TW201034958A - Chain-shaped silica-based hollow fine particles and process for producing same, coating fluid for transparent coating film formation containing the fine particles, and substrate with transparent coating film - Google Patents

Chain-shaped silica-based hollow fine particles and process for producing same, coating fluid for transparent coating film formation containing the fine particles, and substrate with transparent coating film Download PDF

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TW201034958A
TW201034958A TW098142722A TW98142722A TW201034958A TW 201034958 A TW201034958 A TW 201034958A TW 098142722 A TW098142722 A TW 098142722A TW 98142722 A TW98142722 A TW 98142722A TW 201034958 A TW201034958 A TW 201034958A
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chain
cerium oxide
oxide
particles
hollow fine
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Wataru Futagami
Ryo Muraguchi
Masayuki Matsuda
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Jgc Catalysts & Chemicals Ltd
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    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C01P2004/34—Spheres hollow
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Abstract

Chain-shaped silica-based hollow fine particles which each has a cavity extending through the inside of the shell and has a low refractive index. The chain-shaped silica-based hollow fine particles each is made up of silica-based hollow fine particles Primary particles) which each has a shell outside and a cavity inside and which have been connected to one another in a chain arrangement. The chain-shaped particles each has a through-hole formed by the cavities connected to each other. The chain-shaped particles have an average length (L) in the range of 20-1,500 nm, an average width (W) in the range of 10-300 nm, and a refractive index in the range of 1.10-1.35. The shell has a thickness (Is) in the range of 2-100 nm, and the ratio thereof to the average width (W), (Ts)/(W), is in the range of 0.05-0.30.

Description

201034958 六、發明說明： 【發明所屬之技術領域】 本發明關於具有貫通 微粒子，該鍵狀氧化砂系 該鏈狀氧化矽系中空微粒 及於基材表面上形成有含 明被膜的附透明被膜之基 【先前技術】 向來，粒徑爲〇. 1〜 眾所周知（參照專利文獻 使來自矽酸鹼金屬水溶液 外的材料所成的芯上，不 製造由稠密的氧化矽殼所 (參照專利文獻3等）。 〇 再者，具有外周部爲 密且愈內側愈粗的濃度侮 之球狀氧化矽粒子係眾所 又，本案申請人先前 孔性的無機氧化物微粒子 大小之複合氧化物微粒子 案在由氧化矽與氧化矽以 物之核粒子上形成氧化矽 無機氧化物，按照需要被 內部之空洞的鏈狀氧化矽系中空 中空微粒子之製造方法，及含有 子之透明被膜形成用塗佈液，以 有鏈狀氧化矽系中空微粒子之透 材。 300μηι左右的中空氧化矽粒子係 1、專利文獻2等）。又，藉由 的活性氧化矽沈澱在由氧化矽以 破壞氧化矽殼而去除該材料，以 成的中空粒子之方法係眾所周知 殼，中心部爲中空，殼爲外側稠 I斜構造之芯-殻構造的微米大小 周知（參照專利文獻4等）。 提案藉由氧化矽等來完全被覆多 之表面，而得到低折射率的奈米 (專利文獻5參照），而且更提 外的無機氧化物所成的複合氧化 被覆層，接著去除氧化矽以外的 覆氧化矽，則可得到在內部具有 -5- 201034958 空洞的低折射率之奈米大小的氧化矽系微粒子（參照專利 文獻6 )。 另一方面，關於鏈狀的氧化矽粒子，本申請人先前亦 提案藉由在弱酸性條件下對氧化矽粒子進行水熱處理，而 形成鏈狀化的氧化矽粒子（參照專利文獻7 )。於非中空 的粒子中，由於粒子折射率不爲1 · 4 5以下，爲了得到低 折射率的粒子，本申請人更提案藉由在中空氧化砂粒子形 成階段，添加電解質物質，而形成鏈狀化的中空氧化砂粒 子（參照專利文獻8、9 )。 然而，於與上述本案申請人的提案有關的氧化矽系中 空粒子中，取決於粒子的使用目的及用途，有得不到充分 的低折射率效果之情況。即，即使將各個粒子的內部空洞 化，由粒子強度的點來看，空洞容積也有限度，即使低折 射率化，也有極限，故要求具有與以往不同粒子構造的氧 化矽系中空微粒子。 先前技術文獻 專利文獻 專利文獻1 :特開平6-3 3 0606號公報 專利文獻2 :特開平7 - 0 1 3 1 3 7號公報 專利文獻3 :特表2000-5001 1 3號公報 專利文獻4:特開平11-029318號公報 專利文獻5 ··特開平07-133105號公報 專利文獻6 :特開2 0 0 1 - 2 3 3 6 1 1號公報 專利文獻7 :特開20〇4_055298號公報 201034958 專利文獻8:特表2004-099074號公報 專利文獻9:特開2〇05-186435號公報 【發明內容】 發明所欲解決的問題 本發明係以前述專利文獻6記載的發明爲基礎所發展 者’目爲爲得到低折射率的氧化矽系微粒子，藉由使由氧 〇 化矽與氧化矽以外的無機氧化物所成的多孔質之複合氧化 物粒子（一次粒子）成鏈狀化，以氧化矽被覆此鏈狀化粒 子之表面，接著去除氧化矽以外的無機氧化物，而製造具 有貫通外殼內部之空洞的鏈狀氧化矽系中空微粒子之方法 〇 又，本發明之目的爲提供含有前述鏈狀氧化矽系中空 微粒子與被膜形成用基質形成成分，而安定性、膜形成性 等優異的被膜形成用塗料。 Ο 再者，本發明之目的爲提供將含有前述鏈狀氧化矽系 中空微粒子的被膜形成於基材的表面上，而低折射率且與 基材的密接性、強度、耐擦傷性、防反射能力及防眩性能 等優異的附被膜之基材。 解決問題的手段 本發明的鏈狀氧化矽系中空微粒子之特徵爲在外部具 有外殼、在內部具有空洞的氧化矽系中空微粒子（一次粒 子）以鏈狀連結，具有空洞互相貫通的貫通孔，平均長度 201034958 (L )在20〜1 500nm之範圍，平均寬幅（w)在l〇〜 300nm之範圍，折射率在〜1.35之範圍。 較佳爲前述外殻的厚度（Ts)係在2〜100nm之範圍 ，與前述平均寬幅（W)之比（Ts) / (W)係在0.05〜 0.30之範圍。 前述貫通孔的平均直徑（Ds)與前述平均寬幅（W) 之比的（Ds) / (W)較佳在0.1〜0.9之範圍。 較佳爲由氧化矽與氧化矽以外的無機氧化物所構成， 以 M0X表示氧化砂以外的無機氧化物時之莫耳比 MOx/Si〇2 在 0.0001 〜0.2 之範圍。 本發明的鏈狀氧化矽系中空微粒子之製造方法的特徵 爲由下述步驟（a)〜（f)所構成。 (a )將矽酸鹽的水溶液及/或酸性矽酸液與鹼可溶的 無機化合物水溶液同時加到鹼水溶液中，或同時加到固體 成分濃度在0.0 1〜2重量％之範圍的種粒子所分散的鹼水 溶液中’以調製當以Si02表示氧化矽，以MOx表示氧化 矽以外的無機氧化物時的莫耳比M0x/Si02 ( A )在0.1〜2 之範圍的複合氧化物一次粒子分散液之步驟； (b )洗淨前述一次粒子分散液之步驟； (c)將洗淨後的一次粒子分散液，在電解質的存在 下’於5〇〜3 00°C進行水熱處理，以調製鏈狀複合氧化物 粒子分散液之步驟； (d )形成氧化砂或氧化矽.氧化鋁被覆層，調製氧化 矽或氧化矽·氧化鋁被覆鏈狀複合氧化物粒子分散液之步 -8 - 201034958 (e)於氧化矽或氧化矽·氧化鋁被覆鏈狀複合氧化物 粒子分散液中添加酸，去除構成該複合氧化物粒子之矽以 外的元素之至少一部分，而成爲鏈狀氧化矽系中空微粒子 分散液之步驟； (f )洗淨所得的分散液之步驟。 HK述步驟（c)中的電解質較佳爲驗土類金屬鹽。 0 於前述步驟（f)之後’較佳爲接著實施下述步驟（g )0 (g)將鏈狀氧化矽系中空微粒子分散液，在50〜 3 00 °C之範圍進行水熱處理之步驟。 前述步騾（d)較佳爲下述步驟（d-Ι)、下述步驟（ d-2)、下述步驟（d-3)中任一者。 (d- 1 )於前述步驟（c )所得之鏈狀複合氧化物粒子 分散液中’添加鹼水溶液與下述化學式（1 )所示的有機 Ο 矽化合物及/或其部分水解物’在鏈狀複合氧化物粒子上 形成氧化矽被覆層之步驟 R n S i X( 4 - η ) 〔惟’ R:碳數1〜i〇之非取代或取代烴基、丙烯醯基、 環氧基、甲基丙烯醯基、胺基、CF2基；x:碳數1〜4之 垸氧基、砍院醇基、鹵素或氫；n: 〇〜3的整數〕； (d-2)於前述步驟（c)所得之鏈狀複合氧化物粒子 -9 - 201034958 分散液中’添加鹼水溶液與酸性矽酸液’在鏈狀複合氧化 物粒子上形成氧化矽被覆層之步驟； (d-3 )於前述步驟（c )所得之鏈狀複合氧化物粒子 分散液中，添加矽酸鹼水溶液與鋁酸水溶液’在鏈狀複合 氧化物粒子上形成氧化矽被覆層之步驟。 本發明的透明被膜形成用塗佈液之特徵爲含有前述鏈 狀氧化矽系中空微粒子與基質形成成分所成。 本發明的附透明被膜之基材之特徵爲用前述透明被膜 形成用塗佈液所形成的透明被膜係單獨或與其它被膜一起 形成於基材表面上。 發明的效果 若依照本發明，可提供具有貫通外殻內部的空洞之新 穎鏈狀氧化矽系中空微粒子。此新穎鏈狀氧化矽系中空微 粒子係比中空微粒子以鏈狀連結的氧化矽系中空微粒子還 低的折射率。 若依照本發明的製造方法，可提供低折射率的鏈狀氧 化矽系中空微粒子。 又，可提供含有前述鏈狀氧化矽系中空微粒子一被膜 形成用基質形成成分，而安定性、膜形成性等優異的被膜 形成用塗料。 再者’可提供將含有前述鏈狀氧化矽系中空微粒子的 被膜形成於基材的表面上，而低折射率且與基材的密接性 、強度、耐擦傷性及防反射能力等優異的附被膜之基材。 -10- 201034958 實施發明的形態 〔鏈狀氧化矽系中空微粒子〕 首先’說明本發明的鏈狀氧化矽系中空微粒子。 本發明的鏈狀氧化矽系中空微粒子之特徵爲在外部具 有外殻、在內部具有空洞的氧化矽系中空微粒子（一次粒 子）以鏈狀連結，具有空洞互相貫通的貫通孔，平均長度 〇 (L)在20〜UOOnm之範圍，平均寬幅（W)在10〜 3 OOnm之範圍，折射率在1.1〇〜1.35之範圍。 氧化矽系中空微粒子（一次粒子） 鏈狀氧化矽系中空微粒子係在外部具有外殼、在內部 具有空洞氧化矽系中空微粒子（一次粒子）以鏈狀連結。 圖1中顯示本發明的鏈狀氧化矽系中空微粒子之截面 的模型圖。 Ο 本發明中的氧化矽系中空微粒子（一次粒子）的大小 係大約10〜300nm’更以在15〜200nm之範圍爲佳。 當一次粒子的大小未達1 Onm時，有難以鏈狀化而凝 聚的傾向’有難以得到所欲低折射率的鏈狀氧化矽系中空 微粒子之情況。 若一次粒子的大小超過30〇nm，則由於粒子過大，鏈 狀化係困難’還是有難以得到所欲鏈狀氧化矽系中空微粒 子之情況。 鏈狀氧化矽系中空微粒子的平均寬幅（W)係如圖1 -11 - 201034958 所示地’取與一次粒徑相同程度或比其大之値，爲丨〇〜 300nmm’更以在15〜200 nm之範圍爲佳。 鏈狀氧化矽系中空微粒子係一次粒子以鏈狀連結，但 是平均長度（L·)爲20〜1500nm，更以在40〜lOOOnm之 範圍爲佳。 當平均長度（L)未達2〇nm時，意味最小粒徑！ 0nrn 的一次粒子未達2個，無法成爲所欲低折射率的鏈狀氧化 矽系中空微粒子，而平均長度（L)若超過1500nm，則進 行凝聚’或互相交絡，有難以得到所欲鏈狀氧化矽系中空 微粒子之情況。 外殼的厚度（Ts)雖然亦隨著一次粒徑或平均寬幅（ W)而不同’但是爲 2〜100nm，更以在 3〜50nm之範圍 爲佳。 外殼的厚度（Ts )未達2nm者，係在去除後述矽以外 的元素之至少一部分時，有無法保持中空構造之情況，有 難以得到所欲鏈狀氧化矽系中空微粒子之情況。 外殻的厚度（Ts)若超過l〇〇nm，則內部的空隙小， 有難以得到所欲低折射率的鏈狀氧化矽系中空微粒子之情 況。 又，外殼的厚度（Ts)與前述平均寬幅（w)之比（ Ts) /(W)爲0.05〜0.30，更以在〇.05〜0.2之範圍爲佳 〇 當（Ts) / (W)未達0.05時’於去除矽以外的元素 之至少一部分時’有無法保持中空構造之情況，有難以得 -12- 201034958 到鏈狀氧化矽系中空微粒子之情況。 (Ts ) / ( W )若超過0.30，則內部的空隙小，有難以 得到所欲低折射率的鏈狀氧化矽系中空微粒子之情況。 前述貫通孔的平均直徑（Ds)與前述平均寬幅（W) 之比的（Ds) / (W)較佳爲0.1〜0.9，更佳在0.3〜0.8之 範圍。 當（Ds ) / ( W )未達0.1時，貫通孔的空隙小，對低 〇 折射率化的貢獻度小，有難以得到所欲低折射率的鏈狀氧 化矽系中空微粒子之情況。 得到（Ds ) / ( W )超過0.9的鏈狀氧化矽系中空微粒 子係困難。 如此的鏈狀氧化矽系中空微粒子係折射率爲1 . 1 〇〜 1.35’更以在1.10〜1.30之範圍爲佳。 得到鏈狀氧化矽系中空微粒子之折射率未達1 · 1 〇者 係困難，折射率超過1 . 3 5者雖然與基材的密接性、強度 Ο、耐擦傷性優異’但是防反射能力會變不足。 本發明的鏈狀氧化矽系中空微粒子係由氧化矽與氧化 矽以外的無機氧化物所構成，以Μ Ο x表示氧化矽以外的無 機氧化物時的莫耳比MOx/Si〇2較佳在o.oooi〜〇·2之範圍 〇 得到莫耳比Μ Ο x / S i Ο2未達〇 · 〇 〇 〇 1的鏈狀氧化矽系中 空微粒子係困難’莫耳比MOx/Si〇2超過〇.2者係製造方 法如後述’但是由於氧化矽以外的無機氧化物之去除少， 有得不到低折射率的鏈狀氧化矽系中空微粒子之情況。 -13- 201034958 於本發明的鏈狀氧化矽系中空微粒子中，作爲氧化矽 以外的無機氧化物，可舉出 Al2〇3、b2o3、Ti〇2 ' Zr〇2、 Sn02 ' Ce203、P2〇s ' Sb203、Mo03、Zn02、W03 等的 i 種或2種以上。作爲2種以上的無機氧化物，可例示 Ti02-Al203、Ti02-Zr02 等。其中較佳爲 Al2〇3。 再者，本發明的鏈狀氧化矽系中空微粒子之平均長度 (L)、平均寬幅（W)係拍攝鏈狀氧化矽系中空微粒子 的透射型電子顯微鏡照片（TEM )，藉由游標卡尺來測定 1 00個粒子的長度及寬幅，其其平均値。 又，外殼的平均厚度（Ts)、貫通孔的平均直徑（Ds )係可藉由觀察粒子截面的透射型電子顯微鏡照片（TEM )而測定。 再者，折射率係藉由以下的程序來求得。 (1 )於蒸發器中採集鏈狀氧化矽系中空微粒子分散 液’使分散介質蒸發。 (2 )將此在1 20°C乾燥以成爲粉末。 (3 )將折射率已知的標準折射率液滴2、3滴到玻璃 板上’於其中混合上述粉末。 (4 )以各種標準折射率液進行上述（3 )的操作，將 混合液變成透明時的標準折射率液之折射率當作鏈狀氧化 矽系中空微粒子的折射率。 〔_化矽系微粒子的製造方法〕 接著，說明本發明的鏈狀氧化矽系中空微粒子之製造 -14 - 201034958 方法。 本發明之鏈狀氧化矽系中空微粒子的製造方法之特徵 爲由下述步驟（a)〜（f)所構成。 (a )將矽酸鹽的水溶液及/或酸性矽酸液與鹼可溶的 無機化合物水溶液同時加到鹼水溶液中’或同時加到固體 成分濃度在〇 · 〇 1〜2重量％之範圍的種粒子所分散的鹼水 溶液中，以調製當以Si〇2表示氧化矽，以MOx表示氧化 0 矽以外的無機氧化物時的莫耳比M0x/Si02 ( A )在〇.1〜2 之範圍的複合氧化物一次粒子分散液之步驟； (b )洗淨前述一次粒子分散液之步驟； (c )將洗淨後的一次粒子分散液，在電解質的存在 下，於5〇〜3 00°C進行水熱處理，以調製鏈狀複合氧化物 粒子分散液之步驟； (d )形成氧化矽或氧化矽·氧化鋁被覆層，調製氧化 矽或氧化矽·氧化鋁被覆鏈狀複合氧化物粒子分散液之步 〇 驟； (e )於氧化矽或氧化矽·氧化鋁被覆鏈狀複合氧化物 粒子分散液中添加酸，去除構成該複合氧化物粒子之矽以 外的元素之至少一部分，而成爲鏈狀氧化矽系中空微粒子 分散液之步驟； (〇洗淨所得的分散液之步驟。 · 步驟（a ) 作爲砂酸鹽’較宜使用由鹼金屬矽酸鹽、銨矽酸鹽及 -15- 201034958 有機鹼的矽酸鹽所選出的1種或2種以上之矽酸鹽。作爲 鹼金屬矽酸鹽，可舉出矽酸鈉（水玻璃）或矽酸鉀，作爲 有機鹼，可舉出四乙基銨鹽等的4級銨鹽、單乙醇胺、二 乙醇胺、三乙醇胺等的胺類’於銨的矽酸鹽或有機鹼的矽 酸鹽中，亦包含於矽酸液中加有4級銨氫氧化物、胺化合 物等的鹼性溶液。 作爲酸性矽酸液，可使用藉由以陽離子交換樹脂處理 、矽酸鹼水溶液等，去除鹼而得之矽酸液’特佳爲PH2〜 p Η 4、S i Ο 2濃度約7重量％以下的酸性矽酸液。 作爲無機氧化物’可舉出Al2〇3、B2〇3、Ti02、Zr02 、Sn02、Ce2〇3、P2O5、Sb203、Mo03、Zn02、W03 等的 1 種或2種以上。作爲2種以上的無機氧化物’可例示 Ti〇2-Al203、Ti02-Zr02 等。 其中，較佳爲Al2〇3，因爲容易得到球狀的一次粒子 ，容易去除。 作爲如此的無機氧化物之原料’較佳爲使用鹼可溶的 無機化合物，可舉出前述構成無機氧化物的金屬或非金屬 之含氧酸的鹼金屬鹽或鹼土類金屬鹽、銨鹽、4級銨鹽’ 更具體地，鋁酸鈉、四硼酸鈉、碳酸氧锆錢、銻酸鉀、錫 酸鉀、鋁矽酸鈉、鉬酸鈉、硝酸铈銨、磷酸鈉等係合適。 爲了調製複合氧化物一次粒子分散液’可預先個別地 調製前述無機化合物的鹼水溶液’或調製混合水溶液’將 此水溶液按照目的之氧化矽與氧化砂以外的無機氧化物之 複合比例，在鹼水溶液中’較佳爲在pH 1 0以上的鹼水溶 -16- 201034958 液中邊攪拌邊徐徐添加。 添加於鹼水溶液中的氧化矽原料與無機化合物原料之 添加比例，以S i 0 2表示氧化矽成分，以Μ Ο X表示氧化矽 以外的無機化合物時之莫耳比MOx/Si〇2爲〇.01〜2 ’尤其 以在〇·1〜1之範圍爲佳。MOx/Si02若未達〇.〇1 ’則最終 所得之鏈狀氧化矽系中空微粒子的空洞容積係不充分大’ 另一方面，MOx/Si02若超過2，則得到球狀的複合氧化物 0 一次粒子係困難，即使可以也會在去除矽以外的元素之際 破壞球狀的複合氧化物微粒子，結果會得不到在內部具有 空洞的鏈狀氧化矽系中空微粒。 莫耳比M0x/Si02若在0.01〜2之範圍’則複合氧化 物一次粒子的構造主要係成爲矽與矽以外的元素經由氧而 交互鍵結的構造。即，多生成在矽原子的4個結合手鍵結 有氧原子，在此氧原子鍵結有氧化矽以外的元素之構造’ 於後述的步驟（e)中在去除矽以外的元素之際’不會破 〇 壞以鏈狀連結的複合氧化物一次粒子之形狀’而可去除元 素Μ。 複合氧化物一次粒子的平均粒徑爲5〜28 〇nm ’更以 在10〜200nm之範圍爲佳。 複合氧化物一次粒子的平均粒徑未達5 nm時’最終所 得之鏈狀氧化矽系中空微粒子的外殼之比例變多，空洞谷 積的比例變不充分大，而若複合氧化物一次粒子的平均粒 徑超過280nm，則在步驟（b )的鏈狀化係困難’在步驟 (d )的矽以外之元素的去除變不充分’鏈狀氧化砂系中 -17- 201034958 空微粒子的空洞容積不充分大，得到低折射率的粒子會變 困難。 於本發明的製造方法中，在調製複合氧化物一次粒子 分散液之際，較佳爲以種粒子的分散液當作起始原料。 作爲種粒子，使用 Si02、Al2〇3 ' Ti〇2、Zr〇2、Sn02 及Ce02等的無機氧化物或此等的複合氧化物，例如3丨02-AI2O3、Ti〇2_Al2〇3、Ti〇2-Zr〇2、Si〇2-Ti〇2、Si〇2_Ti〇2_ A1203等的微粒子，通常較佳爲使用此等的溶膠。如此的 種粒子之分散液係可藉由習知的方法來調製。例如，可藉 由在對應於上述無機氧化物之金屬鹽、金屬鹽的混合物或 金屬烷氧化物等中添加酸或鹼而進行水解，視需要熟成而 獲得。 於種粒子分散鹼水溶液中，較佳爲在經調整亞pH 1 0 以上的種粒子分散鹼水溶液中，與在上述鹼水溶液中添加 的方法同樣地’邊攪拌邊添加前述化合物的水溶液。如此 地’若以種粒子當作種子而使複合氧化物微粒子成長，則 成長粒子的粒徑控制係容易，可得到粒度一致者。添加於 種粒子分散液中的氧化矽原料及無機氧化物之添加比例， 係與在前述鹼水溶液中添加時相同的範圍。 上述氧化矽原料及無機氧化物原料係在鹼側具有高的 溶解度。然而，若在此溶解度高的pH範圍中混合兩者， 則矽酸離子及鋁酸離子等的含氧酸離子之溶解度降低，此 等複合物析出而成長成膠體粒子，或析出在種粒子上而引 起粒子成長。 -18- 201034958 於本發明中，添加矽酸鹽的水溶液及/或酸性矽酸液 與鹼可溶的無機化合物水溶液，直到複合氧化物一次粒子 的平均粒徑（Dpl )變成5〜280nm爲止，添加可爲連續或 斷續的，較佳爲同時添加兩者。 再者，此時的莫耳比MOx/Si〇2 ( A )雖然在0.01〜2 之範圍，但是亦可以此莫耳比變小的方式邊變更邊添加。 於本發明的步驟（a )中，按照需要亦可在電解質鹽 〇 的存在下調製複合氧化物一次粒子。 此時，電解質鹽的莫耳數（MEa )與Si02的莫耳數（ MSa )之比（MEa ) / ( MSa )可以0 1〜10範圍添加，較佳 以0.2〜8之範圍的添加。 作爲電解質鹽，可舉出氯化鈉、氯化鉀、硝酸鈉、硝 酸鉀、硫酸鈉、硫酸鉀、硝酸銨、硫酸銨、氯化鎂、硝酸 鎂等的水溶性電解質鹽。 使用電解質鹽時，較佳爲在所得之複合氧化物一次粒 〇 子之平均粒徑的大約1 /5〜4/5的時間點進行添加，添加係 可在此時間點全量添加，也可添加鹼金屬矽酸鹽或氧化矽 以外的無機化合物，邊進行複合氧化物微粒子的粒子成長 邊連續或斷續地添加。 電解質鹽的添加量，雖然取決於複合氧化物一次粒子 分散液的濃度’但是當前述莫耳比（MEa ) / ( MSa )未達 o.l時，添加電解質鹽的效果係變不充分，在步驟（e)中 添加酸以去除構成複合氧化物一次粒子的矽以外之元素的 至少一部分之際’無法維持複合氧化物微粒子而破壞，得 -19 - 201034958 到在內部具有空洞的鏈狀氧化矽系中空微粒子係變困難。 關於添加如此電解質鹽的效果，其理由雖然未明確，但是 認爲於經粒子成長的複合氧化物一次粒子之表面上氧化矽 變多，酸不溶性的氧化矽係具有複合氧化物一次粒子的保 護膜之作用。 因此，雖然於後述的步驟（d)中形成氧化矽或氧化 矽·氧化鋁被覆層’但是亦可減薄所形成的氧化矽或氧化 矽·氧化鋁被覆層。 即使前述莫耳比（MEa) /(MSa)超過10，添加前述 電解質的效果也不會升高，而生成新的微粒子，或經濟性 降低。 步驟（b ) 步驟（a )所調製的複合氧化物一次粒子分散液，係 接著進行洗淨而去除陽離子、陰離子、電解質。 作爲洗淨方法，只要可去除陽離子、陰離子、電解質 ’則沒有特別的限制，可採用習知的方法。於本發明中， 由於粒子爲微粒，故合適地採用超濾膜法、離子交換樹脂 法。也可倂用雨者。 若洗淨不充分，則在下一步驟（c )中難以得到鏈狀 複合氧化物一次粒子。 步驟（C ) 於複合氧化物一次粒子分散液中添加電解質，在電解 -20- 201034958 質存在下，於50〜300 °C、更於80〜250 °C進行水熱處理’ 以調製鏈狀複合氧化物粒子分散液。 作爲電解質，只要可將複合氧化物一次粒子鏈狀化， 則沒有特別的限制，但於本發明中’較佳爲鹼土類金屬鹽 〇 作爲鹼土類金屬鹽，可舉出鎂、鈣等的鹽酸鹽、硝酸 鹽、硫酸鹽、有機酸鹽等。 © 於添加電解質之際的複合氧化物一次粒子分散液之濃 度，以固體成分計，爲0.1〜20重量％，更以在0.5〜10 重量％之範圍爲佳。 當複合氧化物一次粒子分散液的濃度以固體成分計未 達0.1重量％時，雖然能進行鏈狀化，但是生產性低，而 若複合氧化物一次粒子分散液的濃度以固體成分計超過20 重量％，則粒子會成爲凝聚體。 又，電解質的添加量，係以分散液中的複合氧化物一 ❹ 次粒子的重量（WP1)與電解質的重量（WEL)之比（WEL )/(Wpi)爲0.001〜0.8，更以在0.01〜0.2之範圍爲佳 〇 當（WEL) / ( WPI )未達0.001時，複合氧化物一次 粒子會不進行鏈狀化，而（WEL) / ( WP1 )若超過0.8，則 複合氧化物的一次粒子會成爲凝聚體。 於本發明中，除了電解質，亦可添加酸性矽酸液。酸 性矽酸液係與後述步驟（d-2 )所用的酸性矽酸液同樣的 酸性矽酸液，酸性矽酸液的添加量係以分散液中的複合氧 -21 - 201034958 化物一次粒子之重量（WP1)與酸性矽酸液的Si〇2之重量 (Ws)的比（Ws) / (Wp丨）在 〇_〇1〜1，更以在 0.02〜 0.5之範圍爲佳。 當（WS ) / ( WP1 )未達〇.〇1時，雖然取決於複合氧 化物一次粒子的粒徑而亦不同，但是會促進鏈狀化，或無 法維持已鏈狀化的複合氧化物一次粒子之鏈狀，而若（WS )/ ( WP1 )超過1，則在後述步驟（e )中矽以外的元素之 去除會變困難，即使可去除也會無法形成鏈狀粒子內部的 空洞互相貫通的貫通孔。 當水熱處理溫度未達50 °C時，鏈狀化係不進行，單分 散的複合氧化物一次粒子大量殘存，而若水熱處理溫度超 過3 00 °C，則凝聚粒子有增大的傾向。 再者，水熱處理時間雖然取決於溫度而亦不同’但是 大約1〜2 4小時。 步驟（d ) 接著，形成氧化矽或氧化矽·氧化鋁被覆層。 爲了形成氧化矽或氧化矽·氧化鋁被覆層，有3個方 法。第1方法係步驟（d-1 )，爲在前述步驟（c )所得之 鏈狀複合氧化物粒子分散液中，添加鹼水溶液與以下述化 學式（1 )所示的有機矽化合物及/或其部分水解物之方法201034958 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to a through-microparticle, the chain-shaped oxidized sand is a chain-shaped cerium oxide-based hollow fine particle, and a transparent film containing a bright film is formed on a surface of a substrate. [Prior Art] The particle size is 〇. 1~ It is well known (refer to the patent document that a core made of a material other than an aqueous solution of an alkali metal citrate is not produced from a dense cerium oxide shell (see Patent Document 3, etc.). Furthermore, the spherical cerium oxide particles having a concentration of 外 in the outer peripheral portion are thicker and thicker in the inner side. In addition, the applicant has previously used a porous oxide particle size composite oxide fine particle case. a method for producing a cerium oxide-based inorganic oxide which forms a cerium oxide inorganic oxide on a core particle of cerium oxide and cerium oxide, and a hollow oxidized hollow granule fine particle formed by a hollow inside, and a coating liquid for forming a transparent film containing the urethane A porous cerium oxide particle system having a chain of cerium oxide-based hollow fine particles, a hollow cerium oxide particle system of about 300 μm, and a patent document 2, etc.). Further, the active cerium oxide is precipitated by cerium oxide to destroy the cerium oxide shell to remove the material, and the method of hollow particles is known as a shell, the central portion is hollow, and the shell is a core-shell of the outer thick I-tilt structure. The micron size of the structure is known (refer to Patent Document 4 and the like). It is proposed to completely cover a large number of surfaces by yttrium oxide or the like to obtain a low refractive index nanometer (refer to Patent Document 5), and to further introduce a composite oxide coating layer made of an external inorganic oxide, followed by removal of cerium oxide. When cerium oxide is coated, a nanometer-sized cerium oxide-based fine particle having a low refractive index of -5 to 201034958 is provided inside (see Patent Document 6). On the other hand, the present applicant has previously proposed to form chain-shaped cerium oxide particles by hydrothermal treatment of cerium oxide particles under weakly acidic conditions (see Patent Document 7). In the non-hollow particles, since the refractive index of the particles is not 1.25 or less, in order to obtain particles having a low refractive index, the applicant further proposes to form a chain by adding an electrolyte substance in the formation stage of the hollow oxidized sand particles. Hollow oxide sand particles (see Patent Documents 8 and 9). However, in