TW200400222A

TW200400222A - Substrate with a hard coating film

Info

Publication number: TW200400222A
Application number: TW092114515A
Authority: TW
Inventors: Masayuki Matsuda; Toshiharu Hirai; Michio Komatsu
Original assignee: Catalysts & Chem Ind Co
Priority date: 2002-05-31
Filing date: 2003-05-29
Publication date: 2004-01-01
Also published as: JP4979876B2; JP2004050810A; CN1461777A; TWI299741B; KR20030044981A

Abstract

This invention provides a substrate with a hard coating film, the substrate having excellent properties of adhesion, anti-scratching, and hardness; it also has an excellent productivity and an good repellency to dust. The substrate has a hard coating film formed thereon and the hard coating film contains matrix component and 5~95% wt of particles of diantimony pentoxide (Sb2O5), the particles of diantimony pentoxide having an average diameter in the range of 2~100 nm.

Description

200400222 玖、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)等停里、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擦知性起見’周知有在基材表面形成硬質覆膜的作法，而進行有作為這樣的硬皙蘧日替位]更貝復朕而在玻璃或塑膠等表面機樹脂膜或無機膜。再者，/亦進行有在有機樹脂薄膜或益機薄膜中調配樹脂粒子或二氧切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、《片材'塑料鏡等基材表面之 =見’周知有在其表面形成反射防止膜之作法周知有藉由塗佈法、蒸錄法、CVD(化學蒸汽沈積)法等， :將如含鼠樹脂、氟化鎂般的低折射率之物質之被膜或塑膠之基材表面，或將含有二氧切微粒子等之 ^射㈣子的㈣液塗佈在基材表m成反射防止用被膜的方法（參考例如，日本專利特開平Mm卢八報寻)。再者，亦有為基材賦與防止帶電之性能、遮：：磁波之性能起1，形成含有金、:：粗的導電性被膜的作法。 h性之魏物微 .^ α 川饭联及/欢導電性被膜時; 為增進抗擦傷性起見， 4 、才進仃令在基材與防 314657 200400222 或導電性被膜之間形成硬質覆膜的作法。美：，歷來之硬質覆膜當中，特別是基材係樹脂製之基材化’有時與基材間之密貼性或衣之不足。胰本身之抗彳祭傷性變得再者，在硬質覆膜上設置防止反射用膜+ ^ 被膜時，歷來之麻所令木士对丁用腰及電性產生擦斤貝⑽當中，有時在硬質覆膜形成後會 τ劳或因静電而附著塵埃，以致所f@ f性被膜之a从> ☆ 双所衣仏的附有導電的問基材之透明性或濁度降低，而有製品之收率降低口此’期待一種能更辦；隹命| 性，且同時能防止塵;^材間的密貼性或抗擦傷發。、付者之附名硬質覆膜之基材的開 =之：來硬質覆膜當中，如增厚膜膜中粒子種類，例如樹脂趣…广以下，則視所用之種類，而使塗料用S ‘.，、機粒子、導電性粒子等便土科用樹脂難於硬化，有時會膜在如此狀況下，本發明。的結果發現，如在而專心硬究產生的靜電，…；爾調配導電性粗子，則除去所，、、，.。不可抑制塵埃等之附著。特別是’如作為導+ 氧化二銻粒子時，驚二粒子而使用具有特定粒徑的五問題的硬質覆膜。7 ’發現’其可製得能解決所有上述 3)4657 6 200400222 〜又、，亦發現如使用五氧化二銻時，在形成硬質覆膜時月匕促進塗佈液中所含被膜成份的硬化，因此如作成特定厚度之硬貝覆膜時即能以極高效率進行被膜之硬化。 [發明内容] 發日本發明之目的在於提供傷性、挪洛斤一月^、岙柯間之密只0性、抗擦 ^ 又寺優異之同時，生產性等亦優卩，且塵埃等之附著少的硬質覆膜的附有被膜之基材。 ϋιϋ之概要有關本發明之附有硬質覆一狀 < 岙苻，係由基材，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」子，兮：r >儿—” 礼化一録（Sb2〇5)粒 μ五乳化一録粒子之平心卞^粒從在2至1 〇0ηηΊ之笳園而硬質覆膜中之五氧化― 年L 1G 一録粒子之冬之範圍。于之3里在5至95重量％前述基質成份合適。係以熱固化樹脂或紫外線固化樹脂較如述硬質覆膜之膜厚圍。再者，前述硬質覆膜之範圍。在前述硬質覆膜上，佳。，較佳為在0.1至20以m之範膜异’更佳為在〇 · 2至I 〇 // m 以再形成有防止反射薄膜者為再者亦可在前述硬質覆版與防止反射薄膜之間形 3I4657 200400222 成有中間膜。 1日月之具體說明以下，就有關本發明之附有硬質覆膜之基材加以說200400222 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to excellent adhesion to the substrate, such as scratch resistance, film hardness, etc., and stopping properties such as electrification prevention performance, transparency, and haze. A substrate with a hard film. " /, [Prior art] —In order to improve the abrasion resistance of the substrate surface of glass, plastic sheet, plastic lens, etc., 'the method of forming a hard film on the substrate surface is well known, Hard-skinned day replacement] Even more complex on the surface of glass or plastic and other resin film or inorganic film. Furthermore, it has been practiced to mix inorganic particles such as resin particles or dioxin in organic resin films or organic films to further improve scratch resistance. ", And" to prevent the surface of glass, "sheets" plastic mirrors and other substrates = see 'the method of forming an antireflection film on its surface is well known. It is well known to use coating methods, vapor deposition methods, CVD (chemical vapor deposition) ) Method, etc .: coating the surface of the film or plastic substrate with low refractive index substances such as rat resin and magnesium fluoride, or coating the solution containing dioxin particles such as dioxin particles on the substrate The material surface m is a method for preventing reflection (refer to, for example, Japanese Patent Laid-Open Publication Mm Lu Babao). In addition, there is also a method for imparting antistatic properties to the base material and shielding: the performance of the magnetic wave is 1. Contains gold :: The method of thick conductive coating. The nature of the Wei Weiwei of the nature. ^ Α Chuanfanlian and / Huan conductive coating; In order to improve the anti-scratch, 4, only in the base material and anti- 314657 200400222 or the method of forming a hard coating between conductive coatings. Beauty: Among the conventional hard coatings, especially the base material is made of resin-based base material, sometimes it has close adhesion with the base material or clothing. Insufficient sacrifice resistance of the pancreas itself, and it is set on a hard film Anti-reflection film + ^ When the film is used, the traditional hemp has caused the wooden man to rub the waist and electricity with the shell. Sometimes, after the hard film is formed, it may cause τ labor or static electricity to adhere to the dust. The f @ f sexual coating of a from > ☆ The double-coating with a conductive substrate has reduced transparency or turbidity, and the yield of some products is reduced. I hope one can do more; | At the same time, it can prevent dust; ^ Adhesiveness between materials or anti-scratch hair. 