TWI299741B - Substrate with a hard coating film - Google Patents

Description

1299741 王久、發明說明 [發明所屬之技術領域] 本發明係有關與基材間優異之密貼性、抗擦傷性、膜 硬度等，以及帶電防止性能、透明性、濁度（haze)等優異 之附有硬質覆膜之基材。 /、 [先前技術] >為增進玻璃、塑膠片材、塑膠透鏡等之基材表面之抗 T :努丨生起見’周知有在基材表面形成硬質覆膜的作法，而 進仃有作為4樣的硬質覆膜而在玻璃或塑膠等表面形成有 機樹脂膜或無機膜。再者，亦進行有在有機樹脂薄膜或無 機薄膜中調配樹脂勒:i k A # ^ 树細祖千或一虱化矽等之無機粒子以謀求更 進一步增進抗擦傷性的作法。 又，為防止玻璃、塑膠片材、塑膠透鏡等基材表面之 反射Μ ’周知有在其表面形成反射防止膜之作法，例如 周兵有猎由塗佈法、蒸鍍法、CVD(化學蒸汽沈積）法等， 氣樹脂、氣化鎂般的低折射率之物質之被膜形成 在玻璃或塑膠之基材表面，或將含有二氧化石夕微粒子等之 低折射率粒子的塗佈液塗 基材表面，以形成反射防止 用被胺的方法（參考例如， 日本專利特開平7-133105號公 報4)。再者，亦有為基材賦 △丄 仍巩只丨方止贡電之性能、遮蔽電 磁波之性能起見，形成含 力乂 3有金屬你u立、導電性氧1299741 WANG Jiu, EMBODIMENT OF THE INVENTION [Technical Fields of the Invention] The present invention relates to excellent adhesion to a substrate, scratch resistance, film hardness, and the like, and excellent in charge prevention performance, transparency, haze, and the like. A substrate coated with a hard film. /, [Prior Art] > In order to enhance the surface resistance of the surface of glass, plastic sheets, plastic lenses, etc., the surface of the substrate is known to have a hard coating on the surface of the substrate. Four kinds of hard films are formed on the surface of glass or plastic to form an organic resin film or an inorganic film. Further, it is also possible to prepare an inorganic particle such as a resin: i k A # ^树细祖千 or 虱 虱 in an organic resin film or an inorganic film to further improve the scratch resistance. Moreover, in order to prevent reflection of the surface of a substrate such as a glass, a plastic sheet or a plastic lens, it is known that an anti-reflection film is formed on the surface thereof, for example, Zhou Bing has a coating method, an evaporation method, and a CVD (chemical vapor). In the deposition method, a film of a material having a low refractive index such as a gas resin or a magnesium oxide is formed on the surface of a glass or plastic substrate, or a coating liquid containing a low refractive index particle such as a silica fine particle is coated. The surface of the material is used to form a method for preventing the amine from being used for the reflection (see, for example, Japanese Patent Laid-Open No. Hei 7-133105). In addition, there are also △ 赋 基材 仍 仍 仍 仍 仍 仍 仍 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材

粒的導電性被膜的作法。 急巩化物U 如此，在設置反射防止用被膜及/或 為增進抗擦傷性起見，進 趿朕才 進饤有在基材與防止反射用膜及/ 314657 1299741 或導電性被膜之間形成硬質覆膜的作法。 然而，歷來之硬質覆膜當中，特別是基材係樹脂製之 基材時’冑時與基材間之密貼性或m本身之抗擦傷性變得 不足。 再者，在硬質覆膜上設置防止反射用膜及/或導電性 被膜時’ &來之硬質覆膜當中，有時在硬質覆膜形成後合 產生擦傷’或因靜電而附著塵埃，以致所製造的附有導電 性被膜之基材之透日m蜀度降低，而有製品之 的問題。 他 因此，期待-種能更增進與基材間的密貼性或抗擦傷 生’且同時能防止塵埃附著之附有硬f覆膜之基材 發0 *如此之歷來硬質覆膜當中，如增厚 =之同時，透明性亦可能降低，另外在ΡΕτ(聚對苯^ ^乙二醇醋）等柔軟基材時，則會發生反龜或彎曲等變 /。又，如硬質覆臈之膜厚成為約5" m以下，列視所 版中粒子種類’例如樹脂粒子、無機粒子、導電性粒子等 之種而使塗料用樹脂難於硬化，有時會膜厚而不硬化。 狀況下，本發明人為解決上述問題而 的、果U ’如在硬質覆膜中調配導電性粒子，則九 產生的靜電，其結果可抑制塵埃等之附著。 承所 ^特別是，如作為導電姓粒子而使用具有 乳化二録粒子時，驚奇地發現，其可製得_ =五 問題的硬質覆膜。 鮮夬所有上述 314657 6 1299741 ^ 又，亦發現如使用五氧化二銻時，在形成硬質覆膜時 7促進塗佈液中所含被膜成份的硬化，因此如作成特定厚 更貝覆膜時即能以極高效率進行被膜之硬化。 [發明内容] 鳘恩^目的 每本發明之目的在於提供具有與基材間之密貼性、抗擦 ^ 硬度等優異之同日寺，生產性等亦優異，且塵埃等之 附著少的硬質覆膜的附有被膜之基材。 有關本發明之附有硬質覆膜之基材，係由基材、及基 材上所形成的硬質覆膜而成，而其特徵為： 該硬質覆膜含有基質成份及五氧化二録（sb2〇5)粒 子，该五氧化二銻粒子之平均粒徑在2至i〇〇nm之範圍， 而硬質覆膜中之五氧化 之範圍。 二録粒子之含量在5至9 5重量％ 前述基質成份，係以熱固化樹脂或紫外線固化樹脂較 合適。 圍 前述硬質覆膜之膜厚 較佳為在〇·1至20 // m之範 更佳為在0.2至10 // m 再者，前述硬質覆膜之膜厚 之範圍。 以再形成有防止反射薄膜者為 在前述硬質覆膜上 佳。 再者’亦可在前述硬質覆膜與防止反射薄膜之間，形 314657 7 1299741 成有中間膜。 說明 以下，就有關本發明之附有硬質覆膜之基材加以說 明0 本發明之附有硬質覆膜 A .^ ^ ^ 胰之暴材，係由基材、及經形 在基材上的硬質覆膜而成。 基材The practice of a conductive film of particles. In the case of providing the film for preventing reflection and/or for improving the scratch resistance, the film is formed between the substrate and the film for preventing reflection and/or 314657 1299741 or the conductive film. The practice of filming. However, among the conventional hard films, particularly in the case of a substrate-based resin substrate, the adhesion between the substrate and the substrate or the scratch resistance of m itself is insufficient. In addition, when the anti-reflection film and/or the conductive film are provided on the hard film, the hard film may be formed after the hard film is formed or the dust may adhere due to static electricity. The surface of the manufactured substrate with the conductive film is reduced in the degree of penetration, and there is a problem in the product. Therefore, he expects a substrate with a hard f-film that can improve the adhesion to the substrate or scratch-resistant and at the same time prevent dust from adhering to the substrate. When the thickness is increased, the transparency may be lowered. In the case of a soft substrate such as ΡΕτ (poly-p-phenylene glycol vinegar), reverse turtle or bending may occur. In addition, when the film thickness of the hard cover is about 5 " m or less, the resin type of the coating, such as resin particles, inorganic particles, and conductive particles, is hardly cured, and the film thickness may be thick. Without hardening. In the case where the present inventors have solved the above problem, if the conductive particles are blended in the hard film, the static electricity generated by the present invention can suppress the adhesion of dust or the like. In particular, when an emulsified second-recorded particle is used as a conductive surname particle, it has surprisingly been found that it can produce a hard film of _= five problems. All of the above-mentioned 314657 6 1299741 ^ Also, it has been found that when a tantalum pentoxide is used, when the hard film is formed, 7 the hardening of the film component contained in the coating liquid is promoted, so that when a specific thick and more mulch film is formed, The film can be hardened with extremely high efficiency. OBJECT OF THE INVENTION The object of the present invention is to provide a hard coating which is excellent in productivity and the like, and has excellent adhesion and the like, and has excellent adhesion to the substrate and excellent rubbing resistance. A substrate to which a film is attached. The substrate with a hard film according to the present invention is formed from a substrate and a hard film formed on the substrate, and is characterized in that: the hard film contains a matrix component and a pentoxide (sb2) 〇 5) Particles, the average particle diameter of the bismuth pentoxide particles is in the range of 2 to i 〇〇 nm, and the range of pentoxide in the hard film. The content of the second recording particles is from 5 to 95% by weight. The aforementioned matrix component is preferably a thermosetting resin or an ultraviolet curing resin. The film thickness of the hard film is preferably in the range of 〇·1 to 20 // m, more preferably 0.2 to 10 // m, and the film thickness of the hard film. It is preferable that the anti-reflection film is formed on the hard film. Further, an intermediate film may be formed between the hard film and the antireflection film in the shape of 314657 7 1299741. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the substrate with a hard film according to the present invention will be described. The hard material of the present invention having a hard film A. ^ ^ ^ pancreas is made of a substrate and a shape on the substrate. Made of hard film. Substrate

本發明所使用$其U 土 ，並不特別限定而可使用周知 者’可例舉：玻璃、聚碳醅The U soil used in the present invention is not particularly limited and can be used by a well-known person's example: glass, polycarbonate

酉日、丙烯酸樹脂、PET、TACG 尿酸二烯丙酯）等之趟微 苴中…二 』膝薄膜等、塑膠面板等 中树月曰系基材較適用。 Μ Μ_ 硬質覆膜，含有基質成份及五氧化二 其特徵為：五氧化二銻粒平 2 5 立（ 之範圍，而硬質覆膜中之五氧：::切在2至⑽謂 羊L "It _錦粒子之合暑太ς = n 重量°/❶之範圍。 了卞又3里在5至9 化—録;子 本發明所使用之五氣化- lOOrm，較佳$ 一才子，係平均粒徑在2至 子乂1土马5至80nm之範圍。 如五氧化二銻粒子之平均粒 B洋，目丨Η日丁 了丨 仅衣滿刖述靶圍之下限 日^，則侍不到增進與基材間之 ”艮 的效果，；^ 0士、ro 山、生或抗擦傷性、膜硬度 扪效禾有％還會降低，又， 、叉厌 足夠的防止帶電之性能。阻增大而可能得不到 314657 8 1299741 如五氧化二銻粒子之亚 士 T卞之千均粒徑超過前述範圍之上限 才雖α五氧化一録粒子之含量而有所不同，惟可能膜之 透明性降低、膜被著色、或濁度增高。 、 硬質覆膜中之五氧化二録粒子之含量，以別办計， 一般在5至95重量。/。，LV + , Λ 里/。以在1〇至80重量％之範圍為佳。 如硬質覆膜中之五氧化二銻粒子之含量，以Sb2〇 計，若未滿前述範圍之下限時，則不能充份獲得與㈣間 之密貼性、抗擦傷性以及膜硬度之增進效果，又因不能呈 見^的=止γ電之性能’因此所得附有硬質覆膜之基材 上容易附著塵埃。因此，在設置後述的有防止反射膜及/ 或中間膜(導電膜、折射率調整膜)的基材之製造時，、所得 的基材之透明性或濁度可能會較劣而製品之收率降低。 又，在形成膜厚在約1〇//m以下再者在5#爪以下， 特別在2"m以下之薄硬質覆膜時，有時會使塗料用樹脂 固化或促進固化的效果不夠。 曰 硬質覆膜中之五氧化二銻粒子之含量，以Sh%計， 如超過前述範圍之上限，則可能與基材間之密貼性降低或 產生空隙（void)，使硬質覆層之硬度降低。又，所得附有 硬質覆膜之基材的透明性或濁度亦不足。再者，更無法促 進前述塗料用樹脂之硬化的效果。 如硬質覆膜中之五氧化二銻粒子之含量，以Sb20 計，在上述範圍内，則除可獲得與基材間的密貼性、2捧 傷性、膜硬度之增進效果、膜固化之促進效果等以外，尚 能提高硬質覆膜本身之折射率（St。5之折射率為2 0)，即 314657 9 1299741 使基材的折射率例如低至1 ·55，或硬質覆膜之基材折射 率例如低於1.55時，由於可增大硬質覆膜與基材間、以 及視需要所形成的防止反射膜間的折射率差距，而可形成 防止反射性能優異的附有被膜之基材。 如此的五氧化二銻粒子係使用依周知之製造方法所製 造者而不特別限定，惟具體的製造方法其平均粒徑在上述 範圍内，並能獲得具有與基材間充份的密貼性或硬度以及 抗擦傷性的附有硬質覆膜之基材，則並不特別限定，惟由 本申請案申請人所申請的日本專利特開平2_18〇71 7號公 報所揭示的五氧化二銻溶膠（sol)之製造方法，由於可製得 粒徑均勻而安定性、透明性優異的五氧化二銻溶膠，因2 了 很適合採用。 詳細而言，對特定莫耳比之三氧化二銻與鹼物質的混 合物中按既定速度添加既定量之過氧化氫，即可製造。 如本發明之在硬質覆膜中含有五氧化二銻粒子，則可 形成與基材間之密貼性優異之同日寺，抗擦傷性、膜硬度優 異的硬質覆膜。在，匕，如此的效果，在導電性氧化物粒； 之中，係五氧化二銻粒子特有者’而在氧化銦、錫摻雜氧 化銦、低次元氧化鈦等導電性氧化物粒子、三氧化二銻粒 子、金屬微粒子等則並不能呈現。 ； 士其理由雖然不明確，惟在基質成份係熱固化性樹脂 呀，可推論為五氧化二銻粒子在促進樹脂之固化。 另外：！五氧化二銻粒子以外之粒子，則有塗料用樹 曰之固化變慢或不會固化的情形。此乃除了五氧化二銻以 314657 10 1299741 而五氧化二銻粒子則可 外之粒子可能有妨礙固化的作用 能有抑制此作用的效果。 以樹脂基質較適 作為硬質覆膜中所含的基質成份 合0 士广種樹脂基質以具體而·r，均可採用周知之熱固化性 树月曰、熱塑性樹脂作為塗料用樹脂。 這種樹脂可例舉如：歷來所使用的聚醋樹脂、聚碳酸 醋樹脂、聚醯胺樹脂、购樹脂' 熱塑性丙浠酸樹脂、 齓化乙烯樹脂、含氟樹脂、醋酸乙烯樹脂、㈣橡膠等之 熱塑性樹脂、聚胺酿樹脂、2聚氰胺樹脂、石夕樹脂、丁縮 越樹脂、反應性矽嗣樹脂、㈣樹脂、環氧樹脂 '不飽和 聚酯樹脂、熱固化性丙烯酸樹脂等之熱固化性樹脂等。再 者’亦：為此等樹脂之2種以上之共聚物或改性物。 此等树知，可為乳液樹脂、水溶性樹脂、親水性樹脂。 、者士係熱固化性樹脂時，可為紫外線固化型者，亦可 為電子線固化型者，而如係熱固化性樹脂時，可含有固化 在本卷月中，特別在熱固化樹脂時，調配有五氧化二 ;:子才之效果(與基材間的密貼性、抗擦傷性以及硬度 之增進效果）較為顯著。 硬質覆膜之厚度 # m較佳，以〇 2至5 如在此範圍之厚度 以〇·1至20/zm為佳，以0.2至 10 # m之範圍者為更佳。 ’則由於硬質覆膜中含有五氧化 314657 11 1299741 在弟粒子之故’此使被膜充份固化之同時，可得薄膜與基材 間的密貼性、抗擦傷性、膜硬度等優異，經濟性亦優異的 附有硬質覆膜基材。 如硬負覆膜之厚度未滿前述範圍之下限時，由於硬質 覆膜薄而不能充足吸收施加至硬質覆膜表面的應力而使鉛 筆硬度不足。 如硬貝覆膜之厚度超過前述範圍之上限時，則難以均 勻塗佈膜厚或均勻乾燥，因而會產生龜裂或空隙，而使所 得硬質覆膜之強度或透明性變得不充份。 