the cerium oxide-based hollow particles related to the proposal of the above-mentioned applicant, depending on the purpose and use of the particles, a sufficient low refractive index effect may not be obtained. In other words, even if the inside of each particle is hollowed out, the void volume is limited from the viewpoint of the particle strength, and there is a limit even if the refractive index is low. Therefore, it is required to have cerium oxide hollow fine particles having a different particle structure from the conventional one. CITATION LIST Patent Literature Patent Literature 1: JP-A-6-3306 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The present invention is based on the invention described in the aforementioned Patent Document 6 on the basis of the invention described in the above Patent Document 6 (Patent Document No. JP-A-2005-99435). In order to obtain a low refractive index cerium oxide-based fine particle, the porous composite oxide particles (primary particles) made of an inorganic oxide other than cerium oxide and cerium oxide are chained. A method of coating the surface of the chain-like particles with cerium oxide and then removing the inorganic oxide other than cerium oxide to produce chain cerium oxide-based hollow fine particles having pores penetrating the inside of the outer casing. Further, the object of the present invention is to provide a The aforementioned chain With the silicon oxide film-based hollow fine particles with a matrix forming component, and is excellent in film stability, film-forming coating material or the like. Further, an object of the present invention is to provide a film containing the chain-like yttria-based hollow fine particles on a surface of a substrate, and having a low refractive index and adhesion to a substrate, strength, scratch resistance, and anti-reflection. Excellent adhesion film substrate such as ability and anti-glare performance. Means for Solving the Problems The chain-shaped yttrium oxide-based hollow fine particles of the present invention are characterized in that the yttrium oxide-based hollow fine particles (primary particles) having a shell on the outside and having voids therein are connected in a chain shape, and have through-holes through which voids are intervening. The length 201034958 (L) is in the range of 20 to 1 500 nm, and the average width (w) is in the range of l 〇 300 300 nm, and the refractive index is in the range of 〜 1.35. Preferably, the thickness (Ts) of the outer casing is in the range of 2 to 100 nm, and the ratio (Ts) / (W) of the average width (W) is in the range of 0.05 to 0.30. The ratio (Ds) / (W) of the ratio of the average diameter (Ds) of the through holes to the average width (W) is preferably in the range of 0.1 to 0.9. Preferably, it is composed of an inorganic oxide other than cerium oxide and cerium oxide, and when the inorganic oxide other than oxidized sand is represented by MOS, the molar ratio MOx/Si 〇 2 is in the range of 0.0001 to 0.2. The method for producing a chain-like cerium oxide-based hollow fine particle of the present invention is characterized by the following steps (a) to (f). (a) simultaneously adding an aqueous solution of a citrate and/or an acidic citric acid solution to an aqueous solution of an alkali-soluble inorganic compound to an aqueous alkali solution, or simultaneously adding a seed having a solid concentration of 0.01 to 2% by weight. In the dispersed aqueous alkali solution, the composite oxide primary particle dispersion in the range of 0.1 to 2 in the range of 0.1 to 2 in the case where the cerium oxide is represented by SiO 2 and the inorganic oxide other than cerium oxide is represented by MOx. a step of washing liquid; (b) a step of washing the primary particle dispersion; (c) hydrothermalizing the washed primary particle dispersion in the presence of an electrolyte at 5 〇 to 300 ° C to prepare a step of forming a chain-like composite oxide particle dispersion; (d) forming an oxide sand or a cerium oxide-alumina coating layer, and preparing a cerium oxide or cerium oxide-alumina-coated chain-like composite oxide particle dispersion step -8 - 201034958 (e) adding an acid to the dispersion of the cerium oxide or the cerium oxide-alumina-coated chain-like composite oxide particles, and removing at least a part of the elements other than the ruthenium constituting the composite oxide particles to form chain cerium oxide-based hollow particles The dispersion step; dispersion of step (f) washing the resultant. The electrolyte in the step (c) is preferably a soil-measuring metal salt. 0 after the above step (f), it is preferred to carry out the following step (g): 0 (g) a step of hydrothermally treating the chain-like cerium oxide-based hollow fine particle dispersion in the range of 50 to 300 °C. The above step (d) is preferably any one of the following steps (d-Ι), the following step (d-2), and the following step (d-3). (d-1) The addition of an aqueous alkali solution to the organic ruthenium compound represented by the following chemical formula (1) and/or a partial hydrolyzate thereof in the chain-like composite oxide particle dispersion obtained in the above step (c) a step of forming a ruthenium oxide coating layer on the composite oxide particles R n S i X( 4 - η ) [only 'R: unsubstituted or substituted hydrocarbon group of carbon number 1 to i 、, acryl fluorenyl group, epoxy group, A Alkyl fluorenyl, an amine group, a CF2 group; x: a decyloxy group having a carbon number of 1 to 4, a decyl alcohol group, a halogen or a hydrogen; n: an integer of 〇~3; (d-2) in the aforementioned step ( c) The obtained chain-like composite oxide particles-9 - 201034958 The step of forming an yttrium oxide coating layer on the chain-like composite oxide particles by adding an aqueous alkali solution and an acidic citric acid solution in the dispersion; (d-3) In the chain-like composite oxide particle dispersion obtained in the step (c), a step of forming a cerium oxide coating layer on the chain-like composite oxide particles by adding an aqueous citric acid solution and an aqueous solution of alumina acid is added. The coating liquid for forming a transparent film of the present invention is characterized in that it contains the chain-like cerium oxide-based hollow fine particles and a matrix-forming component. The transparent film-attached substrate of the present invention is characterized in that the transparent film formed by the coating liquid for forming a transparent film is formed on the surface of the substrate alone or together with another film. EFFECT OF THE INVENTION According to the present invention, it is possible to provide novel chain-like yttrium oxide-based hollow fine particles having a cavity penetrating the inside of the casing. The novel chain-like yttrium oxide-based hollow microparticles have a lower refractive index than the cerium oxide-based hollow microparticles in which the hollow microparticles are linked in a chain. According to the production method of the present invention, chain-like oxidized cerium-based hollow fine particles having a low refractive index can be provided. In addition, it is possible to provide a coating material for film formation which is excellent in stability, film formability, and the like, and the matrix-forming component for forming a matrix of the oxidized cerium oxide-based hollow fine particles. In addition, it is possible to provide a film having the above-mentioned chain-like yttrium oxide-based hollow fine particles on the surface of the substrate, and having excellent refractive index, adhesion to the substrate, strength, scratch resistance, and antireflection ability. The substrate of the film. -10-201034958 MODE FOR CARRYING OUT THE INVENTION [Chain oxidized cerium oxide hollow fine particles] First, the chain cerium oxide-based hollow fine particles of the present invention will be described. The chain-shaped cerium oxide-based hollow fine particles of the present invention are characterized in that the cerium oxide-based hollow fine particles (primary particles) having a shell on the outside and having voids therein are connected in a chain shape, and have through-holes through which voids pass each other, and an average length 〇 ( L) In the range of 20 to UOOnm, the average width (W) is in the range of 10 to 300 nm, and the refractive index is in the range of 1.1 〇 to 1.35. Cerium Oxide-Based Hollow Microparticles (Primary Particles) The chain-shaped cerium oxide-based hollow microparticles have a shell on the outside and hollow yttrium-based hollow microparticles (primary particles) inside. Fig. 1 is a model diagram showing the cross section of the chain yttria-based hollow fine particles of the present invention.矽 The size of the cerium oxide-based hollow fine particles (primary particles) in the present invention is preferably about 10 to 300 nm', more preferably in the range of 15 to 200 nm. When the size of the primary particles is less than 1 Onm, there is a tendency that aggregation is difficult to be chained and it is difficult to obtain a chain-like yttrium oxide-based hollow microparticle having a desired low refractive index. When the size of the primary particles exceeds 30 Å, the particles are too large and the chaining is difficult. It is difficult to obtain the desired chain yttria-based hollow fine particles. The average width (W) of the chain yttria-based hollow microparticles is as shown in Fig. 1 -11 - 201034958 'taken to the same extent as or larger than the primary particle diameter, and is 丨〇~300nmm' more at 15 The range of ~200 nm is better. The linear cerium oxide-based hollow fine particle-based primary particles are linked in a chain shape, but the average length (L·) is 20 to 1,500 nm, and more preferably in the range of 40 to 100 nm. When the average length (L) is less than 2〇nm, it means the smallest particle size! 0nrn has less than two primary particles and cannot be a chain-like yttrium oxide hollow fine particle having a desired low refractive index. When the average length (L) exceeds 1500 nm, aggregation or mutual entanglement is performed, and it is difficult to obtain a desired chain. The case of cerium oxide hollow fine particles. The thickness (Ts) of the outer casing differs depending on the primary particle diameter or the average width (W), but is preferably 2 to 100 nm, more preferably in the range of 3 to 50 nm. When the thickness (Ts) of the outer casing is less than 2 nm, when at least a part of the elements other than the latter are removed, the hollow structure may not be maintained, and it may be difficult to obtain the desired chain-shaped cerium oxide-based hollow fine particles. When the thickness (Ts) of the outer shell exceeds 10 nm, the internal voids are small, and it is difficult to obtain the chain-like cerium oxide-based hollow fine particles having a desired low refractive index. Further, the ratio (Ts) / (W) of the thickness (Ts) of the outer casing to the average width (w) is 0.05 to 0.30, and more preferably in the range of 〇.05 to 0.2 (Ts) / (W). When it is less than 0.05, it is impossible to maintain a hollow structure when at least a part of elements other than ruthenium is removed, and it is difficult to obtain -12-201034958 to a chain yttria-based hollow fine particle. When (Ts) / (W) exceeds 0.30, the internal voids are small, and it is difficult to obtain a chain-like cerium oxide-based hollow fine particle having a desired low refractive index. The ratio (Ds) / (W) of the ratio of the average diameter (Ds) of the through holes to the average width (W) is preferably 0.1 to 0.9, more preferably 0.3 to 0.8. When (Ds) / (W) is less than 0.1, the voids in the through-holes are small, and the contribution to the refractive index of the low enthalpy is small, and it is difficult to obtain the chain-shaped cerium oxide-based hollow fine particles having a desired low refractive index. It is difficult to obtain a chain-like yttrium oxide hollow fine particle system in which (Ds) / (W) exceeds 0.9. Such a chain-like cerium oxide-based hollow fine particle system has a refractive index of 1.1 to 1.35', more preferably in the range of 1.10 to 1.30. It is difficult to obtain a chain yttria-based hollow fine particle having a refractive index of less than 1 · 1 ,, and a refractive index of more than 1.25 is excellent in adhesion to a substrate, strength Ο, and scratch resistance, but anti-reflection ability Not enough. The chain cerium oxide-based hollow fine particles of the present invention are composed of an inorganic oxide other than cerium oxide and cerium oxide, and the molar ratio MOx/Si 〇 2 when Μ 表示 x represents an inorganic oxide other than cerium oxide is preferred. The range of o.oooi~〇·2 is obtained by 莫 / / x / S i Ο 2 〇 未 〇〇〇 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫The production method of the second method is as follows. However, since the removal of the inorganic oxide other than cerium oxide is small, the chain cerium oxide-based hollow fine particles having a low refractive index are not obtained. In the chain cerium oxide-based hollow fine particles of the present invention, examples of the inorganic oxide other than cerium oxide include Al2〇3, b2o3, Ti〇2'Zr〇2, Sn02' Ce203, and P2〇s. 