、 The substrate of the payer's attached hard film is equal to: from hard film, such as thickened film Types of particles, such as resins ... below, depending on the type used, it is difficult to harden the resins for convenience and soil science such as coatings S '., Organic particles, conductive particles, etc. Sometimes the film is in such a condition. As a result, it was found that, if the static electricity generated by the intensive study is carried out, and the conductive coarse particles are deployed, the removal of the dust, etc. is not suppressed. In particular, 'such as conduction + oxidation two In the case of antimony particles, a five-problem hard coating having a specific particle size is used to shock two particles. 7 'Discover' it can be made to solve all the above 3) 4657 6 200400222 ~ Also, also found that when using antimony pentoxide, the moon dagger promotes the hardening of the coating components contained in the coating liquid when forming a hard coating Therefore, if a hard shell coating with a specific thickness is made, the coating can be hardened with high efficiency. [Content of the Invention] The purpose of the invention of Japan is to provide traumatic, norogen, ^, and dense keke. In addition to its excellent properties in terms of resistance and abrasion, it is also excellent in productivity, etc., and has a film-coated base material with a hard film with little adhesion of dust and the like. < 岙苻, is made of a hard film formed on the substrate, and is characterized by: The hard film contains a matrix component and a "zi, Xi: r > er-" Lihua Yilu (Sb2 〇5) Granules of five-emulsion and one-emulsion particles have a range from pentoxide in the hard garden of 2 to 100 ηηΊ, which is the range of the winter of L1G one-equivalent particles. Among the above, 5 to 95% by weight of the aforementioned matrix component is suitable. The thickness of the hard-curing resin or the ultraviolet-curing resin is larger than that of the hard film. In addition, the range of the aforementioned hard coating film. On the aforementioned hard film, it is preferable. The thickness of the film is preferably 0.1 to 20 m, more preferably 0.2 to I 〇 // m to form the anti-reflection film, and also the aforementioned hard coating and anti-reflection film. Between the shape 3I4657 200400222 into an intermediate film. Detailed description of the 1st month The following is a description of the substrate with a hard film of the present invention

明。 1.有硬質彳f膜之H 本卷月之附有硬質覆膜之基材，係由基材、及經形成在基材上的硬質覆膜而成。鲁基材 ^發明所使用之基材，並不特別限定而可使用周知 ^ 玻㈣、聚石厌酸酉旨、丙稀酸樹脂、PET、TAC(氰 jc -义一烯丙g曰）等之塑膠片材、塑膠薄膜等、塑膠面板等。其中樹脂系基材較適用。硬質霜膜 A牯：I “莫：含有基質成份及五氧化二銻(Sb2〇5)粒子 …1乳化：録粒子之平均粒子徑在2至ΙΟΟηπ; 之祀圍，而硬質覆膜中之五氧化二銻粒子之含量在5至重量。/。之範圍。 3里在5至五氧化二子本發明所傕闲令 # 、，之五乳化二録粒子，侍 ΙΟΟππι , Α ς = 你十均拉役在2 1马5至80nm之範圍。如五氧化二銻粒子之時，則得不到辦進盘I# q彳工未滿W述範圍之下限曰違與基材間之密貼性戈括的效果，有時清I^ 及抗榛傷性、胲硬 β可逐會降低，又，粉體雷足夠的防止帶電之性能。增大而可能得不 314657 200400222 士如五虱化二銻粒子之平均粒徑超過前述範圍之上限 :雖因五乳化二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銻粒子之含量，以sb2〇計，般在5至95亩旦。/ » %重里/。，以在10至8〇重量％之範圍為佳。士硬貝覆月吴中之五氧化二銻粒子之含量，以計’若未滿前述笳圚 2 5 之穷貼性” 下限”則不能充份獲得與基材間現二的防膜硬度之增進效果…不能呈上容易附著塵能在因此所得附有硬質覆膜之基材或中間膜(導電脾、折射车:置後述的有防止反射膜及/ 的其从折射率调整膜）的基材之製造時，所得勺土材之透明性或濁度匕曰子乂力叩衣口口之收率降低。特別；’2成膜厚在約1〇…下，再者在^以下， # m以下之薄硬質覆膜時，有時固化或促進固化的效果不夠。 U用树脂硬質覆膜中之五氧化二銻粒子之含量，以如超過前述範g 2 5。十， m 限，則可能與基材間之密貼性降低或產生空隙(鄉使硬質覆層之硬度降低。；低成硬質覆膜之基材的斤付附有、mai 月丨生或濁度亦不足。再者，更無法促進則述塗料用樹脂之硬化的效果。士更貝復版中之五氧化二銻粒子之含量，以Sb2〇. =在上述範圍内，則除可獲得與基材間的密貼性、2⑽ =膜硬度之增進效果、膜固化之促進效果等以外二月匕促问硬質覆膜本身之折射率（Sb2〇5之折射率為2.0)，即 314657 9 200400222 使基材的折射率々，丨a ^ 例如低至〗·55,或硬質覆膜之基材折射率例如低於1 · 5 5日孝丄A , 射日寸，由於可增大硬質覆膜與基材間' 及視需要所形成的卩* λ 防止反射膜間的折射率差距，而可开4 防止反射性能優異的附有被膜之基材。 4 如此的五氧化二銻粒子係使用造者而不特別限宏 w <衣仏方法所製 r“、,」具體的製造方法其平均粒徑在上述乾圍内’並能後得呈右 m ω ”有與基材間充份的密貼性或硬度以及 4几彳祭 <劳性的附有硬曾舜本申唷安卜則並不特別限定，惟由報所:日本專利特開平2-180717號公 ""不的五乳化二録溶朦（so1)之製造方法，由於可製得砬徑均勻而安定性、透衣、很適合採用。 Um容膠5因此，人物：：而言，對特定莫耳比之三氧化二銻與鹼物質的混 “”按既定速度添加既定量之過氧化氯，即可製造：妒二本發明之在硬質覆膜中含有五氧化二銻粒子，則可 $成與基材間之密貼性優显、 .冋犄，抗擦傷性、膜硬度優一、硬負覆膜。在此，如此的效果夕由y ^ ^日] >文果在導電性氧化物粒子· Y ’係五氧化二録粒子特右去 ,,n %有者而在氧化銦、錫摻雜氧化銦、低次元氧化鈦等導電工、入斤毛Γ土虱化物粒子、三氧化二銻粒 J 孟屬微粒子等則並不能呈現。其理由雖然不明痛，惟在基質成份係熱固化性樹脂守’可推論為五氧化二銻粒子在促進樹脂之固化。 J外’在五氧化二録粗子以外之粒子，則有塗料用樹固化變慢或不會固化的情形。此乃除了五氧化二録以 ]〇 314657 200400222Bright. 1. H with a hard 彳 f film The base material with a hard film in this volume is made of a base material and a hard film formed on the base material. Lu base material ^ The base material used in the invention is not particularly limited and can be used ^ glass fiber, polylithic acid, acrylic resin, PET, TAC (cyanide jc-s-iso-allyl g), etc. Plastic sheet, plastic film, plastic panel, etc. Among them, resin-based substrates are more suitable. Hard cream film A 牯: I "Mo: containing matrix components and antimony pentoxide (Sb205) particles ... 1 emulsification: the average particle diameter of the recorded particles is in the range of 2 to 100 ηπ; and five of the hard film The content of the antimony oxide particles is in the range of 5 to weight. The range is 3 to 5 to 5 pentoxides, which is the order of the present invention, and the fifth emulsifies the second recorded particles. Serving ΙΟΟππι, Α ς = you ten equal pulls It is in the range of 21 to 5nm and 80nm. For example, when antimony pentoxide particles are used, it will not be possible to enter the disk. In some cases, the effect of Qing I ^ and its resistance to hazel injury and sclerosis β may be reduced, and powder mines have sufficient anti-charge performance. It may increase if the antimony is increased by 314657 200400222 The average particle size of the particles exceeds the upper limit of the foregoing range: Although the content varies according to the content of the penta-emulsions, the transparency of the film