、如此的硬質覆膜，可藉由形成前述基質成份的基質形 成成伤A s有月)述之五氧化二銻粒子的塗佈液之塗佈而 形成。 另外，調製塗佈液時，為能調製經均勻分散的塗佈液 起見’以將五氧化二録粒子作成經分散在分散媒中的溶膠 後使用者為佳。 經分散在醇等有機溶 面經以周知之石夕烧偶 分散溶膠可任意為水分散溶膠、 媒中的有機溶媒分散溶膠。 再者，五氧化二銻粒子可為其表 合劑所處理者。 當溶===所調製的分散溶膠及基質形成成份在適 等。 疋生起見，亦可添加表面活性劑 又，塗佈液中 溶解基貝形成成份之同時，亦可含有 314657 1299741 能容易揮發的溶劑，而基質形成成份係、熱固化性樹脂時， 了因應需要而調配固化劑。 將這種塗佈液依周知之浸潰法、噴塗法、旋塗法、輥 塗法等方法塗佈在基材上並乾燥，在熱固化性樹脂之固^ 後，在熱塑性樹脂之因應需要在基材之軟化點以下之溫度 施予加熱處理，即可形成硬質覆膜。 本發明之附有硬質覆膜之基材中，可在硬質覆膜上設 置有防止反射膜。。 孩止反射簿睃 本發明之防止反射膜可使用歷來周知之防止反射膜， 祇要是具防止反射性能者則並不特別限定。具體而言，如 折射率車乂月；)述硬質覆膜為低者，則具備有防止反射性能。 這種防止反射膜，係由防止反射膜形成用基質、及視 需要所添加的低折射率成份而成。 防止反射膜形成用基質，係能形成防止反射膜的成 伤而可彳之與基材間之密貼性或硬度以及塗工性等之觀點 選擇使用。 具to而3，可使用與前述硬質覆膜形成成份同樣之基 質成份。 又’作為基質而能使用加水分解性有機矽化合物。具 月豆而a ’如在例如：烷氧矽烷與醇之混合液中，添加水及 .乍為催化片丨的酉夂或鹼’即可成為適合使用之烷氧矽烷之部 份加水分解物。 加水々解性有機矽化合物可使用以通式RnSi(〇R，）4_ 13 314657 1299741 J式中R、R，為烷基、芸A r ^ 方基、乙烯基、丙烯基等之烴基， 一、2或3]所表示的貌她。特別是，四甲她、 四乙氧矽紅、四丙氧矽烷等之四烷氧矽烷很適合使用。 :任思含有之低拆射率成份除％、祕、❿續、 MgF等之低折射率物質之外，尚可例舉如：二氧化矽系6 粒子（二氧化石夕粒子、二氧化石夕中空粒子、二氧化石夕.氧 化銘複合氧化物粒子）、多孔質氧化石夕系粒子等。 7::=，本案申請人所申請的曰本專利特開平 R所揭不的多孔性之無機氧化物微粒子 表面使用一氧化石夕所被覆的複合氧化物微粒子 射率低而防止反射性能優異的防止反射膜。、〜折 :止：射膜中之低折射率成份之含量以％重量％以 入^土 5〇重量％以下為較佳。如低折射率成份之 二超過90重置％時’則被膜之強度可能會降低 貝覆層（如形成有後述的中間膜時為中間層）等之盘A材門 防止反射膜之厚度以50至300nm為佳，更以 200nm之範圍為更佳。 至 如防止反射膜之厚度未滿前述範 止反射性能等會變差。 ㈣強度、防 =止反射膜之厚度超過前述範圍時，則可能會在膜 射性能不龜】：或此膜之強度會降低或膜厚過厚以致防止反 如此的防止反射膜夕加玄， . 之折射率，會因低折射率成份與樹 314657 14 1299741 月曰寻基貝的混合比例及所使用的樹脂等之折射率而有差 之折射率超過二 ·5°之範圍。如防止反射膜 防止則雖因基材之折射率而有不同，惟 下者。《性成可能會不足而難於獲得折射率在U8以 視需：::::：由含有上述防止反射膜形成用基質、及 液之塗佈而形成。編及溶媒的防止反射膜形成用塗佈 使用之溶媒祇要是能 膜不會有f彡響者衫制㈣心對所#防止反射 定1 方止反射膜形成用塗佈液之塗佈方法，並不特別限 塗法 貝伋膜之形成同樣’依浸潰法、喷 即可，特：二塗法等周知之方法塗佈在基材上並乾燥 力… 成成份為熱固化性樹脂的情形，即可，由 加熱處理、紫外線照射處 p了精由 質覆膜之固化，或在形處理等以促進硬 合物 ^ y 77中含有加水分解性有機矽化 物之加水分解.聚㈣處理錢進加水分解性有機石夕化合 中=月中’可在硬質覆膜與防止反射膜之間再設置有酉 、 , Acrylic resin, PET, TACG diallyl urate), etc. 二 二 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝 膝Μ Μ _ Hard film, containing matrix components and pentoxide. Its characteristics are: bismuth pentoxide granules 2 5 vertical (the range, while the hard mulch in the five oxygen::: cut in 2 to (10) is the sheep L &quot ;It _ 锦 之 合 ς = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The average particle size is in the range of 2 to 乂1 to 5 to 80 nm. For example, the average particle of the bismuth pentoxide particles is B, and the target is only the outermost limit of the target circumference. The effect of the "艮" between the substrate and the substrate can not be improved; ^^, ro mountain, raw or scratch-resistant, the film hardness is reduced, and the fork is tired enough to prevent the charging performance. The resistance may increase and may not be obtained. 314657 8 1299741 If the average particle size of the asbestos T of the bismuth pentoxide particles exceeds the upper limit of the above range, although the content of the alpha pentoxide is different, it is possible The transparency of the film is lowered, the film is colored, or the turbidity is increased. The content of the pentoxide particles in the hard film is not limited. Generally, it is in the range of from 1 to 80% by weight in the range of from 5 to 95% by weight, in the range of from 1 to 80% by weight, such as the content of the cerium oxide particles in the hard coating, in the case of Sb2? When the lower limit of the above range is not satisfied, the adhesion between the adhesion to (4), the scratch resistance, and the film hardness may not be sufficiently obtained, and the performance of the γ-electricity may not be exhibited. When the substrate of the film is easily adhered to the substrate, the substrate is provided with an antireflection film and/or an intermediate film (conductive film or refractive index adjusting film), and the transparency of the obtained substrate or The turbidity may be inferior and the yield of the product may be lowered. Further, when the film thickness is about 1 〇//m or less and the thickness is 5 or less, especially when it is a thin hard film of 2 Å or less, sometimes The effect of curing or promoting the curing of the coating resin is insufficient. The content of the cerium oxide particles in the hard coating film is, in terms of Sh%, if it exceeds the upper limit of the above range, the adhesion to the substrate may be lowered. Or creating a void to reduce the hardness of the hard coating. The transparency or turbidity of the base material of the film is also insufficient. Further, the effect of curing the coating resin is not promoted. For example, the content of the ruthenium pentoxide particles in the hard film is within the above range in terms of Sb20. In addition to the adhesion to the substrate, the adhesion of the film, the effect of improving the film hardness, and the effect of promoting the film curing, the refractive index of the hard film itself can be increased (St. 5 refractive index). 20), that is, 314657 9 1299741, such that the refractive index of the substrate is as low as 1.55, or the refractive index of the substrate of the hard film is, for example, less than 1.55, because the hard film and the substrate can be increased, A substrate having a film which is excellent in antireflection performance can be formed by forming a difference in refractive index between the antireflection films formed as needed. Such a ruthenium pentoxide particle is not particularly limited by the use of a known production method, but the specific production method has an average particle diameter within the above range, and can have sufficient adhesion to the substrate. The hardened film-attached substrate having a hardness and a scratch resistance is not particularly limited, and the bismuth pentoxide sol disclosed in Japanese Patent Application Laid-Open No. Hei No. Hei. The production method of sol) is excellent in the stability and transparency of the bismuth pentoxide sol. Specifically, it can be produced by adding a predetermined amount of hydrogen peroxide to a mixture of a specific molar ratio of antimony trioxide and an alkali substance at a predetermined rate. When the ruthenium pentoxide particles are contained in the hard film of the present invention, it is possible to form a hard film which is excellent in adhesion to the substrate and has excellent scratch resistance and film hardness. In the case of the conductive oxide particles, among the conductive oxide particles, the conductive oxide particles such as indium oxide and tin doped indium oxide and low-order titanium oxide are used. Oxidized ruthenium oxide particles, metal microparticles, etc. are not present. Although the reason for the reason is not clear, but the matrix component is a thermosetting resin, it can be inferred that the antimony pentoxide particles promote the curing of the resin. Also:! Particles other than the antimony pentoxide particles may be slow or not cured by the coating of the tree. This is in addition to the bismuth pentoxide to 314657 10 1299741 and the bismuth pentoxide particles may have an effect of inhibiting the curing. The resin matrix is suitable as a matrix component contained in the hard film. The resin matrix of the broad-type resin is specifically used, and a known thermosetting resin, a thermoplastic resin, or a thermoplastic resin can be used as the coating resin. Such a resin may, for example, be a polyester resin, a polycarbonate resin, a polyamide resin, a resin, a thermoplastic acrylic resin, a vinyl halide resin, a fluorine resin, a vinyl acetate resin, or a (four) rubber. Thermoplastic resin, polyamine brewing resin, 2 melamine resin, Shixi resin, butyl resin, reactive oxime resin, (4) resin, epoxy resin 'unsaturated polyester resin, thermosetting acrylic resin, etc. A thermosetting resin or the like. Further, it is also a copolymer or a modified product of two or more kinds of resins. These trees are known to be emulsion resins, water-soluble resins, and hydrophilic resins. When the thermosetting resin is used, it may be an ultraviolet curing type or an electron curing type, and when it is a thermosetting resin, it may be cured in this month, especially in a thermosetting resin. The blending has a pentoxide oxidation; the effect of the sub-component (adhesiveness with the substrate, scratch resistance and hardness enhancement effect) is remarkable. The thickness of the hard film is preferably m to 〇 2 to 5, and the thickness in this range is preferably 〇·1 to 20/zm, more preferably in the range of 0.2 to 10 #m. 