'i or two or more types of Sb203, Mo03, Zn02, W03, etc. Examples of the two or more inorganic oxides include Ti02-Al203 and TiO2-Zr02. Among them, Al2〇3 is preferred. Further, the average length (L) and the average width (W) of the chain yttria-based hollow fine particles of the present invention are transmission electron micrographs (TEM) of the chain-shaped yttria-based hollow fine particles, which are measured by a vernier caliper. The length and width of 100 particles, the average of which is 値. Further, the average thickness (Ts) of the outer casing and the average diameter (Ds) of the through holes can be measured by observing a transmission electron micrograph (TEM) of the cross section of the particles. Furthermore, the refractive index is obtained by the following procedure. (1) A chain-like cerium oxide-based hollow fine particle dispersion was collected in an evaporator to evaporate the dispersion medium. (2) This was dried at 1 20 ° C to become a powder. (3) Dropping of standard refractive index droplets 2, 3 having a known refractive index onto a glass plate, in which the above powder is mixed. (4) The operation of the above (3) is carried out using various standard refractive index liquids, and the refractive index of the standard refractive index liquid when the mixed liquid is made transparent is regarded as the refractive index of the chain-like yttrium-based hollow fine particles. [Method for Producing Chitosan-Based Fine Particles] Next, a method for producing the chain-shaped cerium oxide-based hollow fine particles of the present invention -14 - 201034958 will be described. The method for producing a chain yttria-based hollow fine particle of the present invention is characterized by the following steps (a) to (f). (a) adding an aqueous solution of a citrate and/or an acidic citric acid solution to an aqueous alkali solution simultaneously with an aqueous solution of an alkali-soluble inorganic compound or simultaneously adding a concentration of the solid component in a range of 1 to 2% by weight of 〇·〇 In the aqueous alkali solution in which the particles are dispersed, the molar ratio M0x/SiO 2 (A ) in the range of 〇.1 〜2 when the inorganic oxide other than oxidized 矽 is represented by x 〇 表示a step of a composite oxide primary particle dispersion; (b) a step of washing the primary particle dispersion; (c) a washed primary particle dispersion in the presence of an electrolyte at 5 〇 to 300 ° C is hydrothermally treated to prepare a chain-like composite oxide particle dispersion; (d) forming a cerium oxide or cerium oxide-alumina coating layer, and modulating cerium oxide or cerium oxide-alumina-coated chain-like composite oxide particles dispersed (e) adding an acid to the dispersion of the cerium oxide or the cerium oxide-alumina-coated chain-like composite oxide particles, and removing at least a part of the elements other than the ruthenium constituting the composite oxide particles to form a chain Cerium oxide system The step of emptying the fine particle dispersion; (the step of washing the obtained dispersion. · Step (a) as the sulphate' is preferably used from an alkali metal citrate, an ammonium citrate and a -15-201034958 organic base One or two or more kinds of citrates selected from citrate. Examples of the alkali metal citrate include sodium citrate (water glass) or potassium citrate, and examples of the organic base include tetraethylammonium. An amine such as a salt of a 4-grade ammonium salt such as a salt, a monoethanolamine, a diethanolamine or a triethanolamine, or an ammonium salt of an organic base, is also contained in a citric acid solution, and a quaternary ammonium hydroxide is added. An alkaline solution of a substance, an amine compound, etc. As the acidic citric acid solution, a citric acid solution obtained by removing a base by a cation exchange resin or an aqueous citric acid solution can be used, and it is particularly preferably PH2 to p Η 4. An acidic citric acid solution having a concentration of about 7 wt% or less of S i Ο 2 . Examples of the inorganic oxides include Al 2 〇 3 , B 2 〇 3 , TiO 2 , ZrO 2 , Sn 2 , Ce 2 〇 3 , P 2 O 5 , Sb 203 , Mo 3 , Zn 02 , One or two or more kinds of W03, etc. As two or more types of inorganic oxides, Ti〇2-Al203 and Ti02-Zr02 can be exemplified. Among them, Al2〇3 is preferable because it is easy to obtain spherical primary particles and is easily removed. The raw material of such an inorganic oxide is preferably an alkali-soluble inorganic compound, and the above-mentioned constituent inorganic oxide is exemplified. An alkali metal salt or an alkaline earth metal salt, an ammonium salt, a quaternary ammonium salt of a metal or non-metal oxyacid. More specifically, sodium aluminate, sodium tetraborate, zirconyl carbonate, potassium citrate, stannic acid Potassium, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, sodium phosphate, etc. are suitable. In order to prepare a composite oxide primary particle dispersion ', an aqueous alkali solution of the above-mentioned inorganic compound can be prepared individually or a mixed aqueous solution can be prepared. The aqueous solution is gradually added in an alkali aqueous solution, preferably in an alkali water-soluble-16-201034958 solution having a pH of 10 or more, in accordance with the mixing ratio of the target cerium oxide to the inorganic oxide other than the oxidized sand. The ratio of addition of the cerium oxide raw material to the inorganic compound raw material added to the aqueous alkali solution is represented by S i 0 2 as a cerium oxide component, and when Μ Ο X represents an inorganic compound other than cerium oxide, the molar ratio MOx/Si 〇 2 is 〇 .01~2 ' Especially good in the range of 〇·1~1. If MOx/Si02 does not reach 〇.〇1 ', the void volume of the chain yttria-based hollow fine particles finally obtained is not sufficiently large. On the other hand, if MOx/SiO 2 exceeds 2, a spherical composite oxide is obtained. When the primary particle system is difficult, even if the spherical composite oxide fine particles are destroyed when the elements other than the crucible are removed, the chain-like cerium oxide-based hollow fine particles having voids inside can not be obtained. When the molar ratio M0x/SiO2 is in the range of 0.01 to 2, the structure of the composite oxide primary particles is mainly a structure in which elements other than cerium and lanthanum are alternately bonded via oxygen. In other words, a structure in which an oxygen atom is bonded to four bonding hands of a ruthenium atom, and an element other than yttrium oxide is bonded to the oxygen atom is added to the element other than ruthenium in the step (e) described later. The element Μ can be removed without breaking the shape of the composite oxide primary particles linked in a chain shape. The average particle size of the composite oxide primary particles is preferably from 5 to 28 Å nm' in the range of from 10 to 200 nm. When the average particle diameter of the primary particles of the composite oxide is less than 5 nm, the ratio of the outer shell of the chain-shaped cerium oxide-based hollow fine particles obtained is increased, and the ratio of the void valley product is insufficiently large, and if the composite oxide primary particles are When the average particle diameter exceeds 280 nm, the chaining system in the step (b) is difficult. 'The removal of the element other than the enthalpy of the step (d) is insufficient. 'The void volume of the empty granules in the chain oxidized sand system -17-201034958 If it is not sufficiently large, it becomes difficult to obtain particles having a low refractive index. In the production method of the present invention, when the composite oxide primary particle dispersion is prepared, it is preferred to use a dispersion of seed particles as a starting material. As the seed particles, inorganic oxides such as SiO 2 , Al 2 〇 3 'Ti 〇 2, Zr 〇 2, SnO 2 and Ce 02 or the like, or composite oxides thereof, such as 3 丨 02-AI 2 O 3 , Ti 〇 2 _ Al 2 〇 3 , Ti 使用 are used. For the fine particles of 2-Zr〇2, Si〇2-Ti〇2, Si〇2_Ti〇2_A1203, etc., it is generally preferred to use such a sol. The dispersion of such particles can be prepared by a conventional method. For example, hydrolysis may be carried out by adding an acid or a base to a metal salt or a mixture of a metal salt or a metal alkoxide corresponding to the above inorganic oxide, and if necessary, it may be obtained by aging. In the aqueous solution of the seed-dispersed alkali, it is preferred to add an aqueous solution of the above compound while stirring in the same manner as in the method of adding the above-mentioned aqueous alkali solution to the aqueous solution of the seed particle-dispersed alkali having an adjusted sub-pH of 10 or more. When the composite oxide fine particles are grown by using the seed particles as seeds, the particle size control of the grown particles is easy, and the particle size can be obtained. The addition ratio of the cerium oxide raw material and the inorganic oxide added to the seed particle dispersion is the same as that in the case of adding the above aqueous alkali solution. The above cerium oxide raw material and inorganic oxide raw material have high solubility on the alkali side. However, when the two are mixed in the pH range in which the solubility is high, the solubility of the oxo acid ion such as citrate ion and aluminate ion is lowered, and these complexes are precipitated to grow into colloidal particles or precipitated on the seed particles. And cause the particles to grow. -18- 201034958 In the present invention, an aqueous solution of citrate and/or an aqueous solution of an acidic citric acid solution and an alkali-soluble inorganic compound are added until the average particle diameter (Dpl) of the composite oxide primary particles becomes 5 to 280 nm. The addition may be continuous or intermittent, preferably both. In addition, although the molar ratio MOx/Si〇2 (A) at this time is in the range of 0.01 to 2, it may be added while changing the molar ratio. In the step (a) of the present invention, the composite oxide primary particles can also be prepared in the presence of an electrolyte salt as needed. At this time, the ratio of the molar number of the electrolyte salt (MEa) to the molar number of the SiO 2 (MSa) (MEa) / (MSa) may be added in the range of 0 1 to 10, preferably in the range of 0.2 to 8. The electrolyte salt may, for example, be a water-soluble electrolyte salt such as sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, ammonium nitrate, ammonium sulfate, magnesium chloride or magnesium nitrate. When the electrolyte salt is used, it is preferably added at a time point of about 1/5 to 4/5 of the average particle diameter of the obtained composite oxide primary hazelnut, and the addition system may be added at this time point in full or may be added. The inorganic compound other than the alkali metal ruthenate or cerium oxide is continuously or intermittently added while growing the particles of the composite oxide fine particles. The amount of the electrolyte salt added depends on the concentration of the composite oxide primary particle dispersion 'but when the aforementioned molar ratio (MEa ) / ( MSa ) does not reach ol, the effect of adding the electrolyte salt becomes insufficient, in the step ( e) When an acid is added to remove at least a part of an element other than ruthenium constituting the primary particles of the composite oxide, it is impossible to maintain the composite oxide fine particles and is destroyed, and -19 - 201034958 is obtained to a chain-shaped yttrium oxide hollow having a cavity therein. Microparticle systems become difficult. Although the reason for the addition of such an electrolyte salt is not clear, it is considered that the cerium oxide on the surface of the composite oxide primary particles grown by the particles is increased, and the acid-insoluble cerium oxide-based protective film having the composite oxide primary particles. The role. Therefore, although the ruthenium oxide or ruthenium oxide-alumina coating layer is formed in the step (d) to be described later, the formed ruthenium oxide or ruthenium oxide-alumina coating layer may be thinned. Even if the aforementioned molar ratio (MEa) / (MSa) exceeds 10, the effect of adding the above electrolyte does not increase, and new microparticles are formed, or the economy is lowered. Step (b) The composite oxide primary particle dispersion prepared in the step (a) is subsequently washed to remove cations, anions and electrolytes. The washing method is not particularly limited as long as the cation, anion, and electrolyte can be removed, and a conventional method can be employed. In the present invention, since the particles are fine particles, an ultrafiltration membrane method or an ion exchange resin method is suitably employed. You can also use the rain. If the washing is insufficient, it is difficult to obtain the chain-like composite oxide primary particles in the next step (c). Step (C) adding an electrolyte to the composite oxide primary particle dispersion, and performing hydrothermal treatment at 50 to 300 ° C and more at 80 to 250 ° C in the presence of electrolysis-20-201034958 to modulate chain complex oxidation Particle dispersion. The electrolyte is not particularly limited as long as the composite oxide primary particles are chain-formed. In the present invention, the alkaline earth metal salt is preferably used as the alkaline earth metal salt, and examples thereof include salts of magnesium and calcium. Acid salts, nitrates, sulfates, organic acid salts, and the like. The concentration of the composite oxide primary particle dispersion at the time of adding the electrolyte is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the solid content. When the concentration of the composite oxide primary particle dispersion is less than 0.1% by weight in terms of solid content, although chaining can be performed, productivity is low, and if the concentration of the composite oxide primary particle dispersion exceeds 20 in terms of solid content At % by weight, the particles become aggregates. Further, the amount of the electrolyte added is such that the ratio (WEL) / (Wpi) of the weight (WP1) of the composite oxide in the dispersion to the weight (WEL) of the electrolyte is 0.001 to 0.8, more preferably 0.01. When the range of ~0.2 is better than (WEL) / (WPI) of less than 0.001, the composite oxide primary particles will not be chained, and if (WEL) / (WP1) exceeds 0.8, the composite oxide will be once Particles become aggregates. In the present invention, an acidic citric acid solution may be added in addition to the electrolyte. The acidic citric acid liquid is the same acidic citric acid liquid as the acidic citric acid liquid used in the step (d-2) described later, and the acid citric acid liquid is added in the weight of the composite oxygen--21 - 201034958 primary particle in the dispersion. The ratio (Ws) / (Wp 丨) of (WP1) to the weight (Ws) of the Si 〇 2 of the acidic citric acid solution is preferably 〇_〇1 to 1, more preferably in the range of 0.02 to 0.5. When (WS) / (WP1) does not reach 〇.〇1, although it depends on the particle size of the composite oxide primary particles, it promotes chaining or fails to maintain the chained composite oxide once. When the particles are in a chain shape, if (WS ) / ( WP1 ) exceeds 1, the removal of elements other than ruthenium in step (e ) described later becomes difficult, and even if it is removable, voids inside the chain-like particles cannot be formed. Through hole. When the hydrothermal treatment temperature is less than 50 °C, the chain-forming system does not proceed, and the single-dispersed composite oxide primary particles remain in a large amount, and if the hydrothermal treatment temperature exceeds 300 °C, the aggregated particles tend to increase. Further, although the hydrothermal treatment time varies depending on the temperature, it is about 1 to 24 hours. Step (d) Next, a ruthenium oxide or ruthenium oxide-alumina coating layer is formed. There are three methods for forming a ruthenium oxide or ruthenium oxide-alumina coating layer. The first method is the step (d-1), in which the alkali aqueous solution and the organic hydrazine compound represented by the following chemical formula (1) are added to the chain-like composite oxide particle dispersion obtained in the above step (c) and/or Partially hydrolyzed method