may be reduced, the film may be colored, or the turbidity may be increased. Pentoxide in the hard film The content of the antimony particles, based on sb20, is generally in the range of 5 to 95 mu denier. / »% Wt /, in the range of 10 to 8 The range of weight% is better. The content of antimony pentoxide particles in hard shells and cladding moons is not sufficient if the "lower limit" of the above-mentioned 笳圚 25 is insufficient. The effect of increasing the hardness of the anti-film ... can not be presented on the substrate or intermediate film (conducting spleen, refracting car: the anti-reflection film and / When manufacturing the substrate of the film), the transparency or turbidity of the obtained spoon material is reduced. The yield of the mouth of the cloth is reduced. In particular; When the thickness is below ^ and # m, the effect of curing or accelerating the curing may not be sufficient. The content of antimony pentoxide particles in the resin hard coating for U is more than the above range g 2 5. 10. , M limit, then the adhesion with the substrate may be reduced or voids may be generated (the hardness of the hard coating is reduced. The substrate of the low-hard coating film is attached, maited, or turbid It is also insufficient. Furthermore, it is impossible to promote the hardening effect of coating resins. The content of antimony pentoxide particles in the reproduction is Sb20. = Within the above range, in addition to the adhesion with the substrate, 2⑽ = the improvement effect of film hardness, and the effect of film curing In addition, February asked the refractive index of the hard film itself (the refractive index of Sb205 is 2.0), which is 314657 9 200400222, which makes the refractive index of the substrate 々, a ^, for example, as low as · 55, or a hard coating. The refractive index of the base material of the film is, for example, less than 1.55 days of filial piety A, and it is possible to increase the refractive index between the hard coating and the base material and the 卩 * λ formed if necessary to prevent the refractive index between the reflective films. It can open 4 substrates with a film that has excellent anti-reflection performance. 4 Such antimony pentoxide particles are produced by the manufacturer and are not particularly limited by the macro w < clothing method. The specific manufacturing method has an average particle diameter within the above-mentioned dry range, and can be obtained as shown below. “m ω” has sufficient adhesion or hardness with the substrate, and 4 彳 Ki Matsuri &labor; with hard Zeng Shun, this application is not particularly limited, but by the newspaper: Japanese Patent Laid-Open No. 2-180717 No. "quote" is not a five-emulsion two-recording (so1) manufacturing method, because it can be made with a uniform diameter and stability, permeability, and is very suitable for use. Um Capsule 5 Therefore, People :: In terms of Adding a certain amount of chlorine peroxide at a predetermined rate to a specific mixture of antimony trioxide and an alkaline substance at a certain molar ratio, can be produced: Jealousy II The present invention contains antimony pentoxide particles in a hard coating, It can achieve excellent adhesion between the substrate and the substrate,. 冋犄, abrasion resistance, excellent film hardness, and hard negative film. Here, such effects are described by y ^ ^ 日] > 文果在Conductive oxide particlesY'-type pentoxide particles are especially right, n% are doped with indium oxide and tin Conductive materials such as indium oxide, low-order titanium oxide, enthalpy particles, antimony trioxide particles, Meng particles, etc. cannot be presented. The reason is unknown, but the matrix component is a thermosetting resin. Shou's can be inferred that antimony pentoxide particles are promoting the curing of the resin. J Wai 'particles other than the coarse particles of pentoxide may cause the coating tree to cure slowly or not. This is in addition to pentoxide Second recorded by] 〇314657 200400222

夕卜t每立二?~ *5ΠΓ合匕士 » X 固化的作用，而五氧化二録粒子則可能有抑制此作用的效果。基質成j也作為硬質覆膜.中所含的基質成份，以樹脂基質較適合。士這種樹月旨基質以具體而言，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。 k種樹知可例舉如··歷來所使用的聚酯樹脂、聚碳酸水Ssk胺樹脂、聚苯醚樹脂、熱塑性丙烯酸樹脂、 =乙稀树月曰、含氟樹脂、醋酸乙稀樹脂、石夕酮橡膠等之熱塑性樹脂、?τ_樹脂、三聚氰胺樹脂、石夕樹脂：丁縮 ^樹脂、反應性硬酮樹脂、_樹脂、環氧樹脂、不飽和 ♦ sa树月曰、熱固化性丙烯酸樹脂等之熱固化性樹脂等。再者’亦可為此等樹脂之2種以上之共聚物或改性物。此等樹脂’可為乳液樹脂、水溶性樹脂、親水性樹脂。再者，如係熱固化性樹脂時，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，可含有固化觸媒在内。在本發明中，特別在熱固化樹月旨時，調配有五氧化_ 銻粒子時之效杲(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。硬質覆膜之厚度以0·1至20心為佳’以0.2至10 較佳，以0.2至5ym之範圍者為更佳。如在此範圍之厚度，則由於硬質覆膜中含有五氧化 Π 314657 200400222 銻粒:之故，能使被膜充份固化之同時，可得薄膜與基材間的密貼生、抗擦傷性、膜硬度等優異，經濟性：附有硬質覆膜基材。罗“ ^硬貝覆肤之厚度未滿前述範圍之下限時，由於硬質不能充足吸收施加至硬質覆膜表面的應力而使：聿硬度不足。如硬質覆膜之厚度超過前述範圍之上限時，句塗佈膜厚或均句乾燥，因而會產生龜裂或空而使所付硬質覆膜之強度或透明性變得不充份。 “：此的硬質覆冑，可藉由形成前述基質成份的基質形 ”、及含有前述之五氧化二銻粒子的塗佈液之塗佈而另外’調製塗佈液時’為能調製經均勾分散的塗佈液㈣用氧化二銻粒子作成經分散在分散媒中的溶膠後使用者為佳。分散溶膠可任咅A ρ。心為水刀放么膠' 經分散在醇等有機溶媒中的有機溶媒分散溶膠。氧化一銻粒子可為其表面經以周知之矽烷偶合劑所處理者。可將如此方式所烟制斤5周衣的分散溶膠及基質形成成份在適當溶劑中加以稀釋，7从』、了作成硬質覆膜形成用之塗佈液。再者，塗佈液中，為古^ — 斤马穴阿女疋性起見，亦可添加表面活性劑等。土 β液中，溶解基質形成成份之同時，亦可含有 314657 10 200400222 能容易揮發的溶劑’而基質形成成份係熱固化性樹脂時，可因應需要而調配固化劑。料種塗佈液依周知之浸潰法、冑塗法、旋塗法、報 “ J方法皇佈在基材上亚乾燥’在熱固化性樹脂之固化二：塑性樹脂之因應需要在基材之軟化點以下之溫度也予加熱處理，即可形成硬質覆膜。本發明之附有硬質霸膜其士置有防止反射膜。⑼之基材中，可在硬質覆膜上設祇要：：::：防止反射膜可使用歷來周知之防止反射膜’ 能者則並不特別限定。具體而言，如這硬貝覆為低者，則具備有防止反射性能。需要所A力的反射’係、由防止反射膜形成用基質、及視而要所添加的低折射率成份而成。份，=:Γ成用基質，係能形成防止反射膜的成仞，而可從與基材間之宓乂選擇使用。