'Because the hard film contains pentoxide 314657 11 1299741 in the case of the younger particles, the film is fully cured, and the film and the substrate are excellent in adhesion, scratch resistance, film hardness, etc., and economical. It is also excellent in properties and is provided with a hard coated substrate. If the thickness of the hard negative film is less than the lower limit of the above range, the hardness of the lead pen is insufficient because the hard film is thin and the stress applied to the surface of the hard film is not sufficiently absorbed. When the thickness of the hard shell coating exceeds the upper limit of the above range, it is difficult to uniformly apply the film thickness or to uniformly dry, and cracks or voids are generated, so that the strength or transparency of the obtained hard film is insufficient. Such a hard film can be formed by coating a coating liquid of the ruthenium pentoxide particles in which the matrix of the matrix component is formed. Further, in the case of preparing a coating liquid, it is preferred to prepare a uniformly dispersed coating liquid to form a bismuth pentoxide particle as a sol dispersed in a dispersion medium. The organic solvent is dispersed in an organic solvent such as an alcohol, and the sol can be arbitrarily dispersed as a water-dispersing sol or an organic solvent-dispersing sol in a medium. Further, the antimony pentoxide particles can be treated by the surfactant. When dissolved === the prepared dispersed sol and matrix forming components are in moderation. For the sake of hygiene, a surfactant may be added, and the composition of the base of the coating may be dissolved in the coating liquid, and the solvent which is easily volatilized by the 314657 1299741 may be contained, and when the matrix is formed into a component or a thermosetting resin, it is required. And the curing agent is formulated. The coating liquid is applied onto a substrate by a known method such as a dipping method, a spray coating method, a spin coating method, a roll coating method, and the like, and after the thermosetting resin is cured, it is required for the thermoplastic resin. A heat treatment can be performed at a temperature lower than the softening point of the substrate to form a hard film. In the substrate coated with a hard film of the present invention, an antireflection film may be provided on the hard film. . The antireflection film of the present invention can be used as the antireflection film which is conventionally known, and is not particularly limited as long as it has antireflection properties. Specifically, if the hard coating film is low, the anti-reflection performance is provided. Such an antireflection film is formed by a substrate for preventing formation of a reflection film and a low refractive index component to be added as needed. The substrate for preventing the formation of a reflective film can be selected from the viewpoint of preventing adhesion of the reflective film, adhesion to the substrate, hardness, and workability. With to and 3, the same base component as the above-mentioned hard film forming component can be used. Further, a hydrolyzable organic hydrazine compound can be used as a substrate. Having a yoghurt and a 'such as a mixture of alkoxy decane and an alcohol, adding water and hydrazine as a catalyst for the ruthenium or base of the ruthenium can be a partial hydrolyzate of the alkoxy oxane which is suitable for use. . The hydrolyzable organic ruthenium compound may be a hydrocarbon group of the formula RnSi(〇R,) 4_ 13 314657 1299741, wherein R, R is an alkyl group, a 芸A r ^ square group, a vinyl group, a propylene group or the like, , 2 or 3] expressed her appearance. In particular, tetraalkoxydecane such as tetramethyl, tetraethoxy erythro, tetrapropoxydecane or the like is suitable for use. : Ren Si contains low-removability components in addition to %, secret, suspending, MgF and other low-refractive-index substances, such as: cerium oxide-based 6 particles (cerium dioxide cerium particles, dioxide Evening hollow particles, sulphur dioxide, oxidized composite oxide particles, porous oxidized oxide particles, and the like. 7::=, the composite oxide particles coated on the surface of the porous inorganic oxide fine particles which are not disclosed in the patent application by the applicant of the present application have low incidence of the composite oxide particles and excellent antireflection performance. Prevent reflection film. 〜折折: The content of the low refractive index component in the film is preferably 5% by weight or less by weight % by weight. If the low refractive index component exceeds 90% by reset%, the strength of the film may decrease the thickness of the disk A-layer anti-reflection film of the shell coating (such as an intermediate layer when an intermediate film is formed later). It is preferably up to 300 nm, and more preferably in the range of 200 nm. For example, if the thickness of the reflective film is less than the above, the reflection performance and the like may be deteriorated. (4) When the thickness of the strength and anti-reflection film exceeds the above range, the film may not be in the performance of the film: or the strength of the film may be lowered or the film thickness may be too thick to prevent the anti-reflection film from being reversed. The refractive index is inferior to a range of two to five degrees due to the mixing ratio of the low refractive index component to the 314657 14 1299741 曰 基 基 及 and the refractive index of the resin used. If the anti-reflection film is prevented, it differs depending on the refractive index of the substrate, but the following. "Sexual formation may be insufficient and it is difficult to obtain a refractive index at U8. It is formed as needed by the substrate containing the above-mentioned antireflection film and the coating of the liquid. The solvent used for the coating of the antireflection film for the preparation of the solvent and the solvent for coating the coating film for the formation of the antireflection film is not required. It is not particularly limited to the formation of the film of the beryllium film. It can be applied by the dipping method or the spray, and the method of coating is applied to the substrate by a known method such as the two-coating method and drying. The composition is a thermosetting resin. , that is, by heat treatment, ultraviolet irradiation, p-curing of the fine film, or in the form of treatment to promote the hydrolysis of the hydrolyzable organic telluride in the hard compound y 77. Poly (four) treatment of money Into the water-decomposable organic stone 化 化 = mid-month 'can be placed between the hard film and the anti-reflection film

料：間膜，可設置折射率為16以上者。 則4寸別疋’如基材或硬質覆膜之折射率為1.55以下時， 、只防止反射膜之折射率之間的差距變小，以致防止反射 314657 15 1299741 之性能變得不足夠，因而以形成折射率在1.6以上之中間 膜為佳。 中間膜係、由问折射率之金屬氧化物微粒、及視需要 之中間膜形成用基質而成。 ★中間膜形成用基質，係指能在硬質覆膜表面形成中間 膜的成份之意，而可選自適合與硬質覆膜間的密貼性或塗 工性等之條件的樹脂等使用，具體而f，可例舉如：在前 述硬質覆膜形成用基質中所使用以及在前述防止反射 膜中所例7F的:^氧⑨烧等之加水分解性有機砍化合物等。 N折射率之金屬氧化物微粒以使用折射率在1 ·60以 上之金屬氧化物微粒者為佳。以折射率在i·70以上者為 更佳。這種金屬氧化物微粒，可例舉如：氧化欽（2.5〇)、 ?化辞(2.0)、氧化錯(2·2〇)、氧化鈽(22)、氧化錫(2〇卜 氧化鉈（2.1)、鈦酸鋇（2 4〇)、氧化鋁（173)、氧化鎂（I”）、 氧化紀（1.92)、氧化銻（2·〇)、氧化銦（2〇)等。（括弧内為 折射率） 此中較佳為氧化鈦、氧化飾、氧化錫、氧化銻、氧化 鍅、氧化銦等之導電性微粒，再者，在此等微粒中摻雜有 銻、錫、氟等之異種元素的導電性微粒，因其所得之附有 防止反射膜具有防止反射之性能並具有防止帶電效果、遮 蔽電磁波性能故而適用。 ' 如金屬氧化物微粒之折射率為1 ·6〇以下時，由於所 侍中間膜之折射率無法在1 ·60以上，與防止反射膜間的 折射率之差距小使得防止反射性能不足，故而不能充份發 314657 16 1299741 揮設置中間膜之效果。 又’金屬氧化物微粒之平均粒徑較佳為在5至1〇〇nm 之範圍。更佳範圍為在10至60nm。平均粒徑在5nm以 下之粒子，視金屬氧化物之種類，有時難於製得，而如超 過1〇Onm，則由於可視光線之明顯散射而使被膜之透明性 變差因而不宜。 中間膜中之金屬氧化物微粒之含量，祇要是能製得折 射率在L6以上之中間膜，則並不特別限定，雖然因中間 膜形成用基質或金屬氧化物微粒之折射率而有所異，惟通 常，佳為在3。至⑽重量％、更佳為在5{)至％重量广 之範圍。另外，中間膜可為不含基質 微粒而成者。 土貝而僅由金屬氧化物 广中間膜中之金屬氧化物微粒之含量為％重量％以 下時，雖然因金屬氧化物微粒之種 Μ ^ ^ . 裡娟向有所異，惟由於中 :膜之折射率不會成為以上，因 中間膜之效果。 Τ个主h又置 如此的中間膜，可由含右古 敖、另、目子 3有回折射率之金屬氧化物微 / 視而要之中間膜形成用基質以及溶媒的中 用塗佈液之塗佈而形成。 、形成 再者，使用如此的金屬氧化 用之塗佈液時，較佳為作成…拉以5周製中間膜形成 ^. A 為作成使金屬氧化物微粒分耑扁八Λ 媒中的溶膠使用，可作成水 放在刀散 機、m zt上a本 膠’ |分散在醇等$古 械冷媒中的有機溶媒分散溶膠#之有 理前述微粒子後，將叙分心；者乂周知之偶合劑處 刀放在有機溶媒中的有機溶媒分散 314657 17 1299741 溶膝與塗料用樹脂使用適當卞 間膜形成用之塗佈液。再 &心刎加以稀釋以作成中 i ，泠就、六+ 為增進分散性、安定性辇去巳 見，塗佈液中亦可添加表面活性劑等。 m·"起 可使用的溶媒祇要是能二 射膜、中間膜無不良_者=療發逸散並對所得防止反 Λ〜 響者’則並不特定限定。 中間膜形成用塗佈液之塗 塗佈液之情形同樣，並 〜、方止反射膜形成用 形成用塗佈液者同樣，以，、:^與前述的硬質覆膜 η失之法、嘖塗法、旋 孕比土法寺方法塗佈在基材上 係熱固化性樹脂時，即可醉由力：;/了’特別是形成成份 t.. 0,,+ ^ ρτ猎由加熱處理、紫外線照射處理、 电子線如射處理等以促進中間膜 合古4 八Μ Μ 4杜形成成份中 進力有機石夕化合物時’則可藉由加熱處理以促 進加水*解性有切化合物之加水分解.聚縮合。 質覆=方ί:成中間膜時’首先在基材上形成前述的硬 、後w i巾間膜形成用之塗布液，接著 再視需要按基材之軟仆LV π々、w ώ 、乂、， 之軟化點以下之溫度進行加熱處理，並形 成珂述的防止反射膜即可製得。 特別是在基質成份係熱固化性樹脂時，可在形成各膜 (硬質覆膜、防止反射膜、中間膜)後，實施固化促進處理，、 又’可在硬質覆膜之固化促進處理後形成中間膜並實施固 化促進處理之後，再形成防止反射膜並實施固化促進處 理。 如上所述的有關本發明之附有硬質覆膜之基材，由於 貝復膜中έ有五氧化二録粒子，因而消除所產生的靜 314657 18 1299741 電，其結果可抑制塵埃等之附 與基材間高優異之密貼性、抗 膜本身之硬度亦面，而如硬質 成時’將藉由五氧化二錄以促 度的被膜。 t明之效果 著之同時，形成的硬質覆膜 擦傷性、膜硬度等。又，被 覆膜係由熱固化性樹脂所構 進被膜固化，而可製得高硬 本發明中，由於基材表面所設置的硬質覆膜含有五氧 化二録粒子’目而與基材間具優異之密貼性、抗擦傷性、 膜硬度等’其同時可製得具有防止帶電性能的附有硬質覆 膜之基材X由於含有五氧化二錄粒子而可製得高硬 度，且薄膜與基材間的密貼性、抗擦傷性、膜硬度等優異， 經濟性亦優異的附有硬質覆膜之基材。 再者，當製造在硬質覆膜上之防止反射膜或中間膜與 防止反射薄膜的附有硬質覆膜之基材時，亦不會被刮傷2 附著塵埃等異物，而可以高收率製得透明性、濁度等優異 的附有硬質覆膜之基材。 [實施方式] 以下，藉由實施例而再具體說明本發明，惟本發明並 不因此等實施例而所限定。 實施例1 生質覆膜形成用塗佈浚之調f 在五氧化二銻粒子分散液（觸媒化成工業（股）製： ELCOM PC-14 ’ 平均粒徑 20nm，Sb205 濃度 20 重量 ％， 刀放媒·乙基〉谷域素/乙醇重置比=9 4 / 6 6) 2 0 0 g中混合紫外 19 314657 1299741 線固化樹脂（大日太油蓴（盼、制·很 ㈡不油墨u又）衣·優尼得克V55〇〇)16〇g與 乙基溶纖素64〇g，以調製硬質覆膜形成用塗佈液(H-1)。 Μ有石更貝覆膜基材（F-1)之盤造 將硬質覆膜形成用塗佈液（Η-1)在PET薄膜（厚度：188 ，折射率：165)上，各別依鑲條塗佈加㈣㈣法進 行k佈I 80 C下乾燦1分鐘後照射高壓水銀燈（⑼界/㈣口 分鐘使其固化，以調製附有硬質覆膜之基材（F-i-i)及（F_ 1-2)。此時之硬質覆膜之厚度為5/zrn及〇.3//m。 ^使用表面電阻計（三菱化學（股）製：核列斯達）測定所 得硬質覆膜之表面電阻，其結果示於表i。 又使用薄膜混濁計（haze meter)(蘇佳試驗機（股）製） 測定全光線穿透率及濁度，其結果示於表1。 再者，依下述方法及評估基準評估鉛筆硬度、抗擦傷 性以及密貼性，其結果示於表1。 筆硬；t之測 準照JIS-K-5400，使用鉛筆硬度計（pencil化以以）進 測定。 丁 达差J^J；生之測兔 使用#0000鋼絲絨（steel wool)，以500g/cm2荷重、、風 動50次，並以目視觀察膜表面，依下列基準評估，結果 示於表1。 ’ 古 : 認不出線溝之傷：◎ 可稍微認出線溝之傷：〇 314657 1299741 可認出多數線溝之傷：△ 表面被全體性切削：X t貼性 在附有防止反射膜之基材（F-1)表面使用小刀按縱橫 1 mm之間隙劃傷11條平行傷痕以作成！ 00個方格，對此 黏接玻璃紙帶（cell〇phane tape，登錄商標），接著，當將 玻璃紙f (登錄商標）加以剝離時，將被膜未被剝離而殘留 的方格數目按下列4 P&b段分類，以評估密貼性。將其結果 不於表1。 殘留方格之數目在95個以上：◎ 殘留方格之數目在90至94個：〇 殘留方格之數目在85至89個：△ 殘留方袼之數目在8 4個以下：X 實施例2 用塗佈洛 在五氧化二銻粒子分私、％ ^ 刀放液（觸媒化成工業（股）製： ELCOM PC-14，平均粒經 卞J徂仫2〇nm，sb2〇5濃度2〇重量。/〇， 7刀散媒··乙基溶纖素/乙醇重 坪重里比=94/66)200g中混合紫外 線固化樹脂（大日本油墨（股）,· ^ 、）衣·優尼得克V5500)93.3g與 乙基溶纖素706·7g，以調製硬暂 似亡成拼面 更貝復膜形成用塗佈液（H-2)。 在實施例1中，除使用硬 使你如& , 一 又貝设膜形成用塗佈液以外， 其餘則按與實施例1同樣方 ^ Α _ 工’以調製2片附有硬質覆膜 之基材（F-2-1)及（F-2-2)。此眭+ 守之硬質覆膜之厚度為5// m 314657 21 1299741 及 〇·3 // m 〇 全光線穿透率、濁 其結果示於表1。 就所得的硬質覆膜評估表面電阻 度、鉛筆硬度、抗擦傷性以及密貼性 實施例3 在五氧化一銻粒子分散液(觸媒化成工業(股)製： ELC〇MPC-14,平均粒徑20随，Sb2〇5濃度2〇重量0/〇, 分散媒：乙基溶纖素/乙醇重量㈣4/66)2〇〇g中混合紫外 線固化樹脂（大日本油墨（股）製：優尼得克v55〇〇)4〇g與 土 /合纖素760g，以調製硬質覆膜形成用塗佈液（η」）。 、在實施例1中，除使用硬質覆膜形成用塗佈液（Η-3: 以外其餘則按與實施例i同樣方式，以調製3片附有硬 貝復膜之基材（F-3-1)、（ρ·3_2)以及（F_3_3)。此時之硬質 覆膜之厚度分別為5 " m、i " m、以及〇·3 " m。 就所得的硬質覆膜評估表面電阻、全光線穿透率、濁 度、錯筆硬度、抗擦傷性以及密貼性，其結果示於表1。 實施例4 液（H-4)之調, 在五氧化二銻粒子分散液（觸媒化成工業（股）製： ELC〇M PCM4，平均粒徑20nm，Sb205濃度20重量％， 为放媒·乙基溶纖素/乙醇重量比=94/66)200g中混合紫外 線固化樹脂（大曰本油墨（股）製：優尼得克V5500)40g與 乙基溶纖素782.9g，以調製硬質覆膜形成用塗佈液（H_4)。 22 314657 1299741 覆膜之某姑(T-4)之製造 在實施例1中，除使用硬質覆膜形成用塗佈液 以外’其餘則按與實施例1同樣方式，以調製2片附有硬 質覆膜之基材（F-4-1)及（F-4-2)。