RnSlX(4-n) -22- 201034958 〔惟’ R :碳數1〜10之非取代或取代烴基、丙烯醯基、 環氧基、甲基丙烯醯基、胺基、CF2基；x:碳數1〜4之 烷氧基、矽烷醇基、鹵素或氫；η: 0〜3的整數〕。 作爲該有機矽化合物，具體地可舉出四甲氧基矽烷、 四乙氧基矽烷、四異丙氧基矽烷、甲基三甲氧基矽烷、二 甲基二甲氧基矽烷、苯基三甲氧基矽烷、二苯基二甲氧基 〇 矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、苯基三 乙氧基矽烷 '二苯基二乙氧基矽烷、異丁基三甲氧基矽烷 、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三 (β-甲氧基乙氧基）矽烷、3,3,3-三氟丙基三甲氧基矽烷 、甲基-3,3,3 -三氟丙基一甲氧基砂院、β-( 3,4 -環氧基環 己基）乙基三甲氧基矽烷、γ-環氧丙氧基三丙基三甲氧基 矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧 基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧 〇 基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙 輝醯氧基丙基甲基二乙氧基砂院、γ -甲基丙稀醯氧基丙基 三乙氧基矽烷、Ν-β (胺乙基）胺丙基甲基二甲氧基矽 烷、Ν-β (胺乙基）γ-胺丙基三甲氧基矽烷、Ν-β (胺乙基 )γ -胺丙基三乙氧基矽烷、γ -胺丙基三甲氧基矽烷、γ -胺 丙基三乙氧基矽烷、Ν -苯基- γ-胺丙基三甲氧基矽烷、丫_锍 基丙基三甲氧基矽院、三甲基矽院醇、甲基三氯砂院、甲 基二氯矽烷、二甲基二氯矽烷、三甲基氯矽烷、苯基三氯 矽烷、二苯基二氯矽烷、乙烯基三氯矽烷、三甲基溴矽烷 -23- 201034958 '二乙基矽烷等。 第2方法係步驟（d-2 )，爲於前述步驟（c )所得之 鏈狀複合氧化物粒子分散液中添加鹼水溶液與酸性矽酸液 之方法。 作爲酸性矽酸液，使用矽酸鹼水溶液，例如以離子交 換樹脂將水玻璃脫鹼後的酸性矽酸液。如此的酸性矽酸液 係濃度以S i Ο 2計爲〇. 1〜7重量％，p Η在0.1〜4之範圍。 第3方法係步驟（d-3 )，爲於前述步驟（c )所得之 鏈狀複合氧化物粒子分散液中添加矽酸鹼水溶液與鋁酸水 溶液之方法。 於上述中，氧化矽被覆層之形成時所用的有機矽化合 物或酸性矽酸液之添加量，以固體成分計係鏈狀複合氧化 物粒子的10〜2000重量％，尤其在20〜1000重量％之範 圍。 有機矽化合物或酸性矽酸液之添加量，以固體成分計 未達鏈狀複合氧化物粒子的10重量％時，由於被覆層薄’ 在步驟（e )中，於去除矽以外的元素之際，鏈狀化的粒 子會崩壞，而成爲在外部具有開放的空洞之鏈狀氧化矽系 中空微粒子。 有機矽化合物或酸性矽酸液之添加量以固體成分計若 超過鏈狀複合氧化物粒子的2000重量％，則矽以外的元素 之去除變困難，或由於外殼過厚，而得不到所欲低折射率 的鏈狀氧化矽系中空微粒子。 又，鹼水溶液的添加較佳爲使鏈狀複合氧化物粒子分 -24 - 201034958 散液的pH維持在7〜13·5，尤其以維持在1〇〜13爲佳。 當鏈狀複合氧化物粒子分散液的pH未達7時，鏈狀複合 氧化物粒子會凝聚，均一的被覆層之形成、粒子成長係不 能。 鏈狀複合氧化物粒子分散液的pH若超過13.5，由於 氧化矽、氧化鋁的溶解性高，故氧化矽層、氧化矽.氧化 鋁層的形成 '粒子成長變困難，而得不到所欲的鏈狀氧化 〇 矽系中空微粒子。 又，於步驟（d-3 )中，在氧化矽.氧化鋁被覆層的 形成中添加矽酸鹼水溶液與鋁酸水溶液時，莫耳比 Al203/Si02爲0.01〜0.5，更以在0.05〜0.3之範圍爲佳。 當莫耳比Al203/Si02未達〇.〇1時，與前述形成氧化 矽層者沒有不同，由於氧化矽•氧化鋁被覆層的形成而使 得矽以外的元素之去除容易性降低。 莫耳比Al2 03/Si02若超過0.5，則由於被覆層中的氧 Ο 化鋁過多，在步驟（e )中去除矽以外的元素之際，無法 維持被覆層，而會成爲在外部具有開放的空洞之鏈狀氧化 矽系中空微粒子。 於氧化矽·氧化鋁被覆層的形成中添加矽酸鹼水溶液 與鋁酸水溶液時的添加量，以氧化矽.氧化鋁固體成分計 爲鏈狀複合氧化物粒子的10〜2000重量％’更以在20〜 1 000重量％之範圍爲佳。 矽酸鹼水溶液與鋁酸水溶液的添加量以固體成分計未 達鏈狀複合氧化物粒子的10重量％時，由於被覆層薄’在 -25- 201034958 步驟（e )中，於去除矽以外的元素之際’鏈狀化的粒子 會崩壞，而成爲在外部具有開放的空洞之鏈狀氧化矽系中 空微粒子。 矽酸鹼水溶液與鋁酸水溶液的添加量以固體成分計若 超過鏈狀複合氧化物粒子的2000重量％，則矽以外的元素 之去除變困難，或由於外殻過厚，而得不到所欲低折射率 的鏈狀氧化矽系中空微粒子。 於形成氧化矽層、氧化矽·氧化鋁層之際，鏈狀複合 氧化物粒子分散液的濃度以固體成分計爲0.5〜20重量％ ，更以在1〜1 〇重量％之範圍爲佳。 鏈狀複合氧化物粒子分散液的濃度以固體成分計未達 0.5重量％時，則生產性降，而若超過20重量％，則粒子 會成爲凝聚體。 於形成氧化矽或氧化矽•氧化鋁被覆層之際，溫度通 常爲30〜150 °C，更以在50〜lOOt之範圍爲佳。 於形成氧化矽或氧化矽.氧化鋁被覆層之際，當溫度 未達30°C時’爲了形成氧化矽.氧化鋁被覆層，需要長時 間，或會無法形成所欲厚度的被覆層。 於形成氧化矽或氧化矽.氧化鋁被覆層之際，溫度若 超過150°C ’雖然隨著濃度而不同，但是鏈狀複合氧化物 粒子會凝聚。 步驟（e ) 於氧化ί夕或氧化矽.氧化鋁被覆複合氧化物粒子分散 -26- 201034958 液中添加酸，以去除構成氧化砂或氧化砂·氧化銘被覆複 合氧化物粒子之矽以外的元素之至少一部分，而成爲鏈狀 氧化矽系中空微粒子分散液。 於去除矽以外的元素之際，例如藉由添加礦酸或有機 酸來溶解去除，或使與陽離子交換樹脂接觸而離子交換去 除，或藉由組合此等方法來去除。 於去除矽以外的元素之際，氧化矽或氧化矽·氧化鋁 0 被覆複合氧化物粒子分散液中的氧化矽或氧化矽·氧化鋁 被覆複合氧化物粒子之濃度雖然隨著處理溫度而亦不同， 但是換算成氧化物較佳在0.1〜50重量％，尤其在0.5〜25 重量％之範圍。當氧化矽被覆複合氧化物粒子的濃度未達 0. 1重量％時，生產效率低，若超過5 0重量％，則在矽以 外的元素之含量多的複合氧化物粒子中，會無法均一地或 有效率地以少的次數來去除。 上述元素的去除，基於前述理由較佳爲進行直到所得 Ο 之鏈狀氧化矽系中空微粒子的M0x/Si02成爲0·000 1〜0.2 爲止，尤其成爲0.0001〜〇.1爲止。 步驟（f) 步驟（e )所得之鏈狀氧化矽系中空微粒子分散液’ 主要由於酸、矽以外的元素之陽離子及已溶解的氧化矽存 在，故將此等洗淨而去除。 作爲洗淨方法，係與步驟（b )同樣。洗淨程度較佳 爲進行直到酸、矽以外的元素之陽離子及已溶解的氧化矽 -27- 201034958 係實質上變成沒有爲止。 步驟（g) 對鏈狀氧化矽系中空微粒子分散液，以50 " 更佳爲以80〜25 0°C，進行水熱處理。 於本發明中，可照原樣地使用步驟（f)所 氧化矽系中空微粒子，較佳爲對於前述步驟（f 熱處理。 當水熱處理溫度未達50°C時，所得之鏈狀氧 空微粒子的外殼之緻密化變不充分，取決於鏈狀 中空微粒子的用法，溶劑或透明被膜形成用的基 分會進入空洞內，而得不到低折射率的效果。又 效地減低所得之鏈狀氧化矽系中空微粒子中的齡 等的雜質含量，被膜形成用塗佈液的安定性變不 此所得之被膜的強度會變不充分。 若水熱處理溫度超過3 00°C，則會成爲鏈狀 中空微粒子的凝聚體。 水熱處理後，視需要可與前述步驟（b )同 洗淨。 藉由洗淨，可進一步減低由於水熱處理所溶 /或氨。 再者，於本發明的鏈狀氧化矽系中空微粒子 法中，藉由對所得之鏈狀氧化矽系中空微粒子分 用超濾膜、旋轉式蒸發器等，以有機溶劑進行置 -3〇〇°c， 辱之鏈狀 )進行水 化矽系中 氧化矽系 質形成成 ，無法有 金屬或氨 充分，因 氧化矽系 樣地進行 出的鹼及 之製造方 散液，使 換，而可 -28 _ 201034958 得到有機溶劑分散溶膠。 又，所得之鏈狀氧化矽系中空微粒子，亦可藉由習知 的方法，以矽烷偶合劑等來處理而使用。 再者，於本發明的鏈狀氧化矽系中空微粒子之製造方 法中，在洗淨後，進行乾燥，視需要可進行煅燒。 〔透明被膜形成用塗佈液〕 〇 接著，說明透明被膜形成用塗佈液。 本發明的透明被膜形成用塗佈液係含有前述鏈狀氧化 矽系中空微粒子與基質形成成分。 分散介質 作爲塗佈液的分散介質，可以使用習知的分散介質， 具體地可舉出水、各種有機溶劑。 作爲用於本發明的有機溶劑，只要可溶解或分散後述 〇 的基質形成成分、視需要使用的聚合引發劑，同時可均勻 分散前述鏈狀氧化矽系中空微粒子，則沒有特別的限制， 可使用習知的分散介質·。 具體地’可舉出甲醇、乙醇、丙醇、2 -丙醇（IPA) 、丁醇、二丙酮醇、糠醇、四氫糠醇、乙二醇、己二醇、 異丙二醇等醇類；醋酸甲酯、醋酸乙酯、醋酸丁酯等的酯 類；二***、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇 單丁基醚、乙二醇異丙基醚、二乙二醇單甲基醚、二乙二 醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚等的醚類 -29- 201034958 :丙酮、甲基乙基酮、甲基異丁基酮、丁基甲基酮、環己 酮、甲基環己酮、二丙基酮、甲基戊基酮、二異丁基酮、 異佛爾酮、乙醯丙酮、乙醯乙酸酯等酮類、甲苯、二甲苯 等。此等可單獨使用’也可混合2種以上來使用。 聚合引發劑 於本發明的塗佈液中，連同鏈狀氧化矽系中空微粒子 '基質形成成分，亦可含有聚合引發劑。作爲聚合引發劑 ，沒有特別的限制而可使用眾所周知者，例如可舉出雙（ 2,4,6-三甲基苯甲醯基）苯基膦氧化物、雙（2,6-二甲氧基 苯甲醯基）2,4,4-三甲基-戊基膦氧化物' 2-羥基-甲基-2-甲基-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮 、1-羥基-環己基-苯基-酮、2-甲基-1-〔4-(甲硫基）苯基 〕-2-嗎啉基丙烷-1-酮等。 鏈狀氧化矽系中空微粒子 作爲鏈狀氧化矽系中空微粒子，使用前述鏈狀氧化矽 系中空微粒子。 於本發明的塗佈液中，視需要亦可含有鏈狀氧化矽系 中空微粒子以外的無機氧化物微粒子。 作爲無機氧化物微粒子，可舉出習知的低折射率無機 氧化物微粒子、高折射率無機氧化物微粒子、導電性無機 氧化物微粒子等。 基質形成成分係前述微粒子的分散體，指可在基材的 -30- 201034958 表面上形成被膜的成分，可由與基材的密接性或硬度、塗 佈性等之條件中合適的樹脂等中選擇使用，例如可舉出以 往所用的聚酯樹脂、丙烯酸樹脂、胺甲酸乙酯樹脂、氯乙 烯樹脂、環氧樹脂、蜜胺樹脂、氟樹脂、矽樹脂、縮丁醛 樹脂、酚樹脂、醋酸乙烯酯樹脂、紫外線硬化樹脂、電子 線硬化樹脂、乳化樹脂、水溶性樹脂、親水性樹脂、此等 樹脂的混合物、以及此等樹脂的共聚物或改性體等的塗料 〇 用樹脂、或前述院氧基砂院等的水解性有機砍化合物及此 等的部分水解物等。 透明被膜形成用塗佈液的基質形成成分與鏈狀氧化矽 系中空微粒子之合計濃度以固體成分計爲1〜60重量％， 更佳在2〜5 0重量％之範圍。 當透明被膜形成用塗佈液的固體成分濃度未達1重量 %時’一次塗佈會得不到所必要的膜厚，因此若重複塗佈 、乾燥，則密接性等變不充分，或經濟性不利。 〇 固體成分濃度若超過6 0重量。/。，則所得之透明被膜的 膜厚變不均句，或會發生裂紋。 透明被膜形成用塗佈液中的鏈狀氧化矽系中空微粒子 之濃度’係以所得之透明被膜中的鏈狀氧化矽系中空微粒 子之含量以固體成分計成爲5〜80重量％、尤其成爲1〇〜 5 0重量％之範圍來使用。 當透明被膜中的鏈狀氧化矽系中空微粒子之含量以固 體成分計未達5重量％時會得不到所欲低折射率的透明被 月旲，又，可不論本發明的鏈狀氧化矽系中空微粒子爲何而 -31 - 201034958 使用其它習知的低折射率粒子。 透明被膜中的鏈狀氧化矽系中空微粒子之含量以固體 成分計若超過8 0重量％，則膜的透明性、強度等會變不充 分。 再者，於視需要使用鏈狀氧化矽系中空微粒子以外的 無機氧化物微粒子時，粒子的合計濃度較佳爲亦與前述相 同的範圍。 又，透明被膜形成用塗佈液中的基質形成成分之濃度 ，係以所得之透明被膜中的基質成分之含量以固體成分計 成爲20〜95重量％、尤其成爲50〜90重量％之範圍來使 用。 更具體地，透明被膜形成用塗佈液中的鏈狀氧化矽系 中空微粒子之濃度，係以固體成分計爲0.05〜48重量％， 更以在0.1〜3 0重量％之範圍爲佳。 透明被膜形成用塗佈液中的基質形成成分之濃度，係 以固體成分計爲0.2〜57重量％，尤其以在〜54重量％ 之範圍爲佳。 藉由浸漬法、噴霧法、旋塗法、輥塗法、桿塗法、凹 版印刷法' 微凹版印刷法等周知的方法，將上述透明被膜 形成用塗佈液塗佈於基材上及進行乾燥，藉由紫外線照射 、加熱處理等常用方法使硬化，可形成透明被膜。 所得之透明被膜的膜厚較佳在200nm〜20μιη之範圍 -32- 201034958 〔附透明被膜之基材〕 接著，說明附透明被膜之基材。 本發明的附透明被膜之基材係將用前述透明被膜 用塗佈液所形成的透明被膜單獨或與其它被膜一起形 基材表面上。 基材 〇 作爲基材’係於玻璃、聚碳酸酯、丙烯酸樹脂、 、TAC等的塑膠薄片 '塑膠薄膜、塑膠透鏡、塑膠面 的基材、陰極線管、螢光顯示管、液晶表示板等的基 表面上形成被膜者’雖然依用途而不同，但是被膜係 或於基材上與保護膜、硬塗膜、平坦化膜、高折射率 絕緣膜、導電性樹脂膜' 導電性金屬微粒子膜、導電 屬氧化物微粒子膜、其它視需要所使用的基底膜等組 成。再者’組合使用時，本發明的被膜較佳爲形成在 €)表面上。 如此的透明被膜係可將前述透明被膜形成用塗佈 浸漬法'噴霧法、旋塗法、輥塗法等周知的方法於基 塗佈、乾燥’且再視需要，以加熱或紫外線照射等予 化而得。 上述基材之表面上所形成的透明被膜之折射率， 隨著鏈狀氧化矽系中空微粒子與基質成分等的混合比 所使用的基質之折射率而亦不同，但是爲1 .15〜1.42 折射率。再者’本發明的鏈狀氧化矽系中空微粒子本 形成 成於 PET 板等 材之 單獨 膜、 性金 合形 最外 液以 材上 以硬 雖然 率及 的低 身之 -33- 201034958 折射率爲1 .1 〇〜1 · 3 5。此係因爲本發明的鏈狀氧化矽系中 空微粒子在內部具有空洞，樹脂等的基質形成成分係止於 粒子外部，保持鏈狀氧化矽系中空微粒子內部的空洞。 再者’於上述附透明被膜之基材中，當基材的折射率 爲1.60以下時’推薦在基材表面上形成折射率爲ι ·6〇以 上的被膜（以下亦稱爲中間被膜）後，形成前述本發明之 含有鏈狀氧化矽系中空微粒子的透明被膜。中間被膜的折 射率若爲1 · 6 0以上’則與前述本發明之含有鏈狀氧化矽 系中空微粒子的透明被膜之折射率的差大，而得到防反射 性能更優異的附透明被膜之基材。中間被膜的折射率可藉 由爲了提高中間被膜的折射率所用之金屬氧化物微粒子的 折射率、金屬氧化物微粒子與樹脂等的混合比率及所使用 的樹脂之折射率來調整。 中間被膜的被膜形成用塗佈液係金屬氧化物粒子與被 膜形成用基質的混合液，視需要混合有機溶劑。作爲被膜 形成用基質，可使用與前述本發明之含有氧化矽系微粒子 的被膜同樣者’藉由使用相同的被膜形成用基質，可得到 兩被膜間之密接性優異的附被膜之基材。 藉由以下所示的實施例來更具體說明本發明。 【實施方式】 實施例1 鏈狀氧化矽系中空微粒子（Ρ- 1 )之調製 於100克氧化矽·氧化鋁溶膠（日揮觸媒化成（股） -34- 201034958 製：USBB-120，平均粒徑 25nm，Si02.Al2〇3 濃度 20 重 量％，固體成分中A12〇3含量27重量％ )中添加3 90〇克 純水，加溫到98。(： ’ 一邊保持在此溫度’ 一邊以6小時添 加1 750克當作Si02的濃度1.5重量％之砂酸鈉水溶液與 1 75 0克當作A12〇3的濃度〇.5重量％之鋁酸鈉水溶液’而 得到Si〇2. Al2〇3 —次粒子（P-1)分散液。此時的莫耳比 爲MOx/SiO2 = 0.2。又’此時的反應液之pH爲12.0。此分 0 散液的一次粒子平均粒徑爲3 5 nm。（步驟（a )) 接著，以超濾膜法洗淨si〇2 . Al2〇3 —次粒子（P-1 ) 分散液，進行濃縮而成爲固體成分濃度5重量％的Si〇2· Al2〇3 —次粒子（P-1 )分散液。（步驟（b )) 另途，調製混合有1 3 6克當作s i Ο 2的濃度2重量°/。之 酸性矽酸液與5.4克當作用於鏈狀化的電解質之濃度10 重量％的C a ( Ν Ο 3 ) 2水溶液之水溶液’與3 0 0克固體成 分濃度5重量％的Si02 . Al2〇3 —次粒子（P-1 )分散液混 Ο 合，在其中添加9克濃度2重量％的NaOH水溶液後’於 1 5 0 r進行3小時水熱處理’以調製固體成分濃度5重量％ 的鏈狀複合氧化物粒子（P-1 )分散液。接著冷卻到常溫 。此時的分散液之pH爲10.9。（步驟（C)) 接著，於300克固體成分濃度5重量％的鏈狀複合氧 化物粒子（P - 1 )分散液中添加3 9 0 0克純水’加溫到9 8 °C ，一邊保持此溫度，一邊以1 7小時添加1 5 3 〇克當作S i Ο 2 的濃度1.5重量％之矽酸鈉水溶液與50〇克當作ai2o3的 濃度〇 . 5重量％之鋁酸鈉水溶液’而得到氧化矽·氧化鋁 -35- 201034958 被覆鏈狀複合氧化物粒子（p_1)分散液。（步驟（d)) 隨後，以超濾膜法洗淨’進行濃縮’於500克固體成 分濃度爲13重量％的氧化矽·氧化鋁被覆鏈狀複合氧化物 粒子（P-1 )分散液中添加I，：125克純水’接著滴下濃鹽酸 (濃度35.5重量％)而成爲pHl.O’進行脫鋁處理。其次 ，一邊添加1 〇 L的ρ Η 3之鹽酸水溶液與5 L的純水’一邊 以超濾膜來分離.洗淨所溶解的鋁鹽’而得到固體成分濃 度2 0重量％的鏈狀氧化矽系中空微粒子（Ρ -1 )之水分散 液。（步驟（e ))(步驟（f)) 對於所得之鏈狀氧化矽系中空微粒子（p-1 ) ’測定 平均寬幅、平均長度、外殼厚度、貫通孔的平均直徑、 MOx/Si02 (莫耳比）及折射率，表1中顯示結果。於以下 所示的實施例與比較例中亦同樣地測定’表1中顯不結果 〇 此處，平均粒徑係藉由動態光散射法來測定’折射率 係使用CARGILL製的SeriesA、AA當作標準折射液’以 前述方法來測定。MOx係以ICP發光分光分析裝置（島津 製作所：ICPS-8 100)來測定，Si〇2係使用由在1 000°C煅 燒之際的殘存固體成分之重量去除MOx、Na20的重量後 之値。 附透明被膜之基材（A-1)的製造 對上述所得之固體成分濃度2 0重量％的鏈狀氧化矽系 中空微粒子（P-1 )之水分散液，使用超濾膜，以乙醇置 -36- 201034958 換溶劑，而調製固體成分濃度20重量％的鏈狀氧化矽系中 空微粒子（p-i)之醇分散液。 充分混合50克鏈狀氧化矽系中空微粒子（P-1 )之醇 分散液經乙醇稀釋成固體成分濃度5重量％的分散液、3 克丙烯酸樹脂（Hitaroid 1 007，日立化成（股）製）及47 克異丙醇與正丁醇的1 /1 (重量比）混合溶劑，以調製塗 佈液。 C 以桿塗法將此塗佈液塗佈在PET薄膜上，於80 °C使乾 燥1分鐘，而得到透明被膜之膜厚爲1 〇〇nm的附透明被膜 之基材（A-1 )。表2中顯示此附透明被膜之基材（A-1 ) 的全光線透過率、霧度、波長5 50nm的光線之反射率、被 膜的折射率、密接性、耐擦傷性及鉛筆硬度。於以下所示 的實施例與比較例中亦同樣地測定，表2中顯示結果。 全光線透過率及霧度係藉由霧度計（SUGA試驗機（ 股）製）來測定，反射率係藉由分光光度計（日本分光公 Ο 司，Ubest-55 )來測定。又，被膜的折射率係藉由橢圓偏 光計（ULVAC公司製，EMS-1 )來測定。再者，未塗佈之 PET薄膜係全光線透過率爲90.7%、霧度爲2.0%、波長 5 5 0 n m之光線的反射率爲7.0 %。 鉛筆硬度係根據；FIS K 5400，以鉛筆硬度試驗器來測 定。即，對於被膜表面以4 5度的角度安裝鉛筆，負載指 定的荷重，以一定速度拉引，觀察有無傷痕。 又，於附透明被膜之基材（A -1 )的表面用刀片以縱 橫1 mm的間隔弄出〗1條平行的傷痕以製作1 00個方格’ -37- 201034958 接著在其上黏著賽珞玢膠帶，其次以下列3個等級來分類 將賽珞玢膠帶剝離時被膜未剝離而殘存的方格數，評價密 接性。 殘存方格數90個以上：◎ 殘存方格數85〜89個：〇 殘存方格數8 4個以下：△ 耐擦傷性係使用# 〇〇〇〇鋼絲棉，以荷重5 00g/cm2滑 動50次，目視觀察膜的表面，藉由以下的基準來評價。 沒有看到筋條傷痕：◎ 稍微看到筋條傷痕：〇 看到多數的筋條傷痕：△RnSlX(4-n) -22- 201034958 [only 'R: unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, acryl fluorenyl group, epoxy group, methacryl fluorenyl group, amine group, CF2 group; x: carbon An alkoxy group having 1 to 4, a stanol group, a halogen or hydrogen; η: an integer of 0 to 3). Specific examples of the organic ruthenium compound include tetramethoxy decane, tetraethoxy decane, tetraisopropoxy decane, methyl trimethoxy decane, dimethyl dimethoxy decane, and phenyl trimethoxy. Base decane, diphenyl dimethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, phenyl triethoxy decane 'diphenyl diethoxy decane, isobutyl Trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (β-methoxyethoxy) decane, 3,3,3-trifluoropropyltrimethoxy decane, Methyl-3,3,3-trifluoropropyl-methoxylate, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxytripropyl Trimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-methylpropenyloxypropylmethyldi Methoxydecyl decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propyl methoxy methoxy methyl dimethyl ethoxylate, γ-methyl propyl sulfoxide Propyltriethoxydecane , Ν-β (amine ethyl) amine propyl methyl dimethoxy decane, Ν-β (amine ethyl) γ-aminopropyl trimethoxy decane, Ν-β (amine ethyl) γ - amine C Triethoxy decane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, Ν-phenyl-γ-aminopropyltrimethoxydecane, 丫-mercaptopropyltrimethyl Oxime, trimethyl phenol, methyl trichloride, methyl dichloro decane, dimethyl dichloro decane, trimethyl chloro decane, phenyl trichloro decane, diphenyl dichloro decane , vinyl trichlorodecane, trimethylbromodecane-23- 201034958 'diethyl decane, and the like. The second method is the step (d-2), which is a method of adding an aqueous alkali solution and an acidic citric acid solution to the chain-like composite oxide particle dispersion obtained in the above step (c). As the acidic citric acid solution, an aqueous citric acid solution is used, for example, an acidic citric acid solution obtained by deionizing water glass with an ion exchange resin. The concentration of the acidic citric acid solution is i. 1 to 7 wt%, and p Η is in the range of 0.1 to 4, based on S i Ο 2 . The third method is a step (d-3) of adding a citric acid aqueous solution and an aqueous aluminate solution to the chain-like composite oxide particle dispersion obtained in the above step (c). In the above, the amount of the organic cerium compound or the acidic citric acid solution used for forming the cerium oxide coating layer is 10 to 2000% by weight, particularly 20 to 1000% by weight, based on the solid content. The scope. When the amount of the organic cerium compound or the acidic citric acid solution is less than 10% by weight of the chain-like composite oxide particles, the coating layer is thin, in the step (e), when removing elements other than cerium The chain-like particles collapse and become chain-shaped yttria-based hollow fine particles having open pores on the outside. When the amount of the organic cerium compound or the acidic citric acid solution exceeds 2000% by weight of the chain-like composite oxide particles, the removal of elements other than cerium is difficult, or the outer shell is too thick, and the desired amount is not obtained. Low refractive index chain yttrium oxide hollow fine particles. Further, the addition of the aqueous alkali solution is preferably such that the pH of the chain-like composite oxide particles is maintained at 7 to 13.5, particularly preferably at 1 to 13 . When the pH of the chain-like composite oxide particle dispersion is less than 7, the chain-like composite oxide particles are aggregated, and formation of a uniform coating layer or particle growth is impossible. When the pH of the chain-like composite oxide particle dispersion exceeds 13.5, since the solubility of cerium oxide and aluminum oxide is high, the formation of the cerium oxide layer and the cerium oxide-alumina layer becomes difficult, and the desired particle growth becomes difficult. The chain of cerium oxide is hollow microparticles. Further, in the step (d-3), when an aqueous citric acid solution and an aqueous solution of aluminate are added to the formation of the cerium oxide-alumina coating layer, the molar ratio of Al203/SiO 2 is 0.01 to 0.5, more preferably 0.05 to 0.3. The range is good. When the molar ratio of Al203/SiO2 is less than 〇1〇, it is not different from the above-described formation of the ruthenium oxide layer, and the ease of removal of elements other than ruthenium is lowered due to the formation of the ruthenium oxide-alumina coating layer. When the molar ratio of Mo2 is more than 0.5, the amount of aluminum oxide in the coating layer is too large, and when the element other than cerium is removed in the step (e), the coating layer cannot be maintained, and the coating layer is opened to the outside. A hollow chain of cerium oxide hollow fine