山、或硬度以及塗工性等之觀點具體而言，可你、，質成份。人㈣述硬質覆膜形成成份同樣之基又’作為基質而體而言，如在例如：作為催化劑的酸或鹼份加水分解物。加水分解性有機 T使用加水分解性有機矽化合物。具 k氧石夕垸與醇之混合液中，添加水及 p可成為適合使用之院氧矽烧之部夕化合物可使用以通式R„Si(〇R，）4. 314657 13 200400222 : 基、芳基、乙稀基、丙稀基等之煙基， 2或3]所表不的烧氧碎燒。特別是，四甲氧碎烧、四乙氧石”完、四丙氧偏之四貌氧彻適合使用。 :任意含有之低拆射率成份除CaF2.、NaF、NaAiFe、Xibu t every two? ~ * 5ΠΓ 合合士 »X curing effect, and pentoxide particles may have the effect of inhibiting this effect. The matrix component j also serves as the matrix component contained in the hard film. A resin matrix is more suitable. In particular, such a tree-like substrate can be a known thermosetting resin or a thermoplastic resin as a coating resin. Examples of k types of trees include: polyester resins, polycarbonate Ssk amine resins, polyphenylene ether resins, thermoplastic acrylic resins, ethylene resins, fluororesins, vinyl acetate resins, Thermoplastic resin such as stone ketone rubber, τ_ resin, melamine resin, and stone resin: butyl resin, reactive hard ketone resin, _ resin, epoxy resin, unsaturated Thermosetting resins such as acrylic resins. It is also possible to use two or more copolymers or modified products of these resins. These resins' may be emulsion resins, water-soluble resins, and hydrophilic resins. In the case of a thermosetting resin, it may be a UV-ray-curable type or an electron-wire-curable type. In the case of a thermosetting resin, a curing catalyst may be included. In the present invention, particularly in the case of thermal curing trees, the effect when the antimony pentoxide_antimony particles are prepared (the adhesion to the substrate, the abrasion resistance, and the effect of improving the hardness) is significant. The thickness of the hard film is preferably from 0.1 to 20 centimeters', more preferably from 0.2 to 10, and even more preferably from 0.2 to 5 μm. If the thickness is in this range, because the hard film contains pentoxide 314 657 200400222 antimony particles: Therefore, while the film can be fully cured, the close adhesion between the film and the substrate, anti-scratch resistance, Excellent film hardness, etc., economical: With a hard film substrate. Luo "^ When the thickness of the hard shell skin is less than the lower limit of the aforementioned range, because the hard can not sufficiently absorb the stress applied to the surface of the hard membrane, the hardness is insufficient. If the thickness of the hard membrane exceeds the upper limit of the aforementioned range, The thickness of the coating film is dry or uniform, so cracks or voids may occur, making the strength or transparency of the hard coating film inadequate. ": This hard coating can be formed by forming the aforementioned matrix components. "Matrix shape" and coating of a coating solution containing the aforementioned antimony pentoxide particles, and "when the coating solution is prepared" is a coating solution capable of preparing a homogeneous dispersion. The antimony oxide particles are used to disperse. The user after the sol in the dispersing medium is better. The dispersing sol can be used as A ρ. The heart is the water-knife gel. The organic sol is dispersed in an organic solvent such as alcohol. The antimony oxide particles can be used on the surface. After being treated with a well-known silane coupling agent, the dispersed sol and matrix-forming components of the 5-week clothing made in this way can be diluted in an appropriate solvent, and the coating for forming a hard film can be obtained liquid In addition, the coating solution may be added with a surfactant, etc. for the sake of the females of Jinmaxue. In the soil β solution, it can also contain 314657 10 200400222 while dissolving the matrix-forming ingredients. When the solvent is volatilized and the matrix-forming component is a thermosetting resin, a curing agent can be prepared according to the needs. The coating solution of the material is based on the well-known dipping method, pad coating method, spin coating method, and the method of "J Method" Sub-drying on the substrate 'curing of thermosetting resin 2: Plastic resin needs to be heat-treated at a temperature below the softening point of the substrate to form a hard film. The hard film of the present invention is provided with an anti-reflection film. The base material of ⑼ may be provided on a hard coating film. As long as the anti-reflection film can be used, a conventionally known anti-reflection film can be used, and it is not particularly limited. Specifically, if the hard cover is low, it has anti-reflection performance. A reflection 'system that requires an A force is formed by a substrate for preventing reflection film formation and optionally a low refractive index component. The component, =: Γ formation substrate can form the anti-reflection film, and can be selected from the 宓与 and the substrate. Viewpoints such as mountains, hardness, and workability, etc. Specifically, you can make quality ingredients. It is stated that the same base material for the hard film-forming component is also used as the substrate, for example, as a catalyst, an acid or alkali hydrolysate. Hydrolyzable organic T uses a hydrolyzable organic silicon compound. 314657 13 200400222: The basic solution of the compound with k-oxide stone and alcohol can be added with water and p to make it suitable for use. , Aryl, ethyl, acrylic, etc. Nicotinyl, 2 or 3] Oxygen-burning and burning as shown in [2] or 3]. In particular, tetramethoxy-burning, tetraethoxylate "end", tetrapropoxylate It is suitable for use. : Any low-emissivity component except CaF2., NaF, NaAiFe,