此時之硬質覆膜之厚声 為 5 A in 及 〇.3 # m。 全光線穿透率、濁 其結果示於表1。 就所得的硬質覆膜評估表面電阻 度、錯筆硬度、抗擦傷性以及密貼性 形成用塗佈液（h-5)之調製 在五氧化二銻粒子分散液（觸媒化成工業（股）製· ELCOM PC-14 ,平均粒徑 20nm，Sb205 濃度 20 重量 〇/〇， 刀政媒·乙基溶纖素/乙醇重量比=：94/66)200g中混合雨 酉文樹脂（希他羅伊土 1〇〇7，曰立化成（股）製）4〇g與乙基溶 纖素760g，以調製硬質覆膜形成用塗佈液（H-5)。 膜之某材（F-5)之製造 在實施例1中，除使用硬質覆膜形成用塗佈液（H_5) 以外，其餘則按與實施例1同樣方式，以調製2片附有硬 質覆膜（F-5-1)及（F-5-2)。此時之硬質覆膜之厚度為5“奶 及 〇 · 3 // m 〇 就所得的硬質覆膜評估表面電阻、全光線穿透率、濁 度、鉛筆硬度、抗擦傷性以及密貼性，其結果示於表ι。 貫施例6 形成用塗佈液（H-6)之調製 將五氧化二銻膠體溶液（觸媒化成工業（股）製： 314657 23 1299741 κυ，平均粒徑l〇nm，Sb2〇5濃度1重量％)在旋轉蒸發器 中進行溶媒取代之同時加以濃縮，以調製五氧化二録粒子 分散液（Sb2〇5濃度20重量％，分散媒：乙基溶纖素/乙醇 重量比=94/66)。在此分散液200g中混合紫外線固化樹脂 (大曰本油墨（股）製：優尼得克V5500)4〇g與乙基溶纖素 760g，以調製硬質覆膜形成用塗佈液（H-6)。 BLilk質霜膜之基材（F-6)之製 在實施例1中，除使用硬質覆膜形成用塗佈液（H_6) 以外，其餘則按與實施例1同樣方式，以調製2片附有硬 質覆膜之基材（F-6-1)及（F-6-2)。此時之硬質覆膜之厚度 為 5 // m 及 〇 · 3 // in 〇 就所得的硬質覆膜評估表面電阻、全光線穿透率、濁 度、鉛筆硬度、抗擦傷性以及密貼性，其結果示於表i。 實施例7 石更"質覆酸用塗佑浚m-7、夕，卞 在五氧化二銻膠體溶液（觸媒化成工業（股” ：RSI κυ，平均粒徑10nm，Sb2〇5漠度i重量％)4_中，^ 加卜環氧丙氧基丙基三甲氧石夕燒之石夕烧偶合劑4，在6 C:㈣、:：時。接著，在旋轉蒸發器中進行溶媒取代4 2同二加二：縮’以調製五氧化二銻粒子分散液(Sb20"“ 八重=°’分㈣：乙基溶纖素/乙醇重量㈣綱“ 製：二TV混合紫外線固化樹脂(大曰㈣ ”膜矿忐55〇〇)4〇g與乙基溶纖素760g，以調製对 貝後胺形成用塗佈液（H-7)。 314657 24 1299741 服直AJL覆膜之某材（F-7)之i造 在實施例1中，除使用硬質覆膜形成用塗佈液（H-7) 以外’其餘則按與實施例1同樣方式，以調製2片附有硬 質覆膜之基材（F_7_l)及（F_7_2)。此時之硬質覆膜之厚度 為 5 // m 及 〇. 3 // m。 就所付的硬貝覆膜评估表面電阻、全光線穿透率、濁 度、鉛筆硬度、抗擦傷性以及密貼性，其結果示於表工。 比較例1 成用塗佈液（RH-^之調製 混合紫外線固化樹脂（大曰本油墨 V55〇〇)2〇0g與乙基溶纖素 又衣：優尼得克 塗佈液⑽_υ。 "周製硬質覆膜形成用 服直硬一質覆膜之某材 在實施例1中，除使用硬質覆膜形 以外，其餘則按與實施例i同樣方式，、用塗佈液（RH-1) 膜之基材（RF-1-1)及（rlu)。此萨製附有硬質覆 5 // m及〇.3 # m。 才之石更質覆膜之厚度為 就所得的硬質覆膜評估表面電卩且、入 度、鉛筆硬度、抗擦傷性以及密貼性，王光線穿透率、濁 比較例2 其結果示於表1。 混合丙稀酸樹脂（希他羅伊土 1 〇 〇 製）200g及乙基溶纖素8〇〇g，以調制 曰立化成（股） 液（RH-2)。 、设暝形成用塗佈 314657 25 1299741 服覆膜之某材（RF-2)之 成用塗佈液（RH-2) 以調製2片附有硬 #之硬質覆膜之厚 在實施例1中，除使用硬質覆膜步 以外，其餘則按與實施例1同樣方式， 質覆膜之基材（RF-2-1)及（RF-2-2)。此 度為 5//m 及 Oj#]!!。 全光線穿透率、濁 其結果示於表1。 就所得的硬質覆膜評估表面電阻、 度、鉛筆硬度、抗擦傷性以及密貼性， 比較例3 硬貝後.膜形成用塗佈液（RH- 3 在二氧化矽有機凝膠（觸媒化成 卡1G攻工業（股）製；OSCAL- 1432 ’平均粒徑i2nm，Si〇2濃声壬曰 2 /辰度20重量％，分散媒··異 丙醇）2〇〇g中混合紫外線固化樹脂（大日本油墨（股）製：優 尼得克V5500)40g與乙基溶纖素76〇g，以調製硬質覆膜 形成用塗佈液（RH-3)。 附有硬_質覆膜之基材fRF_3)之，珠 在實施例i中，除使用硬質覆膜形成用塗佈液（rh_3) 以外，其餘則按與實施例！同樣方式，以調製、片附有硬 夤覆膜之基材（RF-3-1)、（RF-3-2)以及（RF-3-3)。此時之硬 質覆膜之厚度為5//m、以及〇3//m。 就所得的硬質覆膜評估表面電阻、全光線穿透率、濁 度、雜筆硬度、抗擦傷性以及密貼性，其結果示於表1。 比較例4 硬膜形成之調製 將二氧化二銻粒子（平均粒徑15〇 # m)按能成為濃度 26 3J4657 1299741 3〇重《%之方式分散在異丙醇中，使用碾砂機（sand mi⑴ 在30 C下粉碎5小時。對此添加異丙醇以調製濃度2〇重 量％之二氧化二銻微粒分散液（平均粒徑5加^)。在此分散 液2〇〇g中混合紫外線固化樹脂（大曰本油墨（股）製··優尼 知克V5500)4〇g與乙基溶纖素76〇g，以調製硬質覆膜形 成用塗佈液（RH-4)。 歷有硬—質覆膜之某材造 成用塗佈液（RH-4) 以調製2片附有硬 時之硬質覆膜之厚 在實施例1中，除使用硬質覆膜形 以外，其餘則按與實施例1同樣方式， 質覆膜之基材（RF-4-1)及（RF-4-2)。此 度為 5 // m 及 0.3 // m。 全光線穿透率、濁 其結果示於表1。 就所得的硬質覆膜評估表面電阻 度、鉛筆硬度、抗擦傷性以及密貼性 314657 27 1299741 表1 附有硬WJf眩夕等材 基材 種類 —~一- _^質箱 [膜 吞粒子 基質 膜厚 Um 全光線 穿透率 % 濁度 % 鉛筆 硬度 抗擦 傷性 密貼性 表面電阻 0/□ 平均粒徑 nm 含量 重量! 種類 含量 重量？6 V 1ΠΒ 實施例1 PET 20 20 紫外線固 化樹脂 80 5 91.9 1.1 3H Ο X ΐυ 10 0.3 92.1 1,2 9U r\ ΟΑ 實施例2 PET 20 30 紫外線固 化樹脂 70 5 91.6 U cn 3H ◎ © DU 6 0.3 91.8 u 2H 〇 12 實施例3 PET 20 50 紫外線固 化樹脂 50 5 91.1 u 3H V·/ Q Q 2 1 91.4 1.7 2H 〇 〇 3 0.3 91.5 1.7 2H rs A 實施例4 PET 20 70 紫外線固 化樹脂 30 5 81.0 1.9 3H w 〇 •f 5 0.3 91,3 H 2.0 2H 〇 8 實施例5 PET 20 50 丙烯酸 樹脂 50 5 91.3 I 1,8 2H @ ◎ 1 0.3 91.5 Ί 1,8 2H 〇 ◎ 3 實施例6 PET 10 50 紫外線固 化樹脂 50 5 9U 1.5 3H e 3 0.3 91,8 1.6 2H o (g) 7 實施例7 PET 10*’ 50 紫外線固 化樹脂 50 5 91.8 1.4 4H © 5 0.3 91.9 1.5 2H 〇 ◎ 10 比較例1 PET — 0 紫外線固 化樹脂 100 5 92.0 j 1.1 2H A △ 10000以上 0.3 92.0 1.1 2B X △ inonnci l· 比較例2 PET 一 0 丙烯酸 樹脂 100 5 91.9 1.1 1H X △ 10000以上 0.3 92.0 1.3 B X △ 10000以 J： 比較例3 PET (S 丨 〇2)*2 50 紫外線固 化樹脂 50 5 91.0 1.β 2H X Δ 10000以上 1 91.4 1.8 2B X Δ 10000以上 0.3 91.6 2.0 3B X A ιππππι^] 1- 比較例4 PET (Sb203)*3 50 紫外線固 化樹脂 50 5 91.0 1 1.6 2H Δ JLa △ 10000以上 0.3 91.5 2.2 J B X A 1ΠΠΠΠΡ丨 寧1:貫死例/保經矽烷偶合劑處理者〇 *2:比較例3係不用五氧化二銻而使用二氧化矽者〇 *3:比較例4係不用五氧化二銻而使用三氧化二銻者。 實施例8 中間膜形成用之塗佈液（Μ-1)之調t 將作為高折射率粒子的氧化鈦膠體（觸媒化成工業（股） 製；歐布多雷克1130Z，折射率2.2，平均粒徑2〇nm，濃 度20重量％)20g，與紫外線固化樹脂（大曰本油墨（股）製； 優尼得克V5500)0.44g以及異丙醇6.7g充份混合以調製 中間被膜形成用塗佈液（Μ-1)。 防止反射膜形成用塗佈液（R-1)之調’ [低折射率複合氧化物微粒分散凝膠之製造] 將曱基甲氧秒烧27.4g>i^合在〉農度〇·65重量％之氫氧 化鈉水溶液872.6g中，在室溫下攪拌1小時，以調製作 314657 28 1299741 為3 3/2的1 · 5 f ! %之無色透明的部份加水分解物。 曲接著，料為籽粒（seed particle)的平均粒徑5·，叫 濃度20重量％之二氧化矽凝膠2〇g與純水38〇g的混合物 加溫至8(TC。此反應母液之pH| 1〇 5，並對該母液中耗 ^ 6小時同時添加作為Si〇2的濃度15重量％之石夕酸納水 /合液900g與上述部份加水分解物之水溶液9⑼g以及作為 Al2〇3的/辰度0.5重量。之鋁酸鈉水溶液18〇〇g。其間，維 持反應母液之溫度為8(rc。反應母液之pH在剛添加後上 升為12.7，其後殆無變化。添加完畢後，將反應液冷卻 至至溫，使用超濾膜（ultra filter)洗淨，以製得固體成份 濃度20重量％之含有甲基之Si〇2. Ai2〇3複合氧化物微粒 (A-ι)之分散液。 對所得的複合氧化物微粒（八-”之分散液25〇g中添加 純水550g並加溫至98。(：，在維持此溫度之下，耗費5小 日守之方式添加以陽離子交換樹脂將矽酸鈉水溶液進行脫驗 而得的矽酸液（Si〇2濃度3.5重量％)1〇〇g，以製得由二氧 化矽所被覆的含有甲基的Si02.Al203複合氧化物微粒（Β_υ 之分散液。接著，使用超濾膜洗淨，並對作成固體成份濃 度13重量％的分散液5〇〇g添加純水i，125g，再滴下濃鹽 酸（農度35.5重量％)而作成ΡΗ1·0以實施從微粒去除鋁的 處理。 接著，在添加pH3 · 0之鹽酸水溶液1 〇公升及純水5 A升之下，使用超濾膜以洗淨去除所溶解的鋁鹽之同時， 進行/辰縮以製付由固體成份濃度1 3重量％之二氧化石夕所 29 314657 1299741 被覆的含有甲基之Si〇2 · α!2〇3複合氧化物微粒（C-1)之分 散液。 將所得複合氧化物微粒（C-1)之分散液uoog，與純 水500g、乙醇l，750g以及濃度28重量％之氨水626g的 浪合液加溫為3 5 °C後，添加石夕酸乙基鹽（s i〇2濃度2 8重 量％) 1 04g，並使用前述二氧化矽加以被覆。使用蒸發器 將此濃縮至固體成份濃度5重量％後，添加濃度1 5重量 %之氨水以作成pHIO，在180。(：下之高壓鍋内加熱處理2 小日^ ’接著’使用超濾膜進行濃縮，製得經以固體成份濃 度10重量％之二氧化矽所完全被覆的含有甲基之Si〇2 · Al2〇3複合氧化物微粒（D-1)之分散液。 该二氧化矽被覆複合氧化物微粒⑴-”之Si〇2/Ai2〇3 莫耳比為278，平均粒徑為34nm，折射率為i 36。 在此，粒子之折射率係依下列方式進行測定者。 (1)將複合氧化物微粒（Dq)之分散液置入蒸發器中，使分 散溶媒蒸發。 (2) 將此在12(rc下乾燥，並作成粉末。 (3) 將已知折射率之標準折射液在玻璃板上滴下23滴， 並對此混合上述粉末。 ⑷使用各種標準折射液實施上述（3)之操作，當混合液（多 為糊質狀）成為透明時之標準折射液之折射率作為微粒之 折射率。 使上述所得的複合氧化物微粒(d])之分散液經過超 〜fe，亚將分散媒之水取代為乙醇。 314657 30 1299741 充份混合該乙醇凝膠（固體成份濃度5重量％)5〇g，與 紫外線固化樹脂（大曰本油墨（股）製；優尼得克V55〇〇)3g 以及異丙醇與正丁醇之ιη(重量比）混合溶媒47g，以調 製防止反射膜形成用塗佈液（n)。 腹_^:硬質霜膜之篡材（F-8)之絮i告 在按與貫施例1同樣方式所調製的硬質覆膜之基材 (F-1-ι)上，依鑲條塗佈法塗佈上述所調製的中間被膜形 成用塗佈液（M-1)，在80。(：下乾燥i分鐘。此時之中間膜 之厚度為80nm，折射率為1 ·80。 接著，依鑲條塗佈法塗佈上述所調製的防止反射膜形 成用塗佈液（R-D，在欧下乾燥i分鐘後，照射高壓水 銀燈（8〇W/cm)1分鐘以使其固化，以調製附有硬質覆膜之 基材（F-8-D。此時之防止反射薄膜之厚度為8〇nm。、 在此，表中所示的硬質覆膜、防止反射膜之各種折射 率，係在石夕晶圓1個別將上述各塗佈液按與上$方法進行 塗佈、乾燥以及固化處理，並使用橢圓對稱計 (ellipS〇meter)(ULVAC 社製，EMS_1}加以測定者。 就所得的附有硬質覆膜之基材評估表面電阻、全光 穿透率、濁度、鉛筆硬度、抗擦傷性以及 …果 示於表2。 ，、、、、σ果Material: The interlayer film can be set to have a refractive index of 16 or more. When the refractive index of the substrate or the hard film is 1.55 or less, the difference between the refractive indices of the reflective film is prevented to be small, so that the performance of the reflection 314657 15 1299741 is not sufficient, so that the performance of the reflection 314657 15 1299741 is insufficient. It is preferred to form an intermediate film having a refractive index of 1.6 or more. The intermediate film system is composed of a metal oxide fine particle having a refractive index and a matrix for forming an intermediate film as needed. The matrix for forming an intermediate film means a component which can form an intermediate film on the surface of the hard film, and can be selected from resins suitable for the adhesion between the hard film and the coating property, etc. Further, f is, for example, a hydrolyzable organic chopping compound or the like which is used in the above-mentioned substrate for forming a hard film, and in the above-mentioned antireflection film, 7F: Oxygen 9 or the like. The metal oxide fine particles having a refractive index of N are preferably those having a metal oxide fine particle having a refractive index of 1.60 or more. It is more preferable that the refractive index is i.70 or more. Such metal oxide fine particles may, for example, be oxidized (2.5 Å), oxidized (2.0), oxidized (2·2 〇), cerium oxide (22), tin oxide (2 〇 铊 铊 ( 2.1), barium titanate (2 4 〇), alumina (173), magnesium oxide (I"), oxidized (1.92), yttrium oxide (2 〇), indium oxide (2 〇), etc. (in brackets The refractive index is preferably a conductive fine particle such as titanium oxide, oxidized tin, tin oxide, antimony oxide, antimony oxide or indium oxide. Further, the fine particles are doped with antimony, tin, fluorine or the like. The conductive fine particles of the different elements are used because they have anti-reflection properties and prevent the charging effect and shield the electromagnetic wave performance. When the refractive index of the metal oxide particles is 1 · 6 〇 or less, Since the refractive index of the intermediate film is not more than 1.60, the difference in refractive index between the antireflection film and the antireflection film is small, so that the antireflection performance is insufficient, so that the effect of the intermediate film can not be sufficiently 314657 16 1299741. The average particle diameter of the oxide fine particles is preferably in the range of 5 to 1 〇〇 nm. The range is from 10 to 60 nm. Particles having an average particle diameter of 5 nm or less are sometimes difficult to produce depending on the type of metal oxide, and if more than 1 〇 Onm, the transparency of the film is changed due to the apparent scattering of visible light. The content of the metal oxide fine particles in the intermediate film is not particularly limited as long as it can produce an intermediate film having a refractive index of L6 or more, although the refractive index of the matrix or metal oxide particles is formed by the intermediate film. However, in general, it is preferably in the range of 3 to (10)% by weight, more preferably in the range of 5{) to % by weight. In addition, the intermediate film may be formed without matrix particles. When the content of the metal oxide fine particles in the metal oxide wide interlayer film is % by weight or less, although the metal oxide fine particles are different in the range of Μ ^ ^ , the refractive index is not It will become the above, because of the effect of the interlayer film. The main film is set up with such an intermediate film, which can be formed by a metal oxide containing a refractive index of the right ancient yttrium, another, and the target 3 Medium coating of substrate and solvent It is formed by coating with a liquid. When such a coating liquid for metal oxidation is used, it is preferable to form an intermediate film formed by a five-week process. A is formed to separate the metal oxide particles. The use of the sol in the scorpion medium can be used as a water in a knife-dispersing machine, m zt on a gelatin' | disperse in an organic solvent dispersion sol in an alcoholic refrigerant such as an alcohol, and the rationality of the aforementioned microparticles will be distracted. The organic solvent dispersion in the organic solvent is known as the coupling agent. 