particles. The amount of addition of the aqueous ceric acid solution and the aqueous solution of alumina in the formation of the cerium oxide-alumina coating layer is 10 to 2000% by weight of the chain-like composite oxide particles based on the solid content of cerium oxide. It is preferably in the range of 20 to 1 000% by weight. When the amount of the aqueous solution of the citric acid and the aqueous solution of the aluminate is less than 10% by weight of the chain-like composite oxide particles, the coating layer is thinner than in the step (e) of -25 to 201034958, At the time of the element, the chain-like particles collapse and become chain-shaped yttria-based hollow fine particles having open pores on the outside. When the amount of the aqueous solution of the citric acid and the aqueous solution of the aluminate exceeds 2000% by weight of the chain-like composite oxide particles, the removal of elements other than ruthenium is difficult, or the outer shell is too thick to be obtained. Chain-like yttrium oxide hollow fine particles having a low refractive index. When the cerium oxide layer or the cerium oxide-alumina layer is formed, the concentration of the chain-like composite oxide particle dispersion is preferably 0.5 to 20% by weight in terms of solid content, more preferably in the range of 1 to 1% by weight. When the concentration of the chain-like composite oxide particle dispersion is less than 0.5% by weight in terms of solid content, the productivity is lowered, and if it exceeds 20% by weight, the particles become aggregates. In the case of forming a ruthenium oxide or ruthenium oxide-alumina coating layer, the temperature is usually from 30 to 150 ° C, more preferably from 50 to 100 Å. When a ruthenium oxide or ruthenium oxide-alumina coating layer is formed, when the temperature is less than 30 °C, it takes a long time or a coating layer of a desired thickness to form a ruthenium oxide-alumina coating layer. When a cerium oxide or cerium oxide-alumina coating layer is formed, the temperature exceeds 150 ° C. Although the concentration varies depending on the concentration, the chain-like composite oxide particles aggregate. Step (e) Adding an acid to the oxidized or yttrium oxide-alumina-coated composite oxide particle dispersion -26- 201034958 to remove elements other than the cerium oxide or the oxidized sand and the oxide-coated composite oxide particles At least a part thereof becomes a chain-like cerium oxide-based hollow fine particle dispersion. When removing elements other than ruthenium, for example, by adding a mineral acid or an organic acid, the solution is dissolved or removed, or contacted with a cation exchange resin to be ion-exchanged, or removed by a combination of these methods. When the element other than cerium is removed, the concentration of cerium oxide or cerium oxide-alumina-coated composite oxide particles in the cerium oxide or cerium oxide-alumina 0-coated composite oxide particle dispersion is different depending on the processing temperature. However, it is preferably converted into an oxide in an amount of from 0.1 to 50% by weight, particularly in the range of from 0.5 to 25% by weight. When the concentration of the cerium oxide-coated composite oxide particles is less than 0.1% by weight, the production efficiency is low, and if it exceeds 50% by weight, the composite oxide particles having a large content of elements other than cerium may not uniformly Or remove it efficiently with a small number of times. The removal of the above-mentioned elements is preferably carried out until the M0x/SiO 2 of the chain yttria-based hollow fine particles of the obtained ruthenium is from 0.000 to 0.22, particularly from 0.0001 to 〇1. Step (f) The chain cerium oxide-based hollow fine particle dispersion liquid obtained in the step (e) is mainly removed by the cation of an element other than an acid or hydrazine and the dissolved cerium oxide. The washing method is the same as in the step (b). The degree of washing is preferably such that the cations of the elements other than the acid or hydrazine and the dissolved cerium oxide -27-201034958 are substantially eliminated. Step (g) The chain cerium oxide-based hollow fine particle dispersion is hydrothermally treated at 50 " more preferably at 80 to 250 °C. In the present invention, the cerium-based hollow fine particles of the step (f) may be used as it is, preferably for the aforementioned step (f heat treatment. When the hydrothermal treatment temperature is less than 50 ° C, the obtained chain oxygen vacancies are obtained. The densification of the outer shell becomes insufficient. Depending on the usage of the chain-like hollow microparticles, the base component for solvent or transparent film formation enters the cavity, and the low refractive index effect is not obtained. The resulting chain yttrium oxide is also effectively reduced. The content of the impurities such as the age of the hollow fine particles, the stability of the coating liquid for forming a film is not sufficient, and the strength of the film obtained is insufficient. If the heat treatment temperature exceeds 300 ° C, it becomes chain-shaped hollow fine particles. After the hydrothermal treatment, if necessary, it can be washed together with the above step (b). By washing, the ammonia and the ammonia dissolved by the hydrothermal treatment can be further reduced. Further, in the chain oxidized cerium hollow of the present invention In the microparticle method, the obtained chain cerium oxide-based hollow fine particles are separated into an ultrafiltration membrane, a rotary evaporator, or the like, and the organic solvent is used to carry out water in a chain-like manner. In silicon-based silicon oxide is formed into a mass-based, metal or ammonia can not fully, and the base for producing a dispersion of silicon oxide-based due to the sample performed in the exchange, but may be -28 _ 201034958 obtain an organic solvent-dispersed sol. Further, the obtained chain cerium oxide-based hollow fine particles can be used by treatment with a decane coupling agent or the like by a conventional method. Further, in the method for producing a chain cerium oxide-based hollow fine particle of the present invention, after washing, drying is carried out, and if necessary, calcination can be carried out. [Coating Liquid for Forming Transparent Film] Next, a coating liquid for forming a transparent film will be described. The coating liquid for forming a transparent film of the present invention contains the chain-shaped cerium oxide-based hollow fine particles and a matrix-forming component. Dispersion medium As the dispersion medium of the coating liquid, a conventional dispersion medium can be used, and specific examples thereof include water and various organic solvents. The organic solvent to be used in the present invention is not particularly limited as long as it can dissolve or disperse the matrix-forming component of the ruthenium, and the polymerization initiator to be used as needed, and uniformly disperse the chain-like cerium oxide-based hollow fine particles. Conventional dispersion medium. Specific examples thereof include alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, decyl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexanediol, and isopropyl glycol; Esters of esters, ethyl acetate, butyl acetate, etc.; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, two Ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether -29- 201034958: acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl amyl ketone, diisobutyl ketone, isophorone, acetoacetone, acetamidine acetate , toluene, xylene, etc. These may be used singly or in combination of two or more. Polymerization Initiator In the coating liquid of the present invention, together with the chain-like cerium oxide-based hollow fine particles, the matrix forming component may contain a polymerization initiator. The polymerization initiator is not particularly limited and may be used. For example, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and bis(2,6-dimethoxy) may be mentioned. Benzobenzyl) 2,4,4-trimethyl-pentylphosphine oxide '2-hydroxy-methyl-2-methyl-phenyl-propan-1-one, 2,2-dimethoxy Base-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-methyl-1-[4-(methylthio)phenyl]-2-? Orolinylpropan-1-one and the like. Chain-shaped cerium oxide-based hollow fine particles As the chain-shaped cerium oxide-based hollow fine particles, the above-mentioned chain-shaped yttrium oxide-based hollow fine particles are used. In the coating liquid of the present invention, inorganic oxide fine particles other than the chain-shaped cerium oxide-based hollow fine particles may be contained as needed. Examples of the inorganic oxide fine particles include conventional low refractive index inorganic oxide fine particles, high refractive index inorganic oxide fine particles, and conductive inorganic oxide fine particles. The matrix-forming component is a dispersion of the above-mentioned fine particles, and means a component which can form a film on the surface of the substrate from -30 to 201034958, and can be selected from suitable resins such as adhesion to the substrate, hardness, and coatability. Examples of the use include polyester resins, acrylic resins, urethane resins, vinyl chloride resins, epoxy resins, melamine resins, fluororesins, oxime resins, butyral resins, phenol resins, and vinyl acetate which have been conventionally used. An ester resin, an ultraviolet curable resin, an electron ray hardening resin, an emulsified resin, a water-soluble resin, a hydrophilic resin, a mixture of such resins, and a coating resin or the like of a copolymer or a modified body of such a resin, or the aforementioned hospital A hydrolyzable organic chopping compound such as an oxygen sand plant or the like, and a partial hydrolyzate thereof. The total concentration of the matrix-forming component and the chain-like cerium oxide-based hollow fine particles of the coating liquid for forming a transparent film is 1 to 60% by weight, more preferably 2 to 50% by weight, based on the solid content. When the solid content concentration of the coating liquid for forming a transparent film is less than 1% by weight, the film thickness required for the primary coating is not obtained. Therefore, if the coating or drying is repeated, the adhesion and the like are insufficient or economical. Sexual disadvantage.若 If the solid content concentration exceeds 60 weight. /. Then, the film thickness of the obtained transparent film becomes uneven, or cracks may occur. The concentration of the chain cerium oxide-based hollow fine particles in the coating liquid for forming a transparent film is such that the content of the chain-shaped cerium oxide-based hollow fine particles in the obtained transparent film is 5 to 80% by weight, particularly 1 in terms of solid content. 〇 ~ 50% by weight range is used. When the content of the chain cerium oxide-based hollow fine particles in the transparent film is less than 5% by weight based on the solid content, the transparent moon-shaped ruthenium having a desired low refractive index is not obtained, and the chain ruthenium oxide of the present invention can be used. What are the hollow microparticles? -31 - 201034958 Other conventional low refractive index particles are used. When the content of the chain cerium oxide-based hollow fine particles in the transparent film is more than 80% by weight based on the solid content, the transparency, strength, and the like of the film may become insufficient. In addition, when inorganic oxide fine particles other than the chain-shaped cerium oxide-based hollow fine particles are used as needed, the total concentration of the particles is preferably in the same range as described above. In addition, the concentration of the matrix-forming component in the coating liquid for forming a transparent film is such that the content of the matrix component in the obtained transparent film is 20 to 95% by weight, particularly 50 to 90% by weight, based on the solid content. use. More specifically, the concentration of the chain cerium oxide-based hollow fine particles in the coating liquid for forming a transparent film is preferably from 0.05 to 48% by weight, more preferably from 0.1 to 30% by weight, based on the solid content. The concentration of the matrix-forming component in the coating liquid for forming a transparent film is preferably from 0.2 to 57% by weight, particularly preferably from -54% by weight, based on the solid content. The coating liquid for forming a transparent film is applied onto a substrate by a known method such as a dipping method, a spray method, a spin coating method, a roll coating method, a bar coating method, or a gravure printing method, a micro gravure printing method. Drying is hardened by a usual method such as ultraviolet irradiation or heat treatment to form a transparent film. The film thickness of the obtained transparent film is preferably in the range of 200 nm to 20 μm -32 - 201034958 [Substrate with transparent film] Next, a substrate with a transparent film will be described. In the substrate with a transparent film of the present invention, the transparent film formed using the coating liquid for a transparent film is formed on the surface of the substrate alone or in combination with other films. The substrate 〇 is used as a substrate for plastic sheets such as glass, polycarbonate, acrylic, TAC, plastic film, plastic lens, plastic substrate, cathode tube, fluorescent display tube, liquid crystal display panel, etc. The film formed on the surface of the substrate is different depending on the application, but the film or the substrate and the protective film, the hard coat film, the flattening film, the high refractive index insulating film, the conductive resin film, the conductive metal fine particle film, The conductive oxide fine particle film, other base film used as needed, and the like. Further, when used in combination, the film of the present invention is preferably formed on the surface of the ?). Such a transparent film can be applied to a base by a known method such as a coating dipping method such as a spray method, a spin coating method, or a roll coating method, and can be applied by heating or ultraviolet irradiation. Get it. The refractive index of the transparent film formed on the surface of the substrate differs depending on the refractive index of the matrix used for the mixing ratio of the