MgF等之低折射率物質外貝之夕卜+可例舉如：二氧化石夕系 4子（-乳切粒子、二氧切中空粒子、二氧化銘複合氧化物粒子)、多孔質氧化石夕系粒子等。如使用將例如，太棄φ今杳所申請的日本專利特開平 3了5號公報中所揭示的多孔性之無機氧化物微粒子 tr氧切所被覆的複合氧化物微粒子，則可得折射率低而防止反射性能優異的防止反射膜。 :止反射膜中之低折射率成份之含量以9。重量⑽ 卜為"ί土 ’更以5 0重| 以τ炎“ 入旦，里/0以下為較佳。如低折射率成份之二1超過9G重量科，則被膜之強度可能會降低，或硬貝覆層（如形成有後述的中間膜時為中間層）等之與的密貼性可能會不足。土曰防止反射膜之厚度以50至3〇〇_為佳，更 2 00nm之範圍為更佳。如防止反射膜之厚度未滿前述範圍時，止反射性能等會變差。又防如防止反射膜之厚度超過前述制時，討能會上產生龜裂、或此膜之強度會降低或膜厚過严·心、射性能不足。子方止反如此的防止反射膜之折射率，t因低折射率成份與樹 314657 14 200400222 月曰寺基質的混合比例及所使用脂異，惟涓杳^ a 4 了 <讲射率而有差义土為在1.28至1.50之範圍。如 =:超過Μ。，則雖因基材之折射率而有不同: 下者反射之性能可能會不足而難於獲得折射率在⑶以 2反射料由含有上述防止反射膜形成用基質、及視而要之低折射率忐於、液之塗佈而形成。浴媒的防止反射膜形成用塗佈膜不= 能容易蒸發逸散並對所得防止反射 V音者均不特別限定。 /防^反射膜形成用塗佈液之塗佈方法，並不特別限疋’而只要與前述的塗法、旋塗法、較洽、去^夺形成同樣，依浸潰法、喷即可，特別β 寺周知之方法塗佈在基材上並乾燥口形成成份為熱固化性樹脂的情加熱處理、紫外蜱日”私* m 丨」错由質覆膜之固化線照射處理等以促進硬合物時，則可夢由力^ 加水分解性有機石夕化 J錯由加熱處理以促進加水分解性有機矽化合物之加水分解·聚縮合。本毛月中，可在硬質覆膜與防止反射膜之中間膜。』丹。又直有 t間膜 ::為：間膜’可設置折射率為16以上者。特別是’如基材或硬質覆膜之折射率為1.55以下時，則與防止反射膜之折射率之間的差距變小，以致防止反射 314657 ]5 200400222 之性能變得不足夠，因而以形成折射率在丨6以上之中間膜為佳。中間膜，係由高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，具體而言，可例舉如：在前述硬負覆膜形成用基質中所使用的；以及在前述防止反射膜中所例示的烷氧矽烷等之加水分解性有機矽化合物等。咼折射率之金屬氧化物微粒以使用折射率在丨以上之金屬氧化物微粒者為佳。以折射率在】· 7 〇以上者為更佳。這種金屬氧化物微粒，可例舉如：氧化鈦（2 5〇)、氧化鋅(2.0)、氧化鍅(2·20)、氧化鈽(22)、氧化錫(2〇)、氧化鉈（2.1)、鈦酸鋇（2.40)、氧化鋁〇.73)、氧化鎂（177)、氧化釔（1.92)、氧化銻（2.0)、氧化銦（2〇)等。（括弧内為折射率）此中較佳為氧化鈦、氧化鈽、氧化錫、氧化銻、氧化釔、氧化銦等之導電性微粒，再者，在此等微粒中摻雜有録、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〗·6〇以下時，由於所仔中間之折射率無法在丨·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 ]6 200400222 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 〇〇如之範圍。更佳範圍為在10至60nm。平均粒徑在5nm :m 下之粒子，視金屬氧化物之種類，有時難於製得，而MgF and other low-refractive-index materials such as: + 4 examples of stone dioxide (-milk-cut particles, dioxon hollow particles, oxide composite oxide particles), porous oxide stones Evening particles and so on. For example, if the composite oxide fine particles covered by the porous inorganic oxide fine particles tr oxygen cut disclosed in Japanese Patent Application Laid-Open No. 3 No. 5 applied by JP Imamoto are used, a low refractive index can be obtained. The antireflection film is excellent in antireflection performance. : The content of the low refractive index component in the antireflection film is 9. Weight ⑽ For "ί 土 'is more than 50 weights | It is better to use τ inflammation" to enter, below li / 0 is better. If the low refractive index component 1 exceeds 9G weight section, the strength of the coating may be reduced , Or a hard shell coating (such as an intermediate layer when an intermediate film described later) is formed, the adhesion may be insufficient. The thickness of the anti-reflection film is preferably 50 to 300 nm, more preferably 200 nm. The range is better. If the thickness of the anti-reflection film is less than the aforementioned range, the anti-reflection performance will be deteriorated. Also, if the thickness of the anti-reflection film exceeds the foregoing system, cracks may occur on the film, or the film may be damaged. The strength of the film will be reduced or the film thickness will be too tight, and the radiation performance will be insufficient. Zifang's anti-reflection film has such a refractive index, because of the low-refractive index component and the tree 314657 14 200400222 Yueyue Temple matrix mixing ratio and the use It ’s different, but it ’s different. ^ A 4 It means the emissivity and the difference is in the range of 1.28 to 1.50. For example, if it exceeds Μ, it is different because of the refractive index of the substrate: The performance may be insufficient and it is difficult to obtain the refractive index in the 3D reflective material by containing the above Reflective film-forming substrate and optionally low-refractive index coating, liquid coating. Anti-reflection film-forming coating film for bath media can not easily evaporate and escape, and prevent reflection V noise They are not particularly limited. The coating method of the coating liquid for forming anti-reflection film is not particularly limited, as long as it is the same as the aforementioned coating method, spin coating method, more compatible, and depletion formation, according to immersion It can be sprayed and sprayed, especially the method known by β Temple is coated on the substrate and dried to form a thermosetting resin. Heat treatment, UV tick day "Private * m 丨" is the curing line of the quality coating When irradiation treatment is used to promote the hard compound, the hydrolyzable organosilicon compound can be treated by heat treatment to promote the hydrolysis and polycondensation of the hydrolyzable organosilicon compound. In this hair month, an intermediate film between a hard coating and an anti-reflection film can be used. Dan. There is also a t-interlayer :: is: the interlayer 'can be set to a refractive index of 16 or higher. In particular, if the refractive index of the substrate or the hard coating is 1.55 or less, the gap between the refractive index of the antireflection film and the antireflection film becomes small, so that the antireflection performance becomes insufficient. An intermediate film having a refractive index of 6 or more is preferred. The interlayer film is made of high refractive index metal oxide fine particles