314657 17 1299741 The coating solution for the knee and coating resin is formed by using an appropriate interlayer film, and then diluted with the heart to make it. , 泠 、, + 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为m·" The solvent that can be used is not particularly limited as long as it is a film that can be used in the film and the film is not defective. In the same manner as in the case of the coating liquid for forming a coating liquid for forming an intermediate film, the method of forming the coating liquid for forming a reflective film is the same as that of the hard coating film η. When the coating method and the spinning method are coated on the substrate and the thermosetting resin is applied, the force can be drunk:; / 'Specially forming the composition t.. 0,, + ^ ρτ hunting by heat treatment, Ultraviolet irradiation treatment, electron beam irradiation treatment, etc. to promote the intermediate film combination of the ancient Μ 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜 杜Decomposition. Polycondensation.质质=方ί: When forming an intermediate film, the coating liquid for forming the hard and the inner wi-film is formed on the substrate first, and then the soft servant LV π 々, w ώ, 乂 according to the substrate is required. The temperature below the softening point is heat-treated to form an anti-reflection film as described above. In particular, when the matrix component is a thermosetting resin, the film can be cured after the formation of each film (hard film, antireflection film, or interlayer film), and can be formed after the curing process of the hard film is accelerated. After the intermediate film is subjected to the curing acceleration treatment, the antireflection film is further formed and a curing promotion treatment is performed. The hard film-coated substrate according to the present invention as described above has a pentoxide-containing particle recorded in the film, thereby eliminating the generated electricity of 314657 18 1299741, and as a result, the adhesion of dust or the like can be suppressed. The adhesion between the substrate is excellent, and the hardness of the film itself is also good, and if it is hard, it will be recorded by the pentoxide. The effect of t-ming is at the same time, the formation of hard film scratches, film hardness and the like. Further, the coating film is cured by a thermosetting resin, and a high hardness can be obtained. In the present invention, since the hard film provided on the surface of the substrate contains the pentoxide particles, the substrate is interposed between the substrates. It has excellent adhesion, scratch resistance, film hardness, etc. It can also produce a hard coated substrate X with antistatic properties. It can produce high hardness due to the inclusion of pentoxide particles. A substrate coated with a hard film which is excellent in adhesion to a substrate, scratch resistance, film hardness, and the like, and is also excellent in economy. Further, when the antireflection film or the intermediate film and the antireflection film are formed on the hard film, the hard film-attached substrate is not scratched, and foreign matter such as dust is adhered to the substrate. A substrate coated with a hard film excellent in transparency, turbidity, and the like. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. Example 1 Coating of a coating for forming a green film was carried out in a coating of cerium pentoxide particles (manufactured by Catalyst Chemical Co., Ltd.: ELCOM PC-14 ' average particle diameter 20 nm, Sb205 concentration 20% by weight, knife Media · Ethyl > gluten / ethanol reset ratio = 9 4 / 6 6) 2 0 0 g mixed UV 19 314657 1299741 line curing resin (Da Ri Tai oil 莼 (hop, system · very (two) no ink u In addition, 16% g of ethyl lysin and 64 〇g of ethyl lysin were prepared to prepare a coating liquid (H-1) for forming a hard film.盘 石 更 贝 覆 覆 覆 F F F F F 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 硬 PET PET PET PET PET PET PET PET Strip coating plus (4) (four) method for k-cloth I 80 C dry for 1 minute, then irradiate high-pressure mercury lamp ((9) boundary / (four) mouth to make it solidify to prepare the substrate with hard film (Fii) and (F_ 1- 2) The thickness of the hard film at this time is 5/zrn and 〇.3//m. ^ The surface resistance of the obtained hard film is measured using a surface resistance meter (manufactured by Mitsubishi Chemical Corporation: Nuclear Lista). The results are shown in Table 1. The total light transmittance and turbidity were measured using a haze meter (manufactured by Sujia Tester Co., Ltd.), and the results are shown in Table 1. Further, the following method was used. The evaluation criteria were used to evaluate pencil hardness, scratch resistance, and adhesion. The results are shown in Table 1. The pen was hard; the measurement of t was JIS-K-5400, which was measured using a pencil hardness tester (pencilization). The difference is J^J; the raw rabbit is made of #0000 steel wool, with a load of 500g/cm2, and the wind is moved 50 times, and the surface of the film is visually observed. The results are shown in Table 1. 'Ancient: I can't recognize the injury of the trench: ◎ I can slightly recognize the wound of the trench: 〇314657 1299741 Can recognize the damage of most trenches: △ The surface is cut by the whole: X t Scratch 11 parallel flaws on the surface of the substrate (F-1) with the anti-reflection film by using a knife with a gap of 1 mm in length and width to make 00 squares, which are bonded to the cellophane tape (cell〇phane tape, When the cellophane f (registered trademark) is peeled off, the number of squares remaining without being peeled off by the film is classified according to the following paragraph 4 P&b to evaluate the adhesion. The result is not in the table. 1. The number of residual squares is more than 95: ◎ The number of residual squares is 90 to 94: the number of residual squares is 85 to 89: △ The number of residual squares is less than 8 4: X implementation Example 2 The coating was applied to the bismuth pentoxide particles, and the % ^ knife was discharged (catalyzed into a chemical system: ELCOM PC-14, average particle size 卞J徂仫2〇nm, sb2〇5 concentration 2 〇 weight. / 〇, 7 knives · · ethyl cellosolve / ethanol heavy ping heavy ratio = 94 / 66) 200g mixed UV Curing resin (Japan ink (share), · ^,) clothing · Unidek V5500) 93.3g and ethyl cellosolve 706·7g, to prepare the hard temporary like a face to form a film Cloth liquid (H-2). In the first embodiment, except that the coating liquid for forming a film is formed by hardening, and the other is the same as in the first embodiment, the two sheets are provided with a hard film. Substrate (F-2-1) and (F-2-2). The thickness of this 眭+ 守硬硬膜 is 5// m 314657 21 1299741 and 〇·3 // m 〇 total light transmittance and turbidity. The results are shown in Table 1. The surface resistivity, pencil hardness, scratch resistance, and adhesion of the obtained hard film were evaluated. Example 3 In a pentoxide pentoxide particle dispersion (catalyzed into a chemical industry: ELC 〇 MPC-14, average granules) Path 20, Sb2〇5 concentration 2〇 Weight 0/〇, Dispersing medium: ethyl cellosolve/ethanol weight (4) 4/66) 2〇〇g mixed with UV-curable resin (Daily Ink (share) system: Youni克克v55〇〇) 4〇g and soil/synthetic cellulose 760g to prepare a coating liquid (η" for forming a hard film. In the first embodiment, except for the coating liquid for forming a hard film (the other than the Η-3:, the same method as in the example i was used to prepare three substrates with a hard shell film (F-3). -1), (ρ·3_2) and (F_3_3). The thickness of the hard film at this time is 5 " m, i " m, and 〇·3 " m. The hard coating evaluation surface obtained Resistance, total light transmittance, turbidity, stagger hardness, scratch resistance, and adhesion. The results are shown in Table 1. Example 4 Liquid (H-4) adjustment, in the bismuth pentoxide particle dispersion (catalytic chemical industry (stock) system: ELC〇M PCM4, average particle size 20nm, Sb205 concentration 20% by weight, for the medium · ethyl cellosolve / ethanol weight ratio = 94 / 66) 200g mixed UV curing resin (Big Sakae ink (manufactured by Utsuka): 40 g of Euphoric Acid V5500) and 782.9 g of ethyl cellosolve to prepare a coating liquid for forming a hard film (H_4). 