chain yttria-based hollow fine particles to the matrix component, etc., but is 1.15 to 1.42. rate. Further, the chain-shaped cerium oxide-based hollow fine particles of the present invention are formed into a single film of a PET board or the like, and a gold-like outermost liquid material is used as a hard surface and a low body-33-201034958 refractive index. It is 1.1 〇~1 · 3 5. In the chain yttria-based hollow fine particles of the present invention, voids are formed inside, and matrix forming components such as resin are stopped outside the particles, and voids inside the chain-shaped cerium oxide-based hollow fine particles are retained. In the substrate having the transparent film, when the refractive index of the substrate is 1.60 or less, it is recommended to form a film having a refractive index of 1⁄6 or more on the surface of the substrate (hereinafter also referred to as an intermediate film). The transparent film containing the chain yttria-based hollow fine particles of the present invention is formed. When the refractive index of the intermediate film is 1600 or more, the difference in refractive index between the transparent film containing the chain yttria-based hollow fine particles of the present invention is large, and the base of the transparent film having excellent antireflection performance is obtained. material. The refractive index of the intermediate film can be adjusted by increasing the refractive index of the metal oxide fine particles used for increasing the refractive index of the intermediate film, the mixing ratio of the metal oxide fine particles and the resin, and the refractive index of the resin to be used. A mixed liquid of the coating liquid metal oxide particles for forming a film for the intermediate film and the substrate for forming a film, if necessary, an organic solvent is mixed. In the same manner as the film containing the cerium oxide-based fine particles of the present invention, the same substrate for forming a film can be used as the substrate for forming a film, whereby a substrate having an adhesive film having excellent adhesion between the two films can be obtained. The invention will be more specifically illustrated by the following examples. [Embodiment] Example 1 Modification of chain cerium oxide-based hollow fine particles (Ρ-1) in 100 g of cerium oxide-alumina sol (Japanese-style catalyst-forming compound) -34-201034958 system: USBB-120, average particle The diameter was 25 nm, the concentration of SiO 2 .Al 2 〇 3 was 20% by weight, and the content of A12 〇 3 in the solid content was 27% by weight. 3 90 gram of pure water was added and the temperature was raised to 98. (: ' While maintaining this temperature', add 1 750 grams of sodium silicate as a concentration of SiO 2 at a concentration of 1.5% by weight for 6 hours, and a concentration of 17.5 g as a concentration of A12〇3 〇.5% by weight of aluminate The aqueous sodium solution was used to obtain a dispersion of Si〇2.Al2〇3—the secondary particles (P-1). The molar ratio at this time was MOx/SiO2 = 0.2. Further, the pH of the reaction solution at this time was 12.0. 0 The average particle diameter of the primary particles of the dispersion is 35 nm. (Step (a)) Next, the Si〇2.Al2〇3-subparticle (P-1) dispersion is washed by an ultrafiltration membrane method and concentrated. It is a dispersion of Si〇2·Al2〇3—subparticle (P-1) having a solid concentration of 5 wt%. (Step (b)) Alternatively, 1 3 6 g of the mixture is prepared and used as the concentration of si Ο 2 The weight of the acidic citric acid solution and 5.4 g of the aqueous solution of the aqueous solution of C a ( Ν Ο 3 ) 2 as a concentration of 10% by weight of the electrolyte used for the chaining, and the solid concentration of 300% by weight of 5% by weight SiO 2 . Al 2 〇 3 - sub-particle (P-1 ) dispersion was mixed, and 9 g of a 2% by weight aqueous NaOH solution was added thereto, followed by 'hydrothermal treatment at 1 50 rpm for 3 hours to prepare a solid. A dispersion of chain-like composite oxide particles (P-1) having a concentration of 5 wt%, followed by cooling to room temperature. The pH of the dispersion at this time was 10.9 (step (C)). Next, at a solid concentration of 300 g. Adding 690 g of pure water to the dispersion of chain-like composite oxide particles (P - 1 ) by weight 'warming to 98 ° C, while maintaining this temperature, adding 1 5 3 g at 1 7 hours The sodium citrate aqueous solution having a concentration of 1.5% by weight of S i Ο 2 and 50 gram of sodium aluminate solution as a concentration of AI2O3 〇. 5 wt% of sodium aluminate aqueous solution to obtain cerium oxide·aluminum oxide-35-201034958 Composite oxide particle (p_1) dispersion. (Step (d)) Subsequently, it is washed by ultrafiltration membrane method to perform "concentration" on 500 g of solid oxide concentration of 13% by weight of cerium oxide-alumina coated chain complex oxidation. I: 125 g of pure water was added to the dispersion of the particle (P-1), and then concentrated hydrochloric acid (concentration: 35.5 wt%) was added dropwise to obtain a pH of 1.0 O. The dealumination treatment was carried out. Next, ρ Η of 1 〇L was added. 3 aqueous hydrochloric acid solution and 5 L of pure water are separated by ultrafiltration membrane. The dissolved aluminum salt is washed. Further, an aqueous dispersion of chain cerium oxide-based hollow fine particles (Ρ-1) having a solid concentration of 20% by weight was obtained (step (e)) (step (f)) with respect to the obtained chain-like cerium oxide-based hollow fine particles ( P-1) 'Measure the average width, average length, shell thickness, average diameter of the through holes, MOx/SiO 2 (mole ratio) and refractive index, and the results are shown in Table 1. In the examples and comparative examples shown below, the results in Table 1 were measured in the same manner. The average particle diameter was measured by dynamic light scattering method. The refractive index was measured using Series A and AA made by CARGILL. The standard refractive liquid 'is determined by the aforementioned method. The MOx was measured by an ICP emission spectroscopic analyzer (Shimadzu Corporation: ICPS-8 100), and the Si〇2 system was obtained by removing the weight of MOx and Na20 from the weight of the residual solid component at the time of calcination at 1 000 °C. Production of the base material (A-1) with a transparent film The aqueous dispersion of the chain cerium oxide-based hollow fine particles (P-1) having a solid content concentration of 20% by weight obtained as described above is placed in an ethanol solution using an ultrafiltration membrane. -36- 201034958 A solvent dispersion was used to prepare an alcohol dispersion of chain cerium oxide-based hollow fine particles (pi) having a solid concentration of 20% by weight. An alcohol dispersion in which 50 g of chain cerium oxide-based hollow fine particles (P-1) was sufficiently mixed was diluted with ethanol to a dispersion having a solid concentration of 5 wt%, and 3 g of an acrylic resin (Hitaroid 1 007, manufactured by Hitachi Chemical Co., Ltd.) And a mixed solvent of 47 g of isopropyl alcohol and n-butanol in a ratio of 1 / 1 (by weight) to prepare a coating liquid. C This coating liquid was applied onto a PET film by a bar coating method, and dried at 80 ° C for 1 minute to obtain a transparent film substrate (A-1) having a transparent film thickness of 1 〇〇 nm. . Table 2 shows the total light transmittance, the haze, the reflectance of light having a wavelength of 50 nm, the refractive index of the film, the adhesion, the scratch resistance, and the pencil hardness of the substrate (A-1) having the transparent film. The results are also measured in the same manner as in the examples and comparative examples shown below, and the results are shown in Table 2. The total light transmittance and haze were measured by a haze meter (manufactured by SUGA Tester Co., Ltd.), and the reflectance was measured by a spectrophotometer (Ubest-55, Jig., Ltd.). Further, the refractive index of the film was measured by an ellipsometer (EMS-1, manufactured by ULVAC). Further, the uncoated PET film had a total light transmittance of 90.7%, a haze of 2.0%, and a reflectance of 7.05% of light having a wavelength of 550 nm. The pencil hardness was determined according to FIS K 5400 using a pencil hardness tester. That is, the pencil was attached to the surface of the film at an angle of 45 degrees, and the specified load was loaded, and pulled at a constant speed to observe the presence or absence of a flaw. Further, on the surface of the base material (A -1 ) with the transparent film, a parallel flaw was made at intervals of 1 mm in the longitudinal and lateral directions to make 100 squares '-37- 201034958, and then adhered thereto. The enamel tape was classified into the following three grades, and the number of squares in which the film was not peeled off when the cellophane tape was peeled off was classified, and the adhesion was evaluated. The number of remaining squares is more than 90: ◎ The number of remaining squares is 85 to 89: 〇 Remaining squares are 8 or less: △ The scratch resistance is # 〇〇〇〇 steel wool, sliding with a load of 500 g/cm2 50 The surface of the film was visually observed and evaluated by the following criteria. Did not see the rib scars: ◎ Slightly see the rib scars: 〇 See most of the rib scars: △

面係全體地被削掉：X 實施例2 鏈狀氧化矽系中空微粒子（P-2)之調製 於實施例1中，除了混合2 7克當作電解質的濃度i 〇 重量％之C a ( Ν Ο 3 ) 2水溶液以外，同樣地得到固體成分 濃度20重量％的鏈狀氧化矽系中空微粒子（P-2 )之水分 散液。 附透明被膜之基材（A-2)的製造 於實施例1中，除了使用固體成分濃度2 0重量％的鏈 狀氧化矽系中空微粒子（P-2 )之水分散液以外，同樣地 得到塗佈液及透明被膜的膜厚爲1 OOnm之附透明被膜之基 -38- 201034958 材（A-〗）。 實施例3 鏈狀氧化矽系中空微粒子（P - 3 )之調製 於實施例1中，除了混合54克當作電解質的濃度1 0 重量％之Ca ( N03 ) 2水溶液以外，同樣地得到固體成分 濃度20重量％的鏈狀氧化矽系中空微粒子（P_3)之水分 〇 散液。 附透明被膜之基材（A-3 )的製造 於實施例1中，除了使用固體成分濃度20重量％的鏈 狀氧化矽系中空微粒子（P-3 )之水分散液以外，同樣地 得到塗佈液及透明被膜之膜厚爲1 OOnm的附透明被膜之基 材（P-3)。 Q 實施例4 鏈狀氧化矽系中空微粒子（P-4)之調製 於實施例1中，除了混合4.9克當作電解質的濃度1〇 重量％之M g ( N 03 ) 2水溶液以外，同樣地得到固體成分 濃度20重量％的鏈狀氧化矽系中空微粒子（P-4)之水分 散液。 附透明被膜之基材（A-4)的製造 於實施例1中，除了使用固體成分濃度20重量°/。的鏈 -39 - 201034958 狀氧化砂系中空微粒子（P_4)之水分散液以外，同樣地 得到塗佈液及透明被膜之膜厚爲1 〇〇nm的附透明被膜之基 材（A - 4 )。 實施例5 鏈狀氧化矽系中空微粒子（P_5)之調製 於100克氧化矽·氧化鋁溶膠（日揮觸媒化成（股） 製：USBB-120，平均粒徑 25nm，Si〇2. Al2〇3 濃度 20 重 量％，固體成分中A1203含量27重量％)中添加3900克 純水，加溫到9 8 °C，一邊保持在此溫度，一邊以6小時添 加405克當作Si02的濃度1.5重量％之矽酸鈉水溶液與 4〇5克當作Al2〇3的濃度0.5重量％之鋁酸鈉水溶液’而得 到S i Ο 2 . A12 〇 3 —次粒子（P - 5 )分散液。此時的莫耳比爲 M0x/Si02 = 〇.2。又，此時的反應液之PH爲12·0。此分散 液的一次粒子平均粒徑爲2 8 n m。（步驟（a )) 接著，以超濾膜法洗淨Si02 · A1203 —次粒子（P-5 ) 分散液，進行濃縮而成爲固體成分濃度5重量％的S i 0 2 · Al2〇3 —次粒子（P-5)分散液。（步驟（b)) 另途，調製混合有136克當作Si〇2的濃度2重量％之 酸性矽酸液與5.4克當作用於' 鏈狀化1的電解質之濃度10 重量％的C a ( Ν Ο3 ) 2水溶液之水溶液’與3 0 0克固體成 分濃度5重量。/。的s 1 〇2 . A12 〇 3 —次粒子（P - 5 )分散液混 合，在其中添加9克濃度2重量％的N a Ο Η水溶液後，於 1 5 0 °C進行3小時水熱處理’以調製固體成分濃度5重量％ -40- 201034958 的鏈狀複合氧化物粒子（P-5 )分散液。接著冷卻到常溫 。此時的分散液之pH爲10.9。（步驟（c)) 接著，於300克固體成分濃度5重量％的鏈狀複合氧 化物粒子（P-5 )分散液中添加3 900克純水，加溫到9S°C ，一邊保持此溫度，一邊以17小時添加1 53 0克當作Si〇2 的濃度1.5重量％之矽酸鈉水溶液與500克當作Al2〇3的 濃度0.5重量％之鋁酸鈉水溶液，而得到氧化矽·氧化鋁 〇 被覆鏈狀複合氧化物粒子（P-5 )分散液。（步驟（d )) 隨後，以超濾膜法洗淨，進行濃縮，於500克固體成 分濃度爲1 3重量％的氧化矽·氧化鋁被覆鏈狀複合氧化物 粒子（P-5 )分散液中添加1，125克純水，接著滴下濃鹽酸 (濃度35.5重量％)而成爲pHl.O，進行脫鋁處理。其次 ，一邊添加10L的pH3之鹽酸水溶液與5L的純水，一邊 以超濾膜來分離•洗淨所溶解的鋁鹽，而得到固體成分濃 度2 0重量％的鏈狀氧化矽系中空微粒子（P - 5 )之水分散 Ο 液。（步驟（e ))(步驟（f)) 附透明被膜之基材（A-5)的製造 於實施例1中，除了使用固體成分濃度20重量％的鏈 狀氧化矽系中空微粒子（P-5 )之水分散液以外，同樣地 得到塗佈液及透明被膜之膜厚爲1 OOnm的附透明被膜之基 材（A - 5 )。 實施例6 -41 - 201034958 鏈狀氧化矽系中空微粒子（P-6 )之調製 於1 00克氧化矽•氧化鋁溶膠（日揮觸媒化成（股） 製：USBB-120,平均粒徑 25nm，Si02. Al2〇3 濃度 20 重 量％，固體成分中Al2〇3含量27重量％ )中添加3900克 純水，加溫到98 °C，一邊保持在此溫度，一邊以6小時添 加20,900克當作Si02的濃度1.5重量％之矽酸鈉水溶液與 20,900克當作Al2〇3的濃度0.5重量％之鋁酸鈉水溶液， 而得到Si02 · A1203 —次粒子（P-6 )分散液。此時的莫耳 比爲MOx/SiO2 = 0.2。又，此時的反應液之pH爲12.0。此 分散液的一次粒子平均粒徑爲70nm。（步驟（a )) 接著，以超濾膜法洗淨Si02 · Al2〇3 —次粒子（P-6) 分散液，進行濃縮而成爲固體成分濃度5重量％的Si02 · Al2〇3 —次粒子（P-6 )分散液。（步驟（b )) 另途，調製混合有1 3 6克當作S i 02的濃度2重量％之 酸性矽酸液與5.4克當作用於鏈狀化的電解質之濃度1 〇 重量％的C a ( Ν Ο 3 ) 2水溶液之水溶液’與3 0 0克固體成 分濃度5重量％的S i Ο 2 · A12 〇 3 —次粒子（P - 6 )分散液混 合，在其中添加9克濃度2重量％的NaOH水溶液後’於 1 5 0 °C進行3小時水熱處理，以調製固體成分濃度5重量％ 的鏈狀複合氧化物粒子（P-6 )分散液。接著冷卻到常溫 。此時的分散液之PH爲10.9。（步驟（c)) 接著，於300克固體成分濃度5重量％的鏈狀複合氧 化物粒子（P-6 )分散液中添加3 900克純水，加溫到98 °C ，一邊保持此溫度，一邊以17小時添加2,000克當作 -42- 201034958The dough was entirely cut off: X Example 2 The formation of chain yttrium oxide hollow fine particles (P-2) was prepared in Example 1, except that 27 g of the concentration of i 〇% by weight of the electrolyte was mixed (C a ( In addition to the aqueous solution, an aqueous dispersion of chain cerium oxide-based hollow fine particles (P-2) having a solid concentration of 20% by weight was obtained in the same manner. The base material (A-2) with a transparent film was produced in the same manner as in Example 1 except that an aqueous dispersion of chain cerium oxide-based hollow fine particles (P-2) having a solid concentration of 20% by weight was used. The coating liquid and the transparent film have a film thickness of 100 nm with a transparent film base-38-201034958 (A-〗). Example 3 Preparation of chain cerium oxide-based hollow fine particles (P - 3 ) In the same manner as in Example 1, except that 54 g of a Ca(N03) 2 aqueous solution having a concentration of 10% by weight as an electrolyte was mixed, a solid component was obtained in the same manner. A moisture dispersing liquid of a chain cerium oxide-based hollow fine particle (P_3) having a concentration of 20% by weight. The base material (A-3) with a transparent film was produced in the same manner as in Example 1 except that an aqueous dispersion of chain cerium oxide-based hollow fine particles (P-3) having a solid concentration of 20% by weight was used. A substrate (P-3) with a transparent film having a film thickness of 100 nm and a transparent film. Q Example 4 Preparation of chain cerium oxide-based hollow fine particles (P-4) In the same manner as in Example 1, except that 4.9 g of an aqueous solution of M g (N 03 ) 2 having a concentration of 1% by weight as an electrolyte was mixed, An aqueous dispersion of chain cerium oxide-based hollow fine particles (P-4) having a solid concentration of 20% by weight was obtained. The substrate (A-4) with a transparent film was produced in Example 1, except that the solid content concentration was 20% by weight. In addition to the aqueous dispersion of hollow granules (P_4) of the oxidized sand-based hollow fine particles (P_4), a substrate (A - 4 ) with a transparent film having a thickness of 1 〇〇 nm of the coating liquid and the transparent film was obtained in the same manner. . Example 5 Modification of chain cerium oxide-based hollow fine particles (P_5) in 100 g of cerium oxide-alumina sol (daily flucene-forming system: