example 10 〇0.S3 〇1.71 Θ 〇 检测 Detected that no detected △ was detected Example 11 Θ 0.47 ® 1.69 @ Θ Θ 检测 Detected detected detected © Comparative Example 11 〇0.72 Δ 1.70 ® . Θ Δ detected no detected Δ detected Example 12 Θ 0.61 〇 1.74 〇 〇 〇 Detected detected 〇 〇 12 12 12 12 12 〇 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 〇 〇 〇 〇 〇 〇 〇 Δ Detected that Δ was detected. Example 13 Θ 0.40 ® 2.01 〇Θ 〇 检测 Detected detected Θ Θ 13 13 13 13 Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Θ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ △ 检测 实施 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Example 15 Θ 0.45 ® 2.21 〇® Θ It was detected that it was detected. 〇Comparative Example 15 〇0.77 Δ 2.21 〇Θ 〇Δ Detected that no △ was detected Detected Example 16 ® 0.36 1.93 〇Θ ® Yes It was detected that a detected 〇 was detected. Comparative Example 16 Δ 0.38 1.93 〇Θ 〇 Δ Detected that no △ was detected. Example 17 Θ 0.33 2.08 Ο © © ® Detected Detected 〇 检测Example 17 Δ 0.38 Θ 2.0Θ 〇Θ 检测 Detected that no △ was detected Detected Example 18 ® 0.36 © 1.91 〇Θ Θ Θ A detected case was detected △ 0.40 @ 1.91 Ο 〇 〇Ο It is detected that no △ is detected. Example 19 Θ 0.37 Θ 2.02 〇 @ Θ It is detected that there is detection detected ～ Comparative Example 19 X 0.37 ® 2.02 〇Δ △ 〇 Detected that there is no detected X Example 20 检测 0.61 〇 1.89 〇© Θ detected Detected 〇 〇 20 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 〇 〇 〇 〇 检测 检测 检测Δ was detected. Example 21 ® 0.29 Θ 1.94 〇Θ 〇 检测 Detected detection detected Θ Comparative Example 21 Ο 0.29 ® 1.94 〇 △ Δ 〇 Detected detection of Δ detected Example 22 Θ 0.44 @ 1.85 〇0 ® Ο Detected detection detected Θ Comparative Example 22 〇0.47 Θ 1.85 〇Δ Δ Ο Detected detection detected Δ Comparative Example 23 X 1.10 △ 1.89. 〇XXX Detected When it is detected that X has been detected, Comparative Example 24 X 1.08 Δ 1.93 〇 XXX has been detected and detected X is detected. Comparative Example 25 X 1.31 Δ 1.89 0 XXX It is detected that there is detection of X Comparative Example 26 @ @ 0.71 Δ 1.78 Θ ® ® Δ detected detected Δ detected. Comparative Example 27 ® 0.72 Δ 2.03 〇Δ Δ detected detected detected Λ Comparative Example 28 0.80 Δ 2.23 〇Λ Δ Detected Detected Δ was detected. Comparative Example 29 ® 2.41 X 1.83 〇@ ® Δ No detected Detected Δ Comparative Example 30 X - One - - XX - No detected X detected Comparative Example 31 ® 1.12 Λ 1.62 Θ ® Δ No detected no detected Δ Comparative Example 32 ® 1.59 X 2.37 〇Θ A Δ No detected No detected X Comparative Example 33 Θ 5.11 X 1.98 〇© Θ 〇 Detected that X is detected. Comparative Example 34 © 3.81 X 1.83 Θ ® Θ Ο It is detected that X is detected. Comparative Example 35 7.02 X 2.04 〇Θ © Θ It is detected that there is detection X -28-201109451 (Simplified drawing) [Fig. 1] is a triangular diagram showing the composition range of yttrium (La), titanium (Ti), and aluminum (A1) elements of the film-forming composition of the present invention. . [Fig. 2] is a triangular diagram showing the composition ratios of lanthanum (La), titanium (Ti), and aluminum (A1) elements in the composition of the examples. [Fig. 3] is a view showing a reading method of the triangular diagrams of Figs. 1 and 2; -29-