22 314657 1299741 A certain film of the film (T -4) In the same manner as in Example 1, except that the coating liquid for forming a hard film was used in the first embodiment, two sheets with a hard film were prepared. (F-4-1) and (F-4-2). The thick sound of the hard film at this time is 5 A in and 〇.3 # m. The total light transmittance and turbidity are shown in Table 1. The obtained hard coating film was used to evaluate the surface resistivity, the erroneous pen hardness, the scratch resistance, and the adhesion forming coating liquid (h-5) in the bismuth pentoxide particle dispersion (catalytic conversion industry) ) ELCOM PC-14, average particle size 20nm, Sb205 concentration 20 weight 〇 / 〇, Knife medium · ethyl cellosolve / ethanol weight ratio =: 94 / 66) 200g mixed rain 酉 resin (Hita Roy soil 1〇〇7, manufactured by 化立化成()) 4〇g and ethyl fibrin 760g to prepare a coating liquid for forming a hard film (H-5). (5) In the same manner as in Example 1, except that the coating liquid for forming a hard film (H_5) was used, the two sheets were prepared with a hard film (F-5-1). And (F-5-2). At this time, the thickness of the hard film is 5" milk and 〇·3 // m 〇, and the obtained hard film is used to evaluate surface resistance, total light transmittance, turbidity, pencil Hardness, scratch resistance and adhesion The results are shown in Table 1. Example 6 Preparation of a coating liquid (H-6) to prepare a ruthenium pentoxide colloidal solution (catalyzed into an industrial product: 314657 23 1299741 κυ, average particle diameter l〇 Nm, Sb2〇5 concentration: 1% by weight) was concentrated while being subjected to solvent substitution in a rotary evaporator to prepare a pentoxide particle dispersion (Sb2〇5 concentration: 20% by weight, dispersing medium: ethyl cellosolve/ Ethanol weight ratio = 94/66). Into 200 g of the dispersion, a UV curable resin (manufactured by Otsuka Ink Co., Ltd.: Union V5500) of 4 〇g and ethyl cellulolytic 760 g was mixed to prepare a coating liquid for forming a hard film (H- 6). The base material (F-6) of the BLilk cream film was prepared in the same manner as in Example 1 except that the coating liquid for forming a hard film (H_6) was used in the first embodiment. There are hard coated substrates (F-6-1) and (F-6-2). At this time, the thickness of the hard film is 5 // m and 〇·3 // in 〇, and the obtained hard film is used to evaluate surface resistance, total light transmittance, turbidity, pencil hardness, scratch resistance, and adhesion. The results are shown in Table i. Example 7 Shijiao"Sulphate-coated acid using Tuyou浚m-7, Xi, 卞 in bismuth pentoxide colloidal solution (catalytic chemical industry (stock): RSI κυ, average particle size 10nm, Sb2〇5 indifference i wt%) 4_, ^ Gabu glycidoxypropyl trimethicone Xishou Shi Xia coupling agent 4, at 6 C: (four), ::: Then, the solvent is carried out in a rotary evaporator Substituting 4 2 with two plus two: shrinking 'to prepare a dispersion of antimony pentoxide particles (Sb20 " "eight weight = ° ' points (four): ethyl fibrin / ethanol weight (four) outline" system: two TV mixed UV curing resin ( Otsuka (4) "membrane ore 忐 55 〇〇) 4 〇 g and ethyl cellulolytic 760 g to prepare a coating solution for the formation of benamine (H-7). 314657 24 1299741 (F-7) i was produced in the first embodiment except that the coating liquid for forming a hard film (H-7) was used, and the other two were prepared in the same manner as in Example 1 to prepare a hard film. The substrate (F_7_l) and (F_7_2). The thickness of the hard film at this time is 5 // m and 〇. 3 // m. The surface resistance, total light transmittance, and the surface transmittance of the hard shell film are evaluated. Turbidity, pencil hard Degree, scratch resistance, and adhesion, the results are shown in the table. Comparative Example 1 Preparation of a coating liquid (RH-^ preparation mixed ultraviolet curing resin (大曰本VV55〇〇) 2〇0g and ethyl Cellulite and clothing: Unitek coating liquid (10) _ υ. " Weekly hard film forming a material of a straight hard film, in the first embodiment, except for the use of a hard film shape, the rest The substrate (RF-1-1) and (rlu) of the coating liquid (RH-1) film were used in the same manner as in Example i. This coating was provided with a hard coating of 5 // m and 〇.3 # m. The thickness of the stone is more qualitative. The surface of the hard coating is evaluated for surface electric conductivity, penetration, pencil hardness, scratch resistance and adhesion. Wang light transmittance and turbidity comparison example 2 It is shown in Table 1. 200 g of a acrylic acid resin (Shita rouge soil 1 〇〇) and 8 〇〇g of ethyl cellosolve were mixed to prepare a ruthenium (RH-2) solution.暝 Formation coating 314657 25 1299741 coating material (RF-2) coating liquid (RH-2) to prepare two sheets of hard film with hard # thick thickness in the first embodiment, In addition to using hard Except for the film step, the substrate (RF-2-1) and (RF-2-2) of the film were coated in the same manner as in Example 1. The degree was 5//m and Oj#]!! The results of total light transmittance and turbidity are shown in Table 1. The surface hardness, degree, pencil hardness, scratch resistance, and adhesion of the obtained hard film were evaluated, and Comparative Example 3 was used for film formation. (RH-3 in cerium oxide organogel (catalyzed into card 1G attack industrial (stock) system; OSCAL-1432 'average particle size i2nm, Si〇2 thick 壬曰 2 / Chen 20% by weight, dispersion medium ··Isopropanol) 2〇〇g mixed with UV curable resin (made by Dainippon Ink Co., Ltd.: Unidek V5500) 40g and ethyl cellosolve 76〇g to prepare a coating for forming a hard film Liquid (RH-3). In the case of the base material fRF_3) to which the hard film is attached, the bead is the same as the embodiment except that the coating liquid for forming a hard film (rh_3) is used in the example i! In the same manner, the substrate (RF-3-1), (RF-3-2), and (RF-3-3) to which the hard film is attached is prepared. The thickness of the hard film at this time was 5 / / m, and 〇 3 / / m. The obtained hard film was evaluated for surface resistance, total light transmittance, turbidity, stray hardness, scratch resistance, and adhesion, and the results are shown in Table 1. Comparative Example 4 Preparation of hard film formation The cerium dioxide particles (average particle size 15 〇 #m) were dispersed in isopropyl alcohol in a manner of a concentration of 26 3J4657 1299741 3 〇 by weight, using a sander (sand Mi(1) was pulverized at 30 C for 5 hours, and isopropyl alcohol was added thereto to prepare a dispersion of cerium dioxide fine particles having a concentration of 2% by weight (average particle diameter: 5), and ultraviolet rays were mixed in the dispersion of 2 〇〇g. A cured resin (manufactured by Otsuka Ink Co., Ltd., U.S. V5500), 4 〇g, and ethyl cellulolytic solution, 76 〇g, to prepare a coating liquid for forming a hard film (RH-4). The coating liquid (RH-4) of a hard-quality film is used to prepare two sheets of hard film with a hard film. In Example 1, except for using a hard film shape, the rest is In the same manner as in Example 1, the substrate (RF-4-1) and (RF-4-2) of the film were coated. The degree was 5 // m and 0.3 // m. The total light transmittance and turbidity were obtained. It is shown in Table 1. The surface resistivity, pencil hardness, scratch resistance, and adhesion of the obtained hard film were evaluated. 314657 27 1299741 Table 1 Attached to the hard WJf glare substrate type - ~一- _^Rat box [film engulfing particle matrix film thickness Um total light transmittance % turbidity % pencil hardness anti-scratch adhesion surface resistance 0 / □ average particle size nm content weight! type content weight? 6 V 1 实施 Example 1 PET 20 20 UV-curable resin 80 5 91.9 1.1 3H Ο X ΐυ 10 0.3 92.1 1, 2 9U r ΟΑ Example 2 PET 20 30 UV-curable resin 70 5 91.6 U cn 3H ◎ © DU 6 0.3 91.8 u 2H 〇12 Example 3 PET 20 50 UV-curable resin 50 5 91.1 u 3H V·/ QQ 2 1 91.4 1.7 2H 〇〇3 0.3 91.5 1.7 2H rs A Example 4 PET 20 70 UV-curable resin 30 5 81.0 1.9 3H w 〇•f 5 0.3 91,3 H 2.0 2H 〇8 Example 5 PET 20 50 Acrylic resin 50 5 91.3 I 1,8 2H @ ◎ 1 0.3 91.5 Ί 1,8 2H 〇 ◎ 3 Example 6 PET 10 50 UV curing Resin 50 5 9U 1.5 3H e 3 0.3 91,8 1.6 2H o (g) 7 Example 7 PET 10*' 50 UV-curable resin 50 5 91.8 1.4 4H © 5 0.3 91.9 1.5 2H 〇 ◎ 10 Comparative Example 1 PET — 0 UV curable resin 100 5 92.0 j 1.1 2H A △ 10000 or more 0.3 92 .0 1.1 2B X △ inonnci l· Comparative Example 2 PET - 0 Acrylic resin 100 5 91.9 1.1 1H X △ 10000 or more 0.3 92.0 1.3 BX △ 10000 to J: Comparative Example 3 PET (S 丨〇 2) * 2 50 UV curing Resin 50 5 91.0 1.β 2H X Δ 10000 or more 1 91.4 1.8 2B X Δ 10000 or more 0.3 91.6 2.0 3B XA ιππππι^] 1-Comparative example 4 PET (Sb203)*3 50 UV-curable resin 50 5 91.0 1 1.6 2H Δ JLa △ 10000 or more 0.3 91.5 2.2 JBXA 1 ΠΠΠΠΡ丨 1 1: 死 死 / 保 矽 偶 偶 偶 处理 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 比较 3 3 3 3 3 3 3 3 3 3 3 3 3 The use of antimony trioxide is not required for antimony pentoxide. Example 8 The coating liquid for forming an intermediate film (Μ-1) was adjusted to be a titanium oxide colloid of a high refractive index particle (catalyzed into a chemical (manufactured by the company); Obdore 1130Z, having a refractive index of 2.2, An average particle diameter of 2 〇 nm, a concentration of 20% by weight) of 20 g, and 0.44 g of an ultraviolet curable resin (manufactured by Otsuka Ink Co., Ltd.; Unid V5500) and 6.7 g of isopropyl alcohol were mixed to prepare an intermediate film. Use a coating solution (Μ-1). The adjustment of the coating liquid (R-1) for preventing the formation of a reflective film [Production of a low-refractive-index composite oxide fine particle dispersion gel] 2 gg of thiol oxysecond squirrel > 〉 The mixture was stirred at room temperature for 1 hour in 872.6 g of a sodium hydroxide aqueous solution of a weight % to prepare a colorless and transparent partial hydrolyzate of 314657 28 1299741 to 3 3/2 of 1 · 5 f %. Next, the average particle size of the seed particles is 5, and a mixture of 2 〇g of a concentration of 20% by weight of cerium oxide gel and 38 〇g of pure water is heated to 8 (TC). pH|1〇5, and adding 9g of a concentration of Si〇2, which is 15% by weight of Si〇2, to the aqueous solution of 900g of the above-mentioned partial hydrolyzate, and 9(9)g of the aqueous solution of the hydrolyzate and as Al2〇 3 / Chen degree 0.5 weight. The sodium aluminate aqueous solution was 18 〇〇 g. During this time, the temperature of the reaction mother liquid was maintained at 8 (rc. The pH of the reaction mother liquid increased to 12.7 immediately after the addition, and thereafter the enthalpy did not change. Thereafter, the reaction liquid was cooled to a temperature, and washed with an ultra filter to obtain a methyl group-containing Si〇2. Ai2〇3 composite oxide particle (A-ι) having a solid concentration of 20% by weight. Adding 550 g of pure water to 25 〇g of the obtained composite oxide fine particles (eight-" dispersion and heating to 98. (:, while maintaining this temperature, it takes 5 hours to keep it. A citric acid solution obtained by de-testing an aqueous solution of sodium citrate with a cation exchange resin (Si〇2 concentration: 3.5% by weight) 1〇〇g, to obtain a dispersion of SiO 2 .Al 203 composite oxide fine particles (Β υ υ 含有 含有 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 5 % of the dispersion liquid was added with pure water i, 125 g, and concentrated hydrochloric acid (availability of 35.5 wt%) was added dropwise to prepare ΡΗ1·0 to carry out treatment for removing aluminum from the fine particles. Next, an aqueous solution of hydrochloric acid having a pH of 3.0·0 was added. 