and, if necessary, a substrate for forming an interlayer film. The substrate for forming an intermediate film refers to a component capable of forming an intermediate film on the surface of a hard film, and can be selected from resins and the like suitable for conditions such as adhesion and coatability with the hard film, and specifically, In other words, examples thereof include those used in the aforementioned hard negative film-forming substrate, and hydrolyzable organosilicon compounds such as the alkoxysilanes and the like illustrated in the aforementioned antireflection film. As the metal oxide particles having a refractive index, it is preferable to use metal oxide particles having a refractive index of ≧ 1. It is more preferable that the refractive index is at least 7 · 0. Examples of such metal oxide fine particles include titanium oxide (250), zinc oxide (2.0), hafnium oxide (2.20), hafnium oxide (22), tin oxide (20), hafnium oxide ( 2.1), barium titanate (2.40), alumina 0.73), magnesium oxide (177), yttrium oxide (1.92), antimony oxide (2.0), indium oxide (20), and the like. (The refractive index in parentheses) Among these, conductive fine particles such as titanium oxide, hafnium oxide, tin oxide, antimony oxide, yttrium oxide, and indium oxide are preferable, and these particles are doped with aluminum, tin, Electrically conductive particles of a different element such as fluorine are suitable because the anti-reflection film provided with the anti-reflection film has an anti-reflection property, an anti-charge effect, and an electromagnetic wave shielding property. ^ 'If the refractive index of the metal oxide particles is less than or equal to 60, the refractive index in the middle cannot be more than 60, and the difference between the refractive index and the antireflection film is small, which makes the antireflection performance insufficient. 314657] 6 200400222 The effect of setting the interlayer film. The average particle diameter of the metal oxide fine particles is preferably in the range of 5 to 1,000. A more preferred range is between 10 and 60 nm. Depending on the type of metal oxide, particles with an average particle size under 5nm: m may be difficult to obtain.

二〇〇-’則由於可視光線之明顯散射而使被膜之透明J 交差因而不宜。中間膜中之金屬氧化物微粒之含量，祇要是能f :::1.“上之中間膜，則並不特別限定，雖然常=用基質或金屬氧化物微粒之折射率而有所異，惟通之：土為在3〇至100重量％、更佳為在50至95重量％之乾圍〇另外，中門瞄叮达微粒而成者。間M可為不含基質，而僅由金屬氧化物女中間胺中之金屬氧化物微粒之含量為3 0重量％以雖羔因金屬乳化物微粒之種類而有所異，惟由於中 :門之折射率不會成為16〇以上，因而可能得不到設置 T間膜之效果。的中問腊粗、及.兩、’可由含有高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間成用塗佈液之塗佈而形成。再者，使用如眇&人p t 用+ I 此的金屬氧化物微粒以調製中間膜形成用之塗佈液時，輕、拔士土為作成使金屬氧化物微粒分散在分散絲中的溶膠使用，鐵、^ ϋ」作成水分散溶膠；經分散在醇等之有、’谷媒中的有機：它 h ^ 7刀散溶膠；或者，以周知之偶合劑處 -則逑微粒子後；咬γ γ 〜赵分散在有機溶媒中的有機溶媒分散 )7 3]4657 200400222 溶膠與塗料用樹脂使用適當的 P气B替丄 Μ〆合劑加以稀釋从Ο·、+ 間㈣成用之塗佈液。再者，為增進分散性希=作成中見’塗饰液中亦可添加表面活性劑等。 *疋性等起可使用的溶媒祇要是能容易射膜、中間膜無不良影響者，則放亚對所得防止反 ^ pa 苍則亚不特定限定。 :間膜形成用塗佈液之塗佈方法與塗佈液之情形同樣，並不特別限定…版：成用形成用塗佈液者同樣，以周、、硬貝覆胰輕塗法等方法塗佈在基材上並;;= 係熱固化性樹脂時，即可拜由加味；4寸別是形成成份電子崎… 猎由力熱處理、紫外線照射處理、、，泉-、射處理等以促進中間膜之含有力…卿有機條物時，則可藉由二=: 進加水分解性有機梅物之加水分解.聚縮：促質形成中間膜時，首先在基材上形成前述的硬 =二；佈中間膜形成用之塗布;夜，接著進行乾燥，，要▲基材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德，孟淤士' k ^ 芡再形成防止反射fe並實施固化促進處理。如上所4的有關本發明之附有硬質覆膜之基材，由於牡〜貝说中含有五氧化二録粒子，因而消除所產生的靜 314657 18 200400222 電’其結果可抑制塵與基材間高停”形成的硬質覆膜膜本身之硬声:丄在貼性、抗擦傷性、膜硬度等。又，被成時，將心=，而如硬質覆膜係由熱固化性樹脂所構度的被/ 氧化二録以促進被膜固化，而可製得高硬本發日月tb 化二銻粒子，E方:基材表面所設置的硬質覆膜含有五氧膜硬度H 與基㈣具優異之密貼性、抗擦傷性、膜之基材二同0=得具！防止帶電性能的附有硬質覆卢曰- 、3有五虱化一銻粒子，而可製得高硬 ^ 與基材間的密貼性、抗擦傷性、膜硬度等優異，、、二^生亦優異的附有硬質覆膜之基材。再者，當t造在硬質覆膜上之防止反射膜或中間㈣防亡反射薄膜的附有硬質覆膜之基材肖，亦不會被到傷或附者塵埃等異物，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。良/、 [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 膜形成用沴佈液之言周f 在五氧化一録粒子分散液（觸媒化成工業（股）穿』· ELCOM PC-]4，平均粒徑 2〇nm，Sb205 濃度 20 重量％，分散媒·乙基溶纖素/乙醇重量比=r 9 4 / 6 6) 2 0 0 g中^八聲外 3]4657 19 200400222 線固化樹腊（大乙基溶纖素 v油墨（股）製··優尼得克V5500)1 60g與200- 'is not suitable because the transparent J of the film is crossed due to the obvious scattering of visible light. The content of the metal oxide fine particles in the interlayer film is not particularly limited as long as it can be f ::: 1. ", Although it usually varies with the refractive index of the matrix or metal oxide particles, However, the reason is that the soil is dry in the range of 30 to 100% by weight, and more preferably 50 to 95% by weight. In addition, the middle door is aimed at Ding Da particles. The content of the metal oxide fine particles in the metal oxide female intermediate amine is 30% by weight. Although the amount varies depending on the type of the metal emulsion fine particles, the refractive index of the middle: gate does not become more than 160, so The effect of providing the T interlayer film may not be obtained. The thickness of the intermediate film is large, and two. The substrate for forming the intermediate film and the coating for the intermediate layer of the solvent may be microscopically dependent on the metal oxide containing a high refractive index. When the coating liquid for the formation of the intermediate film is prepared by using metal oxide fine particles such as 中间 & human pt + I, the metal oxide fine particles are made of light and basalt. The sol dispersed in the disperse filament is used, and iron, ^ ϋ "is used as a water-dispersed sol After being dispersed in alcohol and other organic materials, the grain medium: it h ^ 7 knife loose sol; or, with a well-known coupling agent-after the fine particles; bite