USBB-120, average particle diameter 25 nm, Si〇2. Al2〇3 Adding 3900 g of pure water at a concentration of 20% by weight and a solid content of 27% by weight of A1203), heating to 98 ° C, while maintaining this temperature, adding 405 g for 6 hours as a concentration of SiO 2 of 1.5% by weight An aqueous solution of sodium citrate and 4 〇 5 g of an aqueous solution of sodium aluminate having a concentration of 0.5% by weight of Al 2 〇 3 were used to obtain a dispersion of S i Ο 2 . A12 〇 3 - sub-particles (P - 5 ). The molar ratio at this time is M0x/Si02 = 〇.2. Further, the pH of the reaction liquid at this time was 12.0. This dispersion had a primary particle average particle diameter of 2 8 n m. (Step (a)) Next, the SiO 2 · A1203 - sub-particle (P-5 ) dispersion was washed by an ultrafiltration membrane method, and concentrated to obtain S i 0 2 · Al2 〇 3 of a solid concentration of 5 wt%. Particle (P-5) dispersion. (Step (b)) Alternatively, 136 g of an acidic citric acid solution having a concentration of 2% by weight of Si〇2 and 5.4 g of C a concentration of 10% by weight of the electrolyte used for 'chaining 1' were prepared. ( Ν Ο 3 ) 2 aqueous solution of aqueous solution 'with a solid concentration of 300 g of 5 weight. /. s 1 〇 2 . A12 〇 3 - sub-particle (P - 5 ) dispersion was mixed, and 9 g of a 2% by weight aqueous solution of Na Ο Η was added thereto, followed by hydrothermal treatment at 150 ° C for 3 hours. A chain-like composite oxide particle (P-5) dispersion having a solid content concentration of 5 wt% - 40 - 201034958 was prepared. Then cool to room temperature. The pH of the dispersion at this time was 10.9. (Step (c)) Next, 3,900 g of pure water was added to 300 g of a chain-like composite oxide particle (P-5) dispersion having a solid concentration of 5 wt%, and the temperature was maintained at 9 S ° C while maintaining the temperature. While adding 1 530 g of an aqueous solution of sodium citrate having a concentration of 1.5% by weight of Si〇2 and 500 g of an aqueous solution of sodium aluminate having a concentration of 0.5% by weight of Al2〇3, 17 hours, to obtain cerium oxide·oxidation The aluminum bismuth is coated with a chain-like composite oxide particle (P-5) dispersion. (Step (d)) Subsequently, it is washed by an ultrafiltration membrane method and concentrated, and 500 g of a cerium oxide-alumina-coated chain-like composite oxide particle (P-5) dispersion having a solid concentration of 13% by weight. 1,125 g of pure water was added thereto, and then concentrated hydrochloric acid (concentration: 35.5 wt%) was added thereto to obtain pH 1. O, and dealumination treatment was carried out. Next, while adding 10 L of a hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the dissolved aluminum salt was separated and washed with an ultrafiltration membrane to obtain chain cerium oxide-based hollow fine particles having a solid concentration of 20% by weight ( P - 5 ) water disperses the sputum. (Step (e)) (Step (f)) The substrate (A-5) with a transparent film was produced in Example 1, except that chain cerium oxide-based hollow fine particles having a solid concentration of 20% by weight (P- In addition to the aqueous dispersion of 5), a substrate (A - 5 ) having a transparent coating film having a thickness of 100 nm and a thickness of the coating liquid and the transparent film was obtained in the same manner. Example 6 -41 - 201034958 The chain yttria-based hollow fine particles (P-6) were prepared in 100 g of cerium oxide-alumina sol (daily-flux-catalyzed into a product: USBB-120, average particle diameter 25 nm, Si02. Al2〇3 concentration 20% by weight, solid content of Al2〇3 content 27% by weight) Add 3900 g of pure water, warm to 98 °C, while maintaining this temperature, add 20,900 g for 6 hours. An aqueous solution of sodium citrate having a concentration of SiO 2 of 1.5% by weight and 20,900 g of an aqueous solution of sodium aluminate having a concentration of 0.5% by weight of Al 2 〇 3 were obtained to obtain a dispersion of SiO 2 · A1203 - sub-particle (P-6 ). The molar ratio at this time is MOx/SiO2 = 0.2. Further, the pH of the reaction liquid at this time was 12.0. The primary particle average particle diameter of this dispersion was 70 nm. (Step (a)) Next, the SiO 2 ·Al 2 〇 3 -sub particles (P-6) dispersion was washed by an ultrafiltration membrane method, and concentrated to obtain SiO 2 ·Al 2 〇 3 -sub particles having a solid concentration of 5 wt%. (P-6) Dispersion. (Step (b)) Alternatively, 1 36 g of an acidic citric acid solution having a concentration of 2% by weight of S i 02 and 5.4 g of a concentration of 1 〇% by weight of the electrolyte used for chain formation were prepared. a ( Ν Ο 3 ) 2 aqueous solution of aqueous solution 'mixed with 300 gram of solid concentration 5% by weight of S i Ο 2 · A12 〇 3 - secondary particle (P - 6 ) dispersion, and added 9 gram of concentration 2 After the weight % of the NaOH aqueous solution was subjected to hydrothermal treatment at 150 ° C for 3 hours, a chain-like composite oxide particle (P-6 ) dispersion having a solid concentration of 5 wt% was prepared. Then cool to room temperature. The pH of the dispersion at this time was 10.9. (Step (c)) Next, 3,900 g of pure water was added to 300 g of a dispersion of chain-like composite oxide particles (P-6) having a solid concentration of 5 wt%, and the temperature was maintained at 98 ° C while maintaining the temperature. , adding 2,000 grams in 17 hours as -42- 201034958

Si〇2的濃度1.5重量％之矽酸鈉水溶液與700克當作 Al2〇3的濃度0.5重量。/。之鋁酸鈉水溶液，而得到氧化矽. 氧化鋁被覆鏈狀複合氧化物粒子（P -6 )分散液。（步驟 (d)) 隨後，以超濾膜法洗淨，進行濃縮，於5〇〇克固體成 分濃度爲1 3重量％的氧化矽·氧化鋁被覆鏈狀複合氧化物 粒子（P-6 )分散液中添加1，125克純水，接著滴下濃鹽酸 0 (濃度35.5重量％)而成爲pHl.O，進行脫鋁處理。其次 ，一邊添加10L的pH3之鹽酸水溶液與5L的純水，一邊 以超濾膜來分離•洗淨所溶解的鋁鹽，而得到固體成分濃 度20重量％的鏈狀氧化矽系中空微粒子（P-6)之水分散 液。（步驟（e ))(步驟（f)) 附透明被膜之基材（A-6)的製造 於實施例1中，除了使用固體成分濃度20重量％的鏈 Ο 狀氧化矽系中空微粒子（P-6 )之水分散液以外，同樣地 得到塗佈液及透明被膜之膜厚爲1 OOnm的附透明被膜之基 材（A-6 )。 實施例7 附透明被膜之基材（A-7)的製造 於實施例1中，除了使用3 6.6克鏈狀氧化矽系中空 微粒子（P-1 )之醇分散液經乙醇稀釋成固體成分濃度5 重量％的分散液、3.7克丙烯酸樹脂（Hitaroid 1 007，日立 -43 - 201034958 化成（股）製）及58克異丙醇與正丁醇的1/1 (重量比） 混合溶劑以外，同樣地得到塗佈液及透明被膜之膜厚爲 100nm的附透明被膜之基材（A-7)。 實施例8 附透明被膜之基材（A-8 )的製造 於實施例1中，除了使用55克鏈狀氧化矽系中空微 粒子（P-1)之醇分散液經乙醇稀釋成固體成分濃度5重 量％的分散液、2.75克丙烯酸樹脂（Hitaroid 1007,日立 化成（股）製）及43.1克異丙醇與正丁醇的1/1 (重量比 )混合溶劑以外，同樣地得到塗佈液及透明被膜之膜厚爲 lOOnm的附透明被膜之基材（A-8)。 實施例9 鏈狀氧化矽系中空微粒子（P-7 )之調製 以超濾膜法洗淨，進行濃縮，於5 00克固體成分濃度 爲1 3重量％的氧化矽·氧化鋁被覆鏈狀複合氧化物粒子（ p-1 )分散液中添加1 ,1 25克純水，接著滴下濃鹽酸（濃度 35·5重量％)而成爲pHO.5，進行脫鋁處理。其次，一邊 添加25L的pH3.0之鹽酸水溶液與10L的純水，一邊以超 濾膜來分離.洗淨所溶解的鋁鹽，而得到固體成分濃度20 重量％的鏈狀氧化矽系中空微粒子（P - 7 )之水分散液。（ 步驟（e ))(步驟（f)) . -44 - 201034958 附透明被膜之基材（A-9)的製造 於實施例1中，除了使用固體成分濃度2〇重量％的鏈 狀氧化矽系中空微粒子（P - 7 )之水分散液以外，同樣地 得到塗佈液及透明被膜之膜厚爲1 OOnm的附透明被膜之基 材（A-9)。 比較例1 〇 氧化矽系中空微粒子（RP-1 )的調製 於1 〇〇克氧化矽.氧化鋁溶膠（日揮觸媒化成（股） 製：USBB-120，平均粒徑 25nm、Si02. Al2〇3 濃度 20 重 量％，固體成分中Al2〇3含量27重量％ )添加3 900克純 水，加溫到98 °C，一邊保持在此溫度，一邊以6小時添加 1 7 5 0克當作 s i Ο 2的濃度1 . 5重量％之矽酸鈉水溶液與 1 750克當作ai2〇3的濃度〇.5重量％之鋁酸鈉水溶液，而 得到S i 〇2 . AI 2 Ο 3 —次粒子（P - 1 )分散液。此時的莫耳比 〇 爲MOx/Si〇2 = 0.2。又，此時的反應液之pH爲12.0。此分 散液的一次粒子平均粒徑爲3 5 n m。（步驟（a )) 接著，以超濾膜法洗淨si〇2 · ai2o3 —次粒子（P-1 ) 分散液，進行濃縮而成爲固體成分濃度5重量％的Si02 · Al2〇3 —次粒子（p-i )分散液。（步驟（b )) 隨後，於300克固體成分濃度5重量％的Si 02 . Al2〇3 —次粒子（P-1 )分散液中添力□ 3900克純水，加溫 到9 8 °C，一邊保持此溫度，一邊以1 7小時添加1 5 3 0克當 作Si02的濃度1.5重量％之矽酸鈉水溶液與5〇〇克當作 -45 - 201034958The aqueous solution of sodium citrate having a concentration of Si 〇 2 of 1.5% by weight and 700 g of the concentration of Al 2 〇 3 was 0.5 wt. /. The sodium aluminate aqueous solution is used to obtain cerium oxide. The alumina is coated with a chain-like composite oxide particle (P-6) dispersion. (Step (d)) Subsequently, it is washed by an ultrafiltration membrane method and concentrated to form a cerium oxide-alumina-coated chain-like composite oxide particle (P-6) at a concentration of 13% by weight of a solid content of 13% by weight. 1,125 g of pure water was added to the dispersion, and then concentrated hydrochloric acid 0 (concentration: 35.5 wt%) was added thereto to obtain pH 1. O, and dealumination treatment was carried out. Next, while adding 10 L of a hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the dissolved aluminum salt was separated and washed with an ultrafiltration membrane to obtain chain cerium oxide-based hollow fine particles having a solid concentration of 20% by weight (P). -6) Aqueous dispersion. (Step (e)) (Step (f)) The substrate (A-6) with a transparent film was produced in Example 1, except that the chain-like cerium oxide-based hollow fine particles having a solid concentration of 20% by weight were used (P). In addition to the aqueous dispersion of -6), a substrate (A-6) having a transparent coating film having a thickness of 100 nm and a thickness of the coating liquid and the transparent film was obtained in the same manner. Example 7 The substrate (A-7) with a transparent film was produced in Example 1, except that an alcohol dispersion of 3 6.6 g of chain cerium oxide-based hollow fine particles (P-1) was diluted with ethanol to a solid concentration. 5 wt% of the dispersion, 3.7 g of acrylic resin (Hitaroid 1 007, manufactured by Hitachi-43 - 201034958 Chemicals Co., Ltd.), and 58 g of a mixed solvent of isopropanol and n-butanol in a ratio of 1/1 (by weight) A substrate (A-7) with a transparent film having a thickness of 100 nm of the coating liquid and the transparent film was obtained. Example 8 The substrate (A-8) with a transparent film was produced in Example 1, except that an alcohol dispersion of 55 g of chain cerium oxide-based hollow fine particles (P-1) was diluted with ethanol to a solid concentration of 5 A coating liquid was obtained in the same manner as a mixed solution of a weight % dispersion, 2.75 g of an acrylic resin (Hitaroid 1007, manufactured by Hitachi Chemical Co., Ltd.), and 43.1 g of a mixed solvent of isopropyl alcohol and n-butanol in a ratio of 1/1 (by weight). The base film (A-8) with a transparent film having a film thickness of 100 nm was provided. Example 9 Preparation of chain cerium oxide-based hollow fine particles (P-7) was washed by an ultrafiltration membrane method, and concentrated to form a ruthenium oxide-alumina-coated chain composite of 500 g of a solid content concentration of 13% by weight. To the oxide particle (p-1) dispersion, 1, 25 g of pure water was added, and then concentrated hydrochloric acid (concentration: 35.5% by weight) was added to obtain pHO.5, and dealumination treatment was carried out. Next, 25 L of a hydrochloric acid aqueous solution of pH 3.0 and 10 L of pure water were added, and the dissolved aluminum salt was separated by an ultrafiltration membrane to obtain a chain-like cerium oxide-based hollow fine particle having a solid concentration of 20% by weight. (P-7) aqueous dispersion. (Step (e)) (Step (f)) . -44 - 201034958 The substrate (A-9) with a transparent film was produced in Example 1, except that a chain cerium oxide having a solid concentration of 2% by weight was used. In the same manner as the aqueous dispersion of the hollow fine particles (P - 7 ), a substrate (A-9) having a transparent coating film having a thickness of 100 nm of the coating liquid and the transparent film was obtained in the same manner. Comparative Example 1 Preparation of cerium oxide cerium hollow microparticles (RP-1) in 1 gram of cerium oxide. Alumina sol (daily flucene-forming system: USBB-120, average particle size 25 nm, SiO 2 . Al 2 〇 3 concentration 20% by weight, solid content of Al2〇3 content 27% by weight) Add 3 900g of pure water, warm to 98 °C, while maintaining this temperature, add 1 7 50 grams as 6 hours浓度 2 concentration of 1.5% by weight of sodium citrate aqueous solution and 1 750 g as a concentration of AI2 〇 3 〇 5% by weight of sodium aluminate aqueous solution to obtain S i 〇 2 . AI 2 Ο 3 - secondary particles (P - 1 ) dispersion. The molar ratio at this time is MOx/Si〇2 = 0.2. Further, the pH of the reaction liquid at this time was 12.0. The primary particle of this dispersion has an average particle diameter of 3 5 n m. (Step (a)) Next, the Si〇2 · ai2o3 - sub-particle (P-1) dispersion was washed by an ultrafiltration membrane method, and concentrated to obtain SiO 2 · Al 2 〇 3 - primary particles having a solid concentration of 5 wt%. (pi) dispersion. (Step (b)) Subsequently, 3,900 g of pure water was added to 300 g of a solid concentration of 5 wt% of Si 02 . Al 2 〇 3 - sub-particle (P-1 ) dispersion, and heated to 9 8 ° C. While maintaining this temperature, 1 5 3 0 g was added as a concentration of SiO 2 at a concentration of 1.5% by weight of sodium citrate solution and 5 g was used as -45 - 201034958