1 〇 liter and pure water 5 A liter, using ultrafiltration membrane to wash and remove the dissolved aluminum salt, while carrying out / shrinking to make a solid concentration of 13% by weight of the dioxide dioxide 314657 1299741 A dispersion of a coating of methyl-containing Si〇2·α!2〇3 composite oxide fine particles (C-1). The obtained composite oxide fine particles (C-1) dispersion uoog, and pure water 500g After adding 1,750 g of ethanol and 626 g of ammonia water having a concentration of 28% by weight to a temperature of 35 ° C, an ethyl salt of oxalic acid (28 wt% of si〇2) was added to 104 g, and the above-mentioned dioxide was used.矽 coating. Concentrate to a solid concentration of 5% by weight using an evaporator, add concentration 1 5 wt% of ammonia water is used to make pHIO at 180. (: heat treatment in a lower pressure cooker for 2 hours ^ 'then' is concentrated using an ultrafiltration membrane to obtain a cerium oxide having a solid concentration of 10% by weight. a dispersion of the coated Si〇2·Al2〇3 composite oxide fine particles (D-1) containing the methyl group. The cerium oxide-coated composite oxide fine particles (1)-"Si〇2/Ai2〇3 Mo Er ratio is 278, an average particle diameter of 34 nm, and a refractive index of i36. Here, the refractive index of the particles is measured in the following manner. (1) A dispersion of the composite oxide fine particles (Dq) is placed in an evaporator to evaporate the dispersed solvent. (2) This was dried at 12 (rc) and powdered. (3) A standard refractive solution of a known refractive index was dropped on a glass plate by 23 drops, and the above powder was mixed. (4) Using various standard refractive liquids In the above operation (3), the refractive index of the standard refractive liquid when the mixed liquid (mostly paste-like) becomes transparent is used as the refractive index of the fine particles. The dispersion of the composite oxide fine particles (d) obtained above is passed through ~fe, sub-dispensing the water of the dispersion medium to ethanol. 314657 30 1299741 Fully mix the ethanol gel (solid content concentration 5% by weight) 5 〇g, with UV-curable resin (large 曰 ink (share) system; excellent 3 g of Nidek V55 以及) and 47 g of a solvent (iv ratio) of isopropyl alcohol and n-butanol are mixed to prepare a coating liquid (n) for preventing reflection film formation. Abdominal _^: Coffin of hard frost film (F-8) The above-mentioned intermediate film was coated by a strip coating method on a substrate (F-1-ι) of a hard film prepared in the same manner as in Example 1 The coating liquid for formation (M-1) was dried at 80 ° for (i), and the thickness of the intermediate film at this time was 80 nm. Then, the coating liquid for forming an antireflection film (RD) prepared by the above-described method for coating the antireflection film was applied by a strip coating method, and then irradiated with a high pressure mercury lamp (8 〇 W/cm) for 1 minute. To cure it, to prepare a substrate coated with a hard film (F-8-D. The thickness of the antireflection film at this time is 8 〇 nm. Here, the hard film shown in the table, antireflection The various refractive indices of the film were applied, dried, and cured in each of the above coating liquids on the Shihwa wafer 1. An elliptical symmetry meter (ellip 〇 meter) (ULVAC, EMS_1) was used. The measured surface resistance, total light transmittance, turbidity, pencil hardness, scratch resistance, and the results of the obtained hard coated substrate are shown in Table 2. , , , , , σ

覆膜之基材（F-Qlt _ 基 在按與實施例2同樣方式所調製 1 j衣的附有硬質霜赔 材（F-2-1)上，按與實施例8同樣 八形成中間膜及1¾ 314657 31 1299741 反射膜’以調製附有硬質覆膜之基材（F冬〜 穿透:=附有：質覆媒之基材評估表面電阻、全光線 於表2。 ㈣硬度、抗擦傷性及密貼性，其結果示 及复星農HiiF ] 〇、 在按與實施例3同樣方式所調製 #(F^3 η π , η氣的附有硬質覆膜之基 式U· ηΓ:2):及㈣^ 二(F:r反射膜，以調製附有硬質覆膜之基材 i)、（F-10-2)以及（F-10_3)。 就^所得的附有硬質麗 穿透率、濁产^二 表面電阻、全光線 认主 度、鋁華硬度、抗擦傷性及密貼性…士果_ 於表2。 丹結果不 實施彳 道有堡道之基材（F-11)之絮立告 =按與實㈣4同樣方式所調製的附有硬質覆膜之基 二+…1}上，按與實施例8同樣方式形成中間膜及防止土 反射膜，以調製附有硬質覆膜之基材（F-Hq)。 全光線 其結果 *、就所得的附有硬質覆膜之基材評估表面電阻 穿透率、濁度、鉛筆硬度、抗擦傷性以及密貼性 示於表2。 迸有^1^_膜之基材（F-12)之 在按與實施你]5同#方式所調製的附有硬質覆膜之基 314657 32 1299741 ϋΓΓ)上，按與實施例8同樣方式形成中間膜及防止 夂射膜，以調製附有硬質覆膜之基材（F-m)。 =所：的附有硬質覆膜之基材評估表面電阻、全光線 :透率、濁度、錯筆硬度、抗擦傷性以及密貼性， 不於表2。 ，、、、、。禾The base material of the film (F-Qlt _ base was formed on the hard cream claim material (F-2-1) prepared in the same manner as in Example 2, and the same film as in Example 8 was formed. And 13⁄4 314657 31 1299741 Reflective film 'to prepare a substrate with a hard coating (F winter ~ Penetration: = attached: substrate for the evaluation of surface resistance, total light in Table 2. (4) hardness, anti-scratch The results are shown in the same manner as in Example 3, and the results are shown in the same manner as in Example 3 (F^3 η π , η gas with a hard film-based base U·ηΓ: 2): and (4)^2 (F:r reflective film to prepare the substrate i), (F-10-2) and (F-10_3) with a hard film attached. Permeability, turbidity, surface resistance, total light quality, aluminum hardness, scratch resistance and adhesion... _ _ in Table 2. Dan results in the implementation of the substrate of the ruins of the ruins (F- 11) In the same manner as in the embodiment 8, the intermediate film and the anti-soil reflective film are formed in the same manner as in the case of the embodiment (4). Hard coated substrate ( F-Hq). Results of total light*, evaluation of surface resistance transmittance, turbidity, pencil hardness, scratch resistance and adhesion of the obtained substrate coated with a hard film are shown in Table 2. The film of the film of the film (F-12) was formed in the same manner as in Example 8 on the substrate 314657 32 1299741(R) having a hard film prepared in accordance with the method of the present invention. And preventing the ruthenium film to prepare a substrate (Fm) with a hard film. The surface of the substrate with a hard film is evaluated for surface resistance, total light: permeability, turbidity, stray hardness, and resistance. Scratch and adhesion, not in Table 2. ,,,,,.

實施例1 I 膜之基材 材(F!?、與實施例6同樣方式所調製的附有硬質覆膜之基 反射膜 Γ實施例8同樣方式形成中間膜及防止 反射膜，以調製附有硬質覆膜之基材（1^13_1)。 就所得的附有硬質覆膜之基材評 穿读銮 1 — 1古表面電阻、全光線 牙透率、濁度、鉛筆硬度、抗擦傷性 示於表2。 …及进貼性，其結果 實施例1 4 K 基.材（F-14)之^^ 在與貫施例7同樣方式所調箩 7 1Λ L I的附有硬質覆膜之基 材（F-7-1)上，按與實施例8同樣方 -M ^ Λ化成中間膜及防止 反射潯Μ，以調製附有硬質覆膜之基材 就所得的附有硬質覆膜之基材 穿透率、濁度、錯筆硬度、抗擦傷性=電阻、全光線 示於表2。 生以及岔貼性，其結果 比較 覆膜之基材 在按與比較例1同樣方式所調萝 的附有硬質覆膜之基 314657 33 1299741 材（RF-1-1)上，按與實施例8同樣方式 β Μ勝 ^ 战宁間te及防止 反射，以調製附有硬質覆膜之基材（rf_5_0。 就所得的附有硬質覆膜之基材評估表面電阻、全 穿透率、濁度、鉛筆硬度、抗擦傷性以及 ，：吴 示於表2。 /、、、、σ禾 比較例^ 膜之某材 在按與比較例2同樣方式所調製的附有硬質覆膜之其 材（RF-2-1)上，按與實施例8同 、土 U私万式形成中間膜 反射膜，以調製附有硬質覆膜之基材（RF_6_i)。 就所得的附有硬質覆膜之基材評估表面電阻 穿透率、濁度、錯筆硬度、抗擦傷性以及密貼性…果 示於表2。 /、、、、。果Example 1 I. A base material of a film (F!?, a base film with a hard film prepared in the same manner as in Example 6), and an anti-reflection film were formed in the same manner as in Example 8 to prepare a film. Hard coated substrate (1^13_1). Appearance of the obtained hard coated substrate. 古1 - 1 ancient surface resistance, total light tooth penetration, turbidity, pencil hardness, scratch resistance In Table 2, ... and the adhesion, the results of Example 1 4 K base material (F-14) ^^ in the same manner as in the case of Example 7, 7 1Λ LI with a hard film-based base On the material (F-7-1), in the same manner as in Example 8, -M ^ was converted into an intermediate film and a reflection preventing enthalpy to prepare a hard coating-based substrate obtained by affixing a substrate coated with a hard film. Material penetration rate, turbidity, stagger hardness, scratch resistance = resistance, total light are shown in Table 2. Raw and adhesive properties, and as a result, the substrate of the film was adjusted in the same manner as in Comparative Example 1. On the 314657 33 1299741 material (RF-1-1) with a hard film, in the same manner as in Example 8, β Μ ^ ^ 宁 间 及 and anti-reflection, to modulate A substrate with a hard film (rf_5_0. Evaluation of surface resistance, total penetration, turbidity, pencil hardness, scratch resistance, and the like on the obtained substrate with a hard film:: Wu is shown in Table 2. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , An intermediate film reflective film is formed to prepare a substrate (RF_6_i) to which a hard film is attached. The surface resistivity, turbidity, stray hardness, and scratch resistance of the obtained hard coated substrate are evaluated. And the adhesion... The results are shown in Table 2. /,,,,.