γ γ ~ Zhao organic solvent dispersed in the organic solvent Dispersion) 7 3] 4657 200400222 The sol and coating resin were diluted with a suitable P gas B in place of the 丄 M mixture, and the coating solution for the formation of 0 ·, + intermediate was diluted. Furthermore, in order to improve the dispersibility, it is possible to add a surfactant or the like to the coating solution. * As long as the solvent can be used, as long as it can easily shoot the film and have no adverse effects on the interlayer film, Fangya does not specifically limit the resulting anti-reverse effect. : The coating method for the coating liquid for interlayer formation is the same as the case of the coating liquid, and is not particularly limited ... Plate: For the coating liquid for the formation, the method of coating the pancreas with a hard shell and the like is used. Coated on the substrate and;; = When it is a thermosetting resin, you can add flavor to it; 4-inch is not formed by the electronic saki ... Hunting by force heat treatment, ultraviolet radiation treatment, spring, spring treatment, etc. Promote the strength of the interlayer film ... When organic strips are used, they can be decomposed by adding two hydrolyzable organic plums. Polycondensation: When promoting the formation of interlayer film, the aforementioned hard film is first formed on the substrate = Two; coating for fabric intermediate film formation; night, followed by drying, can be obtained by heating the temperature below the softening point of the substrate and forming a general anti-reflection film. In particular, in the case of a matrix-based thermosetting resin, after each film (a hard coating, an antireflection film, and an intermediate film) is formed, a curing-promoting treatment can be carried out. The middle film is cured and promoted. Meng Yushi 'k ^' is re-formed to prevent reflection and is cured. Regarding the substrate with a hard film of the present invention as described above, since the pentoxide is contained in the substrate, the generated static electricity is eliminated. 314657 18 200400222 Electricity can be suppressed as a result. The hard sound of the hard coating film formed by "high stop": stickiness, abrasion resistance, film hardness, etc. Also, when it is finished, treat the heart =, and for example, the hard coating is made of thermosetting resin Degree of quilt / oxidation to promote the film curing, and can produce high-hardness tb chemical antimony particles, E side: The hard film on the surface of the substrate contains pentaoxide hardness H and base fixture Excellent adhesion, anti-scratch, and film substrate are the same as 0 = have! It has a hard cover with anti-charge performance, 3, and 5 antimony particles, which can make high hardness ^ and Excellent adhesion between substrates, scratch resistance, film hardness, etc., and substrates with a hard film are also excellent. Moreover, when the anti-reflection film or In the middle, the base material of the hard reflective film with a hard film will not be injured or foreign matter such as dust, A substrate with a hard film excellent in transparency, turbidity, etc. can be produced in a high yield. Good / [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not intended to wait for this. Example 1 The wording of the cloth solution for film formation is week f in the pentoxide pentoxide particle dispersion (Catalyst Chemical Industries, Ltd.) ELCOM PC-] 4, with an average particle size of 20 nm , Sb205 concentration 20% by weight, dispersing medium · ethyl lysin / ethanol weight ratio = r 9 4/6 6) 2 0 0 g medium ^ eight sound outside 3] 4657 19 200400222 linear curing wax (large ethyl solvent Cellulose v ink (stock) system · · Unideck V5500) 1 60g and

附有硬質母/〇g，以調製硬質覆膜形成用塗佈液（Η—1)。將硬質霜_ 、、，成用塗佈液（Η-1)在PET薄膜（厚度·· 1 88 // m，折射率·, — ·)上’各別依鑲條塗佈（bar coater)法進 4丁盒佈，在8〇。厂下乾燥1分鐘後照射高壓水銀燈（8〇W/cm)l 分鐘使宜㈤儿 ” ，以調製附有硬質覆膜之基材及（F_ 此化之硬質覆膜之厚度為5 // m及〇·3 " m。 ^曰歸ί ^面電阻計（三菱化學（股）製··核列斯達）測定所于貝復朕之表面電阻，其結果示於表工。 …又使用潯膜混濁計（haze meter)(蘇佳試驗機（股）製）測定全光線穿透率及濁度，其結果示於表卜再者依下述方法及評估基準評估叙筆硬度、抗擦傷性以及密貼性，其結果示於表1。 #._董雙^度之測定準照jis-k-54〇0，使用叙筆硬度計（penci] tes 測定。抗擦傷」^生之測定使用刪00鋼絲織（steei wo〇l),以5〇〇gW荷重滑動50 :欠，並以目視觀察膜表面，依下列基準評估，結果不於表1。評估基_準：認不出線溝之傷：◎ 可稍微認出線溝之傷：〇 314657 20 200400222 可認出多數線溝之傷·· △ 表面被全體性切削：X 查』占性在附有防止反射膜之基材（F_i)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1 〇〇個方格，對此 ‘接玻璃紙帶（celloPhne tape，登錄商標），接著，當將玻璃紙帶（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階段分類，以評估密貼性。將其結果示於表1。歹欠留方格之數目在9 5個以上：◎ 殘留方袼之數目在9 〇至9 4個：〇殘留方袼之數目在85至89個：△ 殘留方袼之數目在8 4個以下：X 實施例 2 用塗佈液1^2)之調製在五氧化二録粒子分散液（觸媒化成工業（股）製·· ELCOM PCM4，平均粒徑2〇nm，Sb2〇5濃度2〇重量％ , 分散媒：乙基溶纖素/乙醇重量比=94/66)2〇〇g中混合紫外線固化樹脂（大曰本油墨（股）製：優尼得克V55〇〇)93 3g與乙基溶纖素706.7g，以調製硬質覆膜形成用塗佈液（h_2)。硬質覆膜之基材（F_^之製造在實施例i中，除使用硬質覆膜形成用塗佈液以外，其餘則按與實施例！同樣方a，以調製2片附有硬質覆膜之基導2-]跡2_2)。此時之硬質覆膜之厂呈度為5” 334657 2] 200400222 及〇 · 3 // m。就所得的硬質覆膜評估表面電限、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1。實施例 3 之調 t 在五氧化二銻粒子分散液（觸媒化成工業（股）製： ELCOM PCM4，平均粒徑2〇nm，sb2〇5濃度20重量％，分散媒：乙基溶纖素/乙醇重量比==94/66)20(^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76〇g，以調製硬質覆膜形成用塗佈液（H-3)。歷-有硬鬣之製造在實施例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1同樣方式，以調製3片附有硬質覆膜之基材（F-3-l)、（F_3_2)以及（F-3-3)。