Al2 03的濃度0.5重量％之鋁酸鈉水溶液，而得到氧化矽· 氧化鋁被覆複合氧化物粒子（RP-1 )分散液。 其次，以超濾膜法洗淨，進行濃縮，於500克固體成 分濃度爲1 3重量％的氧化矽·氧化鋁被覆複合氧化物粒子 (RP-1 )分散液中添加1，1 25克純水，接著滴下濃鹽酸（ 濃度35.5重量％)而成爲pH 1.0，進行脫鋁處理。其次， 一邊添加1 〇 L的p Η 3之鹽酸水溶液與5 L的純水，一邊以 超濾膜來分離·洗淨所溶解的鋁鹽，而得到固體成分濃度 20重量％的單分散氧化矽系中空微粒子（RP-1 )之水分散 液。水分散液中的氧化矽系中空微粒子（RP-1 )既不鏈狀 化也不凝聚。 附透明被膜之基材（RA-1)的製造 於實施例1中，除了使用固體成分濃度20重量％的氧 化矽系中空微粒子（RP-1 )之水分散液以外，同樣地得到 塗佈液及透明被膜之膜厚爲1 OOnm的附透明被膜之基材（ RA-1 )。 比較例2 鏈狀氧化矽系中空微粒子（RP-2 )之調製 於實施例1中，除了混合1 40克當作電解質的濃度1 0 重量。/。之Ca ( N03 ) 2水溶液以外，同樣地實施步驟（c) °此時’由於得到凝聚粒子，故以後的步驟不實施。 -46- 201034958 比較例3 鏈狀氧化矽系中空微粒子（RP-3)之調製 於實施例1中’除了混合〇. 1克當作電解質的濃度i 〇 重量％之C a ( Ν Ο3 ) 2水溶液以外，同樣地得到固體成分 濃度2 0重量％的鏈狀氧化矽系中空微粒子（rp _ 3 )之水分 散液。然而，多爲與比較例1同樣的單分散之氧化矽系中 空微粒子。對於一部分的鏈狀氧化矽系中空微粒子（RP_ 3 0 )，與實施例1同樣地測定物性，表1中顯示結果。 附透明被膜之基材（RA-3)的製造 於實施例1中，除了使用固體成分濃度2 0重量％的鏈 狀氧化矽系中空微粒子（R P - 3 )之水分散液以外，同樣地 得到塗佈液及透明被膜之膜厚爲1 OOnm的附透明被膜之基 材（RA-3 )。 〇 比較例4 附透明被膜之基材（RA-4 )的製造 對氧化矽溶膠（日揮觸媒化成（股）製·· Cataloid-SI-45P,平均粒徑45nm, Si〇2濃度40重量％ )，使用超濾膜 ，以乙醇置換溶劑，而調製固體成分濃度5重量％的氧化 矽有機溶膠。 充分混合5 0克固體成分濃度5重量％的氧化矽有機溶 膠、3克丙烯酸樹脂（Hitaroid 1 007,日立化成（股）製 )及47克異丙醇與正丁醇的1 /1 (重量比）混合溶劑，以 -47- 201034958 調製塗佈液。 於8 Ot使乾 附透明被膜 以桿塗法將此塗佈液塗佈在P E T薄膜上， 燥1分鐘，而得到透明被膜之膜厚爲1 OOnm的 之基材（RA-4 )。 -48- 201034958 ❹ 〇 〔I谳〕 屮 折射 率 m CN < vn (N r-H (N \Ti cs r-^ CN CO v〇 m <N cn (N CN (N 1 H ii 0.001 0.001 0.001 I o.ooi 0.001 I o.ooi I 0.001 1 o.ooi 0.0002 0.001 1 0.001 1 (Ds)/ (W) o yri O o uo o 寸 o o o i〇 o iTi o 1 1 o 1 鏟 味 娜 fK 1 貫通孔平 均直徑 (Ds) nm fN fN in CN in 卜 Ό <N ^T) CN iTi cs 1 1 (N 1 外殼 厚度 (Ts) nm ΙΥΊ ^T) in in ^T) cn r-H LT) in rO 1 1 1 i 1麗§旨 CO On 沄 1 1 沄 1 平均 長度 (L) nm 寸 in (N 1-H m 寸 cn t-H 00 <N 1 < o\ in 1—( 1 1 o 1 f S旨 iTi cn *r> m w-i m m OO <N 〇 in m m m CO m CO vr> m jn F的製造 被覆層 添加量 Si〇2(.Al2〇3)/ 鏈狀複合粒子 重量％ O r- O r—^ o 〇 〇 r-H (N (N 〇 ο 卜 o 卜 o 1 o 鏈狀氧化矽系中空微粒·^ 氧化砂 使用量 >>m 一一 l|Sl 〇〇 »—H d oo o 00 O OO o OO r-H o OO c5 00 »—H o oo — < ο 00 T—^ c> 1 00 o 00 r—H o 電解質 使用量1 (WEL)/ (WPI) 重量比 0.036 0.018 | 0.360 I | 0.033 I 0.036 | i 0.036 | 0.036 | 1 0.036 1 0.036 〇 m On 〇 0.0007 1 種類 Ca(N03)2 Ca(N03)2 | Ca(N〇3)2 I | Mg(N〇3)2 I Ca(N03)2 | Ca(N〇3)2 I Ca(N03)2 | 1 Ca(N〇3)2 1 Ca(N03)2 1 Ca(N03)2 Ca(N03)2 1 1實施例l] 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 I比較例i 比較例2 丨比較例3 1 比較例4 -49- 201034958 Μ 耐擦 傷性 ◎ ◎ 〇 ◎ ◎ 〇 ◎ 〇 ◎ 〇 1 〇 〇 1 鉛筆| 硬度1 1 X X ffi ffi ffi ffi PQ ffi ffi 1 ffi ffi 密接 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ 1 ◎ ◎ 紘 DAD 4HE iH 〇\ 〇 Ο r-H On 〇 s § o’ ιτ> 00 ο Ο 〇\ CN 1 On (N m 霧度 CM 〇 ίΝ Ο 寸 〇 m d o r- ο Ο 00 ο CN d cs d 1 m ο m o 全光線 透過率 % ON 芸 m Q\ 窆 σ\ CO 〇\ 1 <N m 〇\ 折射 掛 04 T-H σ\ rn ο i—Η r-H $ r-H 1 等 附透明被膜之基材 膜厚 I 〇 〇 Ο ο o o o o ο ο o o ο ο ο Ο ο o H 1 Ο o o 基質成分 含量 重量％ t ιη t IT) 艺· ΙΛ) VO in in 1 ^Τ) iTi t 讎 丙烯酸樹脂 丙烯酸樹脂 丙烯酸樹脂 丙烯酸樹脂 丙烯酸樹脂 丙烯酸樹脂 丙烯酸樹脂 丨丙烯酸樹脂 丙烯酸樹脂 丙烯酸樹脂 1 丙烯酸樹脂 丙烯酸樹脂 Μ嶷 If 含量 重量％ <Τ) jo yr> r〇 rn ΓΛ ο in 寸 in in 对 1 iT) jn in $ 基材 Η PLJ 〇4 Η ω Η m Ρη H ω Oh Η ω CU Η ω CU Η W Ρη Η ω Η ω PL. Η ω Oh 1 Η ρ-} Ρη H m Ph 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 比較例1 比較例2 比較例3 比較例4 -50- 201034958 【圖式簡單說明】 圖1係本發明的鏈狀氧化矽系中空微粒子之截面的模 型圖。A 0.5% by weight aqueous sodium aluminate solution of Al2 03 was obtained to obtain a cerium oxide-alumina-coated composite oxide particle (RP-1) dispersion. Next, it was washed by an ultrafiltration membrane method and concentrated, and 1,25 g of pure was added to 500 g of a cerium oxide-alumina-coated composite oxide particle (RP-1) dispersion having a solid concentration of 13% by weight. Water, followed by dropping concentrated hydrochloric acid (concentration: 35.5 wt%) to pH 1.0, and subjected to dealumination treatment. Next, while adding 1 〇L of p Η 3 aqueous hydrochloric acid solution and 5 L of pure water, the dissolved aluminum salt was separated and washed with an ultrafiltration membrane to obtain monodisperse cerium oxide having a solid concentration of 20% by weight. It is an aqueous dispersion of hollow microparticles (RP-1). The cerium oxide-based hollow fine particles (RP-1) in the aqueous dispersion are neither chained nor aggregated. In the first embodiment, the base material (RA-1) containing the transparent film was obtained in the same manner as the aqueous dispersion of cerium oxide-based hollow fine particles (RP-1) having a solid concentration of 20% by weight. And a transparent film-coated substrate (RA-1) having a film thickness of 100 nm. Comparative Example 2 Modification of chain yttrium oxide hollow fine particles (RP-2) In Example 1, except that 1 40 g of a concentration of 10 0 of the electrolyte was mixed was used. /. In the same manner as the Ca(N03) 2 aqueous solution, the step (c) is carried out in the same manner. Since the aggregated particles are obtained, the subsequent steps are not carried out. -46- 201034958 Comparative Example 3 Modification of chain cerium oxide hollow fine particles (RP-3) in Example 1 'except for mixing 〇. 1 gram of electrolyte as a concentration i 〇% by weight of C a ( Ν Ο 3 ) 2 In the same manner as the aqueous solution, an aqueous dispersion of chain cerium oxide-based hollow fine particles (rp _ 3 ) having a solid concentration of 20% by weight was obtained in the same manner. However, most of them are monodisperse cerium oxide-based hollow fine particles as in Comparative Example 1. The physical properties were measured in the same manner as in Example 1 for a part of the chain-like cerium oxide-based hollow fine particles (RP_30), and the results are shown in Table 1. The base material (RA-3) with a transparent film was produced in the same manner as in Example 1 except that an aqueous dispersion of chain cerium oxide-based hollow fine particles (RP-3) having a solid concentration of 20% by weight was used. The coating liquid and the transparent film were made of a transparent film substrate (RA-3) having a film thickness of 100 nm. 〇Comparative Example 4 Production of a substrate (RA-4) with a transparent film, a cerium oxide sol (made by Catalyst Chemical Co., Ltd., Cataloid-SI-45P, an average particle diameter of 45 nm, and a Si〇2 concentration of 40% by weight) The ultrafiltration membrane was used, and the solvent was replaced with ethanol to prepare a cerium oxide organosol having a solid concentration of 5 wt%. 50 g of a cerium oxide organosol having a solid concentration of 5 wt%, 3 g of an acrylic resin (Hitaroid 1 007, manufactured by Hitachi Chemical Co., Ltd.), and 47 g of isopropyl alcohol and n-butanol in a ratio of 1:1 (by weight) A mixed solvent was prepared to prepare a coating liquid at -47 to 201034958. The transparent coating was dried at 8 Ot. This coating liquid was applied onto the P E T film by a bar coating method, and dried for 1 minute to obtain a substrate (RA-4) having a transparent film thickness of 100 nm. -48- 201034958 ❹ 〇 [I谳] 屮 refractive index m CN < vn (N rH (N \Ti cs r-^ CN CO v〇m <N cn (N CN (N 1 H ii 0.001 0.001 0.001 I O.ooi 0.001 I o.ooi I 0.001 1 o.ooi 0.0002 0.001 1 0.001 1 (Ds)/ (W) o yri O o uo o inch oooi〇o iTi o 1 1 o 1 shovel na fK 1 through hole average Diameter (Ds) nm fN fN in CN in Divination <N ^T) CN iTi cs 1 1 (N 1 shell thickness (Ts) nm ΙΥΊ ^T) in in ^T) cn rH LT) in rO 1 1 1 i 1丽§§CO On 沄1 1 沄1 average length (L) nm inch in (N 1-H m inch cn tH 00 <N 1 < o\ in 1—( 1 1 o 1 f S Cn *r> m wi mm OO <N 〇in mmm CO m CO vr> m jn F production coating layer addition amount Si〇2(.Al2〇3)/chain composite particle weight% O r- O r— ^ o 〇〇rH (N (N 〇ο 卜o 卜 o 1 o chain yttrium oxide hollow particles·^ oxidized sand usage>>m 一l|Sl 〇〇»—H d oo o 00 O OO o OO rH o OO c5 00 »—H o oo — < ο 00 T—^ c> 1 00 o 00 r—H o Electrolyte usage 1 (WEL) / (WPI) Weight ratio 0.0 36 0.018 | 0.360 I | 0.033 I 0.036 | i 0.036 | 0.036 | 1 0.036 1 0.036 〇m On 〇0.0007 1 Type Ca(N03)2 Ca(N03)2 | Ca(N〇3)2 I | Mg(N〇 3) 2 I Ca(N03)2 | Ca(N〇3)2 I Ca(N03)2 | 1 Ca(N〇3)2 1 Ca(N03)2 1 Ca(N03)2 Ca(N03)2 1 1 Embodiment 1] Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 I Comparative Example i Comparative Example 2 丨 Comparative Example 3 1 Comparative Example 4 -49- 201034958 耐Scratch ◎ ◎ 〇 ◎ ◎ 〇 ◎ 〇 〇 〇 1 〇〇 1 pencil | hardness 1 1 XX ffi ffi ffi ffi PQ ffi ffi 1 ffi ffi ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ 1 ◎ ◎ 纮 纮 DAD 4HE iH 〇\ 〇Ο rH On 〇s § o' ιτ> 00 ο Ο 〇\ CN 1 On (N m Haze CM 〇 Ν Ν 〇 〇 mdo r- ο Ο 00 ο CN d cs d 1 m ο mo Full light transmission Rate % ON 芸m Q\ 窆σ\ CO 〇\ 1 <N m 〇\ Refraction hanging 04 TH σ\ rn ο i—Η rH $ rH 1 The film thickness of the substrate with a transparent film I 〇〇Ο oooo ο ο oo ο ο ο Ο ο o H 1 Ο oo matrix component content weight % t ιη t IT) 艺· ΙΛ) VO in in 1 ^Τ) iTi t 雠 acrylic resin acrylic resin acrylic resin acrylic resin acrylic resin acrylic resin 丨 acrylic resin acrylic resin acrylic resin 1 acrylic resin acrylic resin Μ嶷 If content Weight % <Τ) jo yr> r〇rn ΓΛ ο in inch in in pair 1 iT) jn in $ substrate Η PLJ 〇4 Η ω Η m Ρη H ω Oh Η ω CU Η ω CU Η W Ρη Η ω ω ω PL. ω ω Oh 1 Η ρ -} Ρη H m Ph Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparative Example 4 - 50 - 201034958 [Brief Description of the Drawings] Fig. 1 is a model diagram of a cross section of the chain-shaped yttria-based hollow fine particles of the present invention.

-51 --51 -

Claims (1)

201034958 七、申請專利範圍： 1. 一種鏈狀氧化矽系中空微粒子，其特徵爲在外部 具有外殼、在內部具有空涧的氧化矽系中空微粒子（一次 粒子）以鏈狀連結，具有空洞互相貫通的貫通孔，平均長 度（L)在20〜1 500nm之範圍，平均寬幅（w)在1〇〜 300nm之範圍，折射率在1.1〇〜135之範圍。 2 ·如申請專利範圍第1項之鏈狀氧化矽系中空微粒 子，其中前述外殻的厚度（Ts)在2〜100ηιη之範圍，與 前述平均寬幅（W)之比（Ts) / (W)在0.05〜0.30之範 圍。 3 ·如申請專利範圍第1或2項之鏈狀氧化矽系中空 微粒子’其中前述貫通孔的平均直徑（Ds)與前述平均寬 幅（W)之比（Ds) / (W)在〇.1〜〇.9之範圍。 4. 如申請專利範圍第1〜3項中任一項之鏈狀氧化矽 系中空微粒子’其係由氧化矽與氧化矽以外的無機氧化物 所構成’當以Μ〇χ表示氧化矽以外的無機氧化物時，其莫 耳比MOx/Si〇2在0.0001〜0.2之範圍。 5. —種鏈狀氧化矽系中空微粒子之製造方法，其特 徵係由下述步驟（a )〜（f)所構成， (a )將矽酸鹽的水溶液及/或酸性矽酸液與鹼可溶的 無機化合物水溶液同時加到鹼水溶液中，或同時加到固體 成分濃度在0·01〜2重量％之範圍的種粒子所分散的鹼水 溶液中’以調製當以S i 〇2表不氧化砂，以Μ Ο x表示氧化 矽以外的無機氧化物時的莫耳比M0x/Si02 ( A )在0. 1〜2 -52- 201034958 之範圍的複合氧化物一次粒子分散液之步驟； (b )洗淨前述一次粒子分散液之步驟； (c)將洗淨後的一次粒子分散液，在電解質的存在 下，於50〜3 00°C進行水熱處理，以調製鏈狀複合氧化物 粒子分散液之步驟； (d )形成氧化砂或氧化砂.氧化銘被覆層，調製氧化 矽或氧化矽·氧化鋁被覆鏈狀複合氧化物粒子分散液之步 〇 驟； (e )於氧化矽或氧化矽·氧化鋁被覆鏈狀複合氧化物 粒子分散液中添加酸，去除構成該複合氧化物粒子之砂以 外的元素之至少一部分，而成爲鏈狀氧化矽系中空微粒子 分散液之步驟； (f )洗淨所得的分散液之步驟。 6 _如申請專利範圍第5項之鏈狀氧化矽系中空微粒 子之製造方法，其中前述步驟（c)中的電解質係驗土類 〇 金屬鹽。 7.如申請專利範圍第5或6項之鏈狀氧化矽系中空 微粒子之製造方法，其中在前述步驟（f)之後，接著實 施下述步驟（g ): (g )將鏈狀氧化矽系中空微粒子分散液，在5 〇〜 300°C之範圍進行水熱處理之步驟。 8 _如申請專利範圍第5〜7項中任一項之鏈狀氧化砍 系中空微粒子之製造方法，其中前述步驟（d)係下述步 驟（d-Ι ): -53- 201034958 (d-1 )於前述步驟（c )所得之鏈狀複合氧化物粒子 分散液中，添加鹼水溶液與下述以化學式（1 )所示的有 機矽化合物及/或其部分水解物，在鏈狀複合氧化物粒子 上形成氧化矽被覆層之步驟 RnSiX(4_n) · · · (1) 〔惟，R :碳數1〜1 〇之非取代或取代烴基、丙烯醯基、 環氧基、甲基丙烯醯基、胺基、CF2基；X:碳數1〜4之 烷氧基、矽烷醇基、鹵素或氫；η: 0〜3的整數〕。 9. 如申請專利範圍第5〜7項中任一項之鏈狀氧化矽 系中空微粒子之製造方法，其中前述步驟（d)係下述步 驟（d - 2 ) (d-2 )於前述步驟（c )所得之鏈狀複合氧化物粒子 分散液中’添加鹼水溶液與酸性矽酸液，在鏈狀複合氧化 物粒子上形成氧化矽被覆層之步驟。 10. 如申請專利範圍第5〜7項中任一項之鏈狀氧化 矽系中空微粒子之製造方法，其中前述步驟（d)係下述 步驟（d - 3 ): (d-3 )於前述步驟（c )所得之鏈狀複合氧化物粒子 分散液中，添加矽酸鹼水溶液與鋁酸水溶液，在鏈狀複合 氧化物粒子上形成氧化矽被覆層之步驟。 11. 一種透明被膜形成用塗佈液，其特徵爲含有申請 專利範圍第1〜1 0項之鏈狀氧化矽系中空微粒子與基質形 -54 - 201034958 成成分所成。 12. 一種附透明被膜之基材，其特徵爲用申請專利範 圍第1 1項之透明被膜形成用塗佈液所形成的透明被膜， 係單獨或與其它被膜一起形成於基材表面上。201034958 VII. Patent application scope: 1. A chain-shaped yttrium oxide-based hollow microparticle characterized by oxidized yttrium-based hollow microparticles (primary particles) having an outer shell and an open interior, which are connected in a chain shape and have a cavity interpenetrating The through hole has an average length (L) in the range of 20 to 1 500 nm, an average width (w) in the range of 1 〇 to 300 nm, and a refractive index in the range of 1.1 〇 to 135. 2. The chain cerium oxide-based hollow fine particles according to claim 1, wherein the thickness (Ts) of the outer casing is in the range of 2 to 100 ηηη, and the ratio of the average width (W) (Ts) / (W) ) in the range of 0.05 to 0.30. 3. The chain yttria-based hollow microparticles of claim 1 or 2 wherein the ratio of the average diameter (Ds) of the through-holes to the average width (W) is (D) / (W). 1 ~ 〇.9 range. 4. The chain-shaped cerium oxide-based hollow fine particles of any one of the first to third aspects of the invention are composed of an inorganic oxide other than cerium oxide and cerium oxide. In the case of an inorganic oxide, the molar ratio MOx/Si 〇 2 is in the range of 0.0001 to 0.2. A method for producing a chain-like cerium oxide-based hollow fine particle, which comprises the following steps (a) to (f), wherein (a) an aqueous solution of a citrate and/or an acidic citric acid solution and a base The aqueous solution of the soluble inorganic compound is simultaneously added to the aqueous alkali solution, or simultaneously added to the aqueous alkali solution in which the concentration of the solid component is in the range of 0·01 to 2% by weight, in the case of the modulation, when S i 〇 2 a step of a composite oxide primary particle dispersion having a molar ratio M0x/SiO 2 (A ) in the range of 0.1 to 2 -52 to 201034958, wherein Μ Ο x represents an inorganic oxide other than cerium oxide; b) a step of washing the primary particle dispersion; (c) hydrothermalizing the washed primary particle dispersion in the presence of an electrolyte at 50 to 300 ° C to prepare a chain-like composite oxide particle a step of dispersing liquid; (d) forming oxidized sand or oxidized sand, oxidizing a coating layer, and modulating a cerium oxide or cerium oxide-alumina-coated chain-like composite oxide particle dispersion; (e) in cerium oxide or Cerium oxide·aluminum oxide coated chain composite oxide particles Adding an acid dispersion, the removal of at least a portion of the outer element constituting the composite oxide particles of sand, silicon oxide becomes a linear step-based dispersion of hollow fine particles; the dispersion of step (f) washing the resultant. 6 - A method for producing a chain-like cerium oxide-based hollow fine particle according to the fifth aspect of the invention, wherein the electrolyte in the aforementioned step (c) is a soil-based metal salt. 7. The method for producing a chain cerium oxide-based hollow fine particle according to claim 5 or 6, wherein after the step (f), the following step (g) is carried out: (g) a chain yttrium oxide system The hollow fine particle dispersion is subjected to a hydrothermal treatment step in the range of 5 Torr to 300 °C. The method for producing a chain oxidized chopped hollow microparticle according to any one of claims 5 to 7, wherein the aforementioned step (d) is the following step (d-Ι): -53- 201034958 (d- 1) In the chain-like composite oxide particle dispersion obtained in the above step (c), an alkali aqueous solution and an organic hydrazine compound represented by the following chemical formula (1) and/or a partial hydrolyzate thereof are added in the chain complex oxidation Step of forming a cerium oxide coating layer on the particles RnSiX(4_n) · (1) [R, R: an unsubstituted or substituted hydrocarbon group having a carbon number of 1 to 1 fluorene, an acryl fluorenyl group, an epoxy group, or a methacryl oxime a group, an amine group, a CF2 group; X: an alkoxy group having a carbon number of 1 to 4, a stanol group, a halogen or hydrogen; and an integer of η: 0 to 3. 9. The method for producing a chain cerium oxide-based hollow fine particle according to any one of claims 5 to 7, wherein the step (d) is the following step (d-2) (d-2) in the aforementioned step (c) a step of adding an aqueous alkali solution and an acidic citric acid solution to form a cerium oxide coating layer on the chain-like composite oxide particles in the obtained chain-like composite oxide particle dispersion. 10. The method for producing a chain cerium oxide-based hollow fine particle according to any one of claims 5 to 7, wherein the step (d) is the following step (d-3): (d-3) In the chain-like composite oxide particle dispersion obtained in the step (c), a citric acid aqueous solution and an aqueous solution of alumina are added to form a cerium oxide coating layer on the chain-like composite oxide particles. A coating liquid for forming a transparent film, which comprises a chain-like cerium oxide-based hollow fine particle of the first to tenth aspects of the patent application and a matrix-shaped composition of -54 - 201034958. A substrate comprising a transparent film, which is characterized in that the transparent film formed by the coating liquid for forming a transparent film of the invention of claim 11 is formed on the surface of the substrate alone or together with another film. -55--55-
TW098142722A 2008-12-18 2009-12-14 A chain-like silica-based hollow fine particles and a method for producing the same, a coating liquid for forming a transparent film containing the fine particles, and a substrate coated with a transparent film TWI510434B (en)

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