實施例1 S 一------- 用之塗佈液 及將肖酸銦79.98溶解在水686g中所得的溶液， =溶解在濃度1G重量％之氫氧化卸溶液 。。的：液’亚將此等溶液以2小時添加經保持在50 C的1 OOOg之純水中。在此當 w α^ 保持系内之pH為11。 伙所付的錫摻雜氧化銦水合物八 , 物刀放液中濾別·洗淨錫摻雜 虱化銦水合物後，加以乾燥 ^ ^ ^ , 接者，在空氣中在35〇t之 士 在二乳中以6〇〇°C之溫度燒成2 d 時，以製得錫摻雜氧化銦微粒m h 凡成2小 3〇重詈。/之μ w Q )°將此按濃度能成為 更里A之方式分散在姊k 士 珧夂中，再以硝酸水溶液調整ρΉ 314657 34 1299741 :、·5後，在保持此混合液為3 0 之下使用碾砂機粉碎3 、寸以凋製，破膠。其次，使用離子交換樹脂處理此凝膠 二去除硝酸離子，接著，使用異丙醇進行溶媒取代，以調 ‘有錫的氧化銦（ITO)微粒之分散液（折射率1.9〇，平 均粒也2〇nm，濃度20重量％)。 接著，充份混合摻雜有錫的氧化銦（IT〇)微粒之分散 液2〇g，與紫外線固化樹脂（大日本油墨（股）製；優尼得克 V550〇)().44gA異丙醇6 7g，以調製中間被膜形成用塗佈 液（M-2)〇 之基材（F-1 5)之 _ j告 在實施例8中，除使用中間膜形成用塗佈液（M-2)以 外，其餘則按與實施例8同樣方式形成中間膜及防止反射 膜，以調製附有硬質覆膜之基材斤-丨^丨）。 ★就所得的附有硬質覆膜之基材評估表面電阻、全光絲 穿透率、濁度、鉛筆硬度、抗擦傷性以及密貼性，其結果 示於表2。 實施例丄6Example 1 S---coating solution used and a solution obtained by dissolving indium sulphate 79.98 in 686 g of water = dissolved in a concentration of 1 G% by weight of a hydrolytic solution. . The solution was added in 1 gram of pure water maintained at 50 C for 2 hours. Here, the pH in the w α^ retention system is 11. The tin-doped indium oxide hydrate that the group pays is eight. The filter is filtered in the liquid knife. After washing the tin-doped indium telluride hydrate, it is dried. ^ ^ ^, in the air, at 35 〇t When the steel is fired at a temperature of 6 ° C for 2 d in the second milk, the tin-doped indium oxide fine particles mh are made into 2 small 3 〇. /μμw Q )° This is dispersed in the 姊k 珧夂 按 according to the concentration of the aliquot A, and then adjusted to ρΉ 314657 34 1299741 with a nitric acid aqueous solution :, ·5, after maintaining the mixture is 3 0 Under the use of a sand mill to crush 3, inch to wither, broken glue. Next, the gel was treated with an ion exchange resin to remove nitrate ions, followed by solvent substitution using isopropyl alcohol to adjust the dispersion of tin-doped indium oxide (ITO) particles (refractive index of 1.9 Å, average granules also 2 〇nm, concentration 20% by weight). Next, 2 μg of a dispersion of tin-doped indium oxide (IT〇) fine particles was sufficiently mixed with an ultraviolet curable resin (manufactured by Dainippon Ink Co., Ltd.; Unid V550®) (44 g) 6 g of the alcohol to prepare a base material (F-1 5) of the coating liquid (M-2) for forming an intermediate film, in Example 8, except that the coating liquid for forming an intermediate film was used (M- Except for 2), an intermediate film and a reflection preventing film were formed in the same manner as in Example 8 to prepare a substrate to which a hard film was attached. ★ The surface resistance, the full-filament transmittance, the turbidity, the pencil hardness, the scratch resistance, and the adhesion were evaluated on the obtained substrate coated with a hard film. The results are shown in Table 2. Example 丄 6

社κ施例8中 …、个v从π τ间胰以外，其餘則泰 實施例8同樣方式’以調製附有硬質覆膜之基材（F4 ，就所得的附有硬質覆膜之基材評估表面電阻、全另 :透率/蜀度、鉛筆硬度、抗擦傷性以及密貼性，其、麵 示於表2。 /…1" 比較例7 314657 35 Ϊ299741 覆膜之基材（RF _7)之紫$告 在按與比較例3同樣方式所調製的附有硬質覆膜之基 方（、F夂1)、（RF_3-2)以及（RF_3-3)上，按與實施例8同樣 式形成中間膜及防止反射膜，以調製附有硬質覆膜之基 才（RF-7-l)、（RF-7-2)以及（Rf_7_3)。 土 〜就所得的附有硬質覆膜之基材評估表面電阻、全光線 一透率濁度、錯筆硬度、抗擦傷性以及密貼性，其 示於表2。 膜之基材 在按與比較例4同樣方式所調萝的 m I的附有硬質覆膜之基 材（RF-4-1)上，按與實施例8 保万式形成中間膜及防止 反射膜，以調製附有硬質覆膜之基材（RF_8_i)。 卜就所得的附有硬質覆膜之基材評估表面電阻、全光線 牙透率、濁度、鉛筆硬度、抗捧 示於表2。 “山及密貼性’其結果 314657 36 1299741In the case of κ 8 ... 、 、 、 、 、 、 、 、 、 、 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 以外 π π π π Evaluate surface resistance, full: permeability/twist, pencil hardness, scratch resistance, and adhesion. The surface is shown in Table 2. /...1" Comparative Example 7 314657 35 Ϊ299741 Film-coated substrate (RF _7 In the same manner as in Comparative Example 3, the base of the hard film (F夂1), (RF_3-2), and (RF_3-3) prepared in the same manner as in Comparative Example 3 was the same as in Example 8. The intermediate film and the anti-reflection film are formed to prepare a base film (RF-7-1), (RF-7-2), and (Rf_7_3) with a hard film. The soil is obtained by attaching a hard film. The substrate was evaluated for surface resistance, total light transmittance, turbidity, stray hardness, scratch resistance, and adhesion, and is shown in Table 2. The substrate of the film was m I adjusted in the same manner as in Comparative Example 4. On the substrate (RF-4-1) with a hard film, an intermediate film and a reflection preventing film were formed in the same manner as in Example 8 to prepare a substrate (RF_8_i) to which a hard film was attached. The surface of the obtained hard coated substrate was evaluated for surface resistance, total light tooth penetration, turbidity, pencil hardness, and resistance. Table 2 shows the results of "mountain and adhesion" 314657 36 1299741

Ml 附有硬質覆 膜之基材 硬質覆膜 中間膜 防止反射膜 膜厚 //m 折射 率 厚度 nm 折射 率 膜厚 nm 表面電阻 Q/D X10· 全光線 穿透率 % 濁度 % 反射 率 \ 鉛筆 硬度 抗擦 傷性 密貼 性 實施例8 實施例1 5 1.80 80 1.44 80 5 94.5 1.5 0.50 4H © ◎ 實施例9 實施例2 5 1.80 80 1.44 B0 3 94.6 1.6 0.48 4H ◎ ◎ 實施例10 實施例3 5 1.80 80 1.44 80 1 94.6 1.9 0.46 4H @ ◎ 1 1.80 80 1.44 80 1 94.6 1.9 0.48 3H ◎ ◎ 0.3 1.80 80 1.44 80 1 94.6 1.9 0.50 3H ◎ © 實施例11 實施例4 5 1.80 80 1.44 80 5 95,0 2.0 0.46 4H 0 〇 實施例12 實施例5 5 1.80 80 1.44 80 1 94.9 2.0 0.46 4H @ ◎ 實施例13 實施例6 5 1.80 80 M4 80 2 94.8 1.6 0.48 4H ◎ ◎ 實施例14 實施例7 5 1.80 80 1.44 80 3 94.8 1.6 0.49 5H ◎ ◎ 實施例15 實施例1 5 1.70 80 1.39 80 0.002 94.5 1.5 0.55 4H ◎ ◎ 實施例代 實施例1 5 一 一 1.39 80 8 94.6 1.5 0.90 4H @ ◎ 比較例5 比較例1 5 1.80 80 1.44 80 10000以上 94.5 1.5 0.50 2H Δ Δ 比較例β 比較例2 5 1,80 80 1.44 80 10000以上 94.3 1.5 0.49 2H Δ Δ 比較例*7 比較例3 5 1.80 80 1.39 80 10000以上 94.5 1.5 0.51 2H Δ Δ 1 1.80 80 1.39 80 10000以上 94.6 1.6 0.54 B Δ Δ 0.3 1.80 80 1.39 80 10Q00以上 94,7 1.7 0.55 2B △ Δ 比較例8 比較例4 5 1.B0 80 1.39 80 10000以上 94.4 1.5 0.50 2H Δ Δ 37 314657Ml with hard coating substrate hard film interlayer film to prevent reflection film thickness / m refractive index thickness nm refractive index film thickness nm surface resistance Q / D X10 · total light transmittance % turbidity % reflectivity \ Pencil Hardness and Scuffing Adhesion Example 8 Example 1 5 1.80 80 1.44 80 5 94.5 1.5 0.50 4H © ◎ Example 9 Example 2 5 1.80 80 1.44 B0 3 94.6 1.6 0.48 4H ◎ ◎ Example 10 Example 3 5 1.80 80 1.44 80 1 94.6 1.9 0.46 4H @ ◎ 1 1.80 80 1.44 80 1 94.6 1.9 0.48 3H ◎ ◎ 0.3 1.80 80 1.44 80 1 94.6 1.9 0.50 3H ◎ © Example 11 Example 4 5 1.80 80 1.44 80 5 95, 0 2.0 0.46 4H 0 〇 Example 12 Example 5 5 1.80 80 1.44 80 1 94.9 2.0 0.46 4H @ ◎ Example 13 Example 6 5 1.80 80 M4 80 2 94.8 1.6 0.48 4H ◎ ◎ Example 14 Example 7 5 1.80 80 1.44 80 3 94.8 1.6 0.49 5H ◎ ◎ Example 15 Example 1 5 1.70 80 1.39 80 0.002 94.5 1.5 0.55 4H ◎ ◎ Example 1 Example 1 5 1.39 80 8 94.6 1.5 0.90 4H @ ◎ Comparative Example 5 Comparison Example 1 5 1.80 80 1.44 80 10000 or more 94.5 1.5 0 .50 2H Δ Δ Comparative Example β Comparative Example 2 5 1,80 80 1.44 80 10000 or more 94.3 1.5 0.49 2H Δ Δ Comparative Example *7 Comparative Example 3 5 1.80 80 1.39 80 10000 or more 94.5 1.5 0.51 2H Δ Δ 1 1.80 80 1.39 80 10000 or more 94.6 1.6 0.54 B Δ Δ 0.3 1.80 80 1.39 80 10Q00 or more 94,7 1.7 0.55 2B △ Δ Comparative Example 8 Comparative Example 4 5 1.B0 80 1.39 80 10000 or more 94.4 1.5 0.50 2H Δ Δ 37 314657

Claims (1)

第92114515號專利申請案 (97年1月30曰） 拾、申請專利範i 種附有硬質覆膜之基材，係由基材、及基材上所形成 的硬質覆膜而成，其特徵為： 該硬質覆膜含有基質成份及五氧化二銻（Sb205)粒 子，該五氧化二銻粒子之平均粒徑在2至丨〇〇nm之範 圍’而硬質覆膜中之五氧化二録粒子之含量在5至％ 重里/。之範圍，且前述硬質覆膜之膜厚在至 之範圍。 2· $申請專利範圍第丨項之附有硬質覆膜之基材，其中， 刚述基質成份係熱固化樹脂或紫外線固化樹脂者。 3· ^申請專利範圍第1項之附有硬質覆膜之基材，其中， 前述硬質覆膜之膜厚，為在〇·2至10/ZIn之範圍。 如申明專利範圍第！項至第3項中任一項之附有硬質覆 膜之基材，丨中，在前述硬質覆膜i，再形成有防止反 射膜者。 如:明專利範圍第4項之附有硬質覆膜之基材，其中， 在則述硬貝覆膜與防止反射膜之間，形成有中間膜者。 (修正本)314657 38Patent Application No. 92114515 (January 30, 1997) Picking up, applying for a patent, a substrate coated with a hard film, which is formed by a hard film formed on a substrate and a substrate, and is characterized by The hard film contains a matrix component and bismuth pentoxide (Sb205) particles, and the bismuth pentoxide particles have an average particle diameter in the range of 2 to 丨〇〇nm and the pentoxide particles in the hard film The content is in the range of 5 to % by weight. The range is such that the film thickness of the hard film is in the range of up to. 2· The scope of the patent application is attached to the hard coated substrate, wherein the matrix component is a thermosetting resin or an ultraviolet curing resin. 3. The substrate of the hard coating according to the first aspect of the patent application, wherein the film thickness of the hard film is in the range of 〇·2 to 10/ZIn. Such as the scope of the patent claim! A substrate coated with a hard coating according to any one of the items 3 to 3, wherein the anti-reflection film is formed on the hard film i. For example, in the fourth aspect of the patent scope, a substrate coated with a hard film is used, and an intermediate film is formed between the hard shell film and the anti-reflection film. (Revised) 314657 38