此時之硬質後膜之厚度分別為5 " ni、1 " m、以及0.3 # 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4A hard mother / 0 g was attached to prepare a coating solution (Η-1) for forming a hard film. Apply a hard cream coating solution (， -1) to a PET film (thickness ·· 1 88 // m, refractive index ·, — ·) on a bar coater Method into 4 small box cloth, at 80. After drying under the factory for 1 minute, irradiate the high-pressure mercury lamp (80W / cm) for 1 minute to make it suitable for use. ”To adjust the substrate with a hard film and (F_ the thickness of this hard film is 5 // m And 〇 · 3 " m. The surface resistance meter (Mitsubishi Chemical Co., Ltd. ·· Hilesta) was used to measure the surface resistance at Beifujing, and the results are shown in a watchmaker. The haze meter (made by Sujia Testing Machine Co., Ltd.) measures the total light transmittance and turbidity. The results are shown in the table below, and the pen hardness and scratch resistance are evaluated according to the following methods and evaluation criteria. The properties and adhesion are shown in Table 1. # ._ 董双 ^ 度的测准准 jis-k-54〇0, measured using a pen hardness tester (penci) tes. Anti-abrasion test The steel wire 00 (steei wo01) was used to slide 50: 500 under a load of 500 gW, and the surface of the film was visually observed. The results were evaluated according to the following criteria, and the results are not in Table 1. Evaluation base_standard: The line was not recognized Groove injury: ◎ Slight line groove injury can be recognized slightly: 03314657 20 200400222 Most line groove injuries can be recognized ... △ The surface is cut in its entirety: X check. The surface of the substrate (F_i) with the anti-reflection film was scratched with a small knife at a gap of 1 mm in length and height to scratch 11 parallel scars to form 1000 squares. To this, a celloPhne tape (registered trademark) was attached. Then, when the cellophane tape (registered trademark) was peeled off, the number of cells remaining without peeling off the film was classified into the following four stages to evaluate the adhesiveness. The results are shown in Table 1. 歹留留方The number of cells is more than 95: ◎ The number of residual squares is between 90 and 94: The number of residual squares is between 85 and 89: △ The number of residual squares is below 84: X Example 2 Prepared with the coating solution 1 ^ 2) in a dispersion of pentoxide particles (manufactured by Catalytic Chemical Industries, Ltd., ELCOM PCM4, with an average particle size of 20 nm and an Sb205 concentration of 20% by weight, dispersed Vehicle: ethyl lysin / ethanol weight ratio = 94/66) 200 g of ultraviolet curable resin (daiyin ink (stock): Unideck V5500) 93 g with ethyl cellulose 706.7g to prepare a coating solution (h_2) for forming a hard film. The base material of the hard film (F_ ^ In Example i, except for using a coating film for forming a hard film, the rest of the method is the same as in Example! A, to prepare two pieces of the base film with a hard film 2-] trace 2_2). The hardness of the hard coating was 5 ”334657 2] 200400222 and 0.3 / m. The obtained hard coating was evaluated for surface electrical limit, total light transmittance, turbidity, pencil hardness, abrasion resistance, and denseness. The results of adhesion are shown in Table 1. The tone of Example 3 was in an antimony pentoxide particle dispersion (manufactured by Catalytic Chemical Industries, Ltd .: ELCOM PCM4, with an average particle diameter of 20 nm, and an sb205 concentration of 20 weight). %, Dispersing medium: ethyl lysinolysin / ethanol weight ratio == 94/66) 20 (^ mixed with UV curable resin (made by Daibonbon Ink (stock): Unideck V5500) 40g with ethyl cellulose 760 g to prepare a coating solution (H-3) for forming a hard film. Calendar-manufactured with hard iguana In Example 1, except that the coating liquid (Η-3) for forming a hard film was used, the rest was prepared in the same manner as in Example 1 to prepare 3 sheets with a hard film Substrates (F-3-l), (F_3_2), and (F-3-3). The thickness of the hard back film at this time is 5 " ni, 1 " m, and 0.3 # m. The obtained hard film was evaluated for surface resistance, total light transmittance, turbidity, stylus hardness, abrasion resistance, and adhesion. The results are shown in Table 1. Example 4

在五氧化二銻粒子分散液（觸媒化成工業（股）製： ELCOM PCM4，平均粒徑2〇nm，sb2〇5濃度2〇重量％，分散媒：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 200400222 附有硬質覆膜之基材（F-4)之製造在實施例1中，除使用硬質覆膜形成用塗佈液（H-4) 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度為 5// m 及 0.3// m。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1。實施例5 硬質覆膜形成用塗佈液（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 0/〇，分散媒：乙基溶纖素/乙醇重量比=94/66)200g中混合丙烯酸樹脂（希他羅伊土 1 007，曰立化成（股）製）40g與乙基溶纖素760g，以調製硬質覆膜形成用塗佈液（H-5)。附有硬質覆膜之基材（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/zm 及 0.3 " m。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，其結杲示於表1。實施例6 硬質覆膜形成用塗佈液（H-6)之調製將五氧化二銻膠體溶液（觸媒化成工業（股）製：RSB- 23 314657 200400222 KU，平均粒徑10nm，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，以調製五氧化二銻粒子分散液（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2〇〇g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 760g ’以調製硬質覆膜形成用塗佈液（H-6)。之基材造在實施例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-Π)及（F-6_2)。此時之硬質覆膜之厚度為 5 // m 及〇.3 # ηι。就所得的硬質覆膜評估表面電阻、全光線穿透率、濁度、斜筆硬度、抗擦傷性以及密貼性，其結果示於表i。實施例 7 成用塗佈液（H-7)之調在五氧化二銻膠體溶液（觸媒化成工業（股）製·· rsB_ κυ，平均粒徑10nm，Sb2〇5濃度i重量％)4=二中，添加卜環氧丙氧基丙基三甲氧石夕燒之石夕坑偶合劑二，在60 2料1小時。接著，在旋轉蒸m進行㈣取代之 ^ W以濃縮’以調製五氧化二録粒子分散液（sb，05滚度此八：、/°’分散媒θ乙基溶纖素/乙醇重量比韻6)。在二:;夜：广中混合紫外線固化樹脂(大曰本油墨(股) 付克：)，與乙基溶纖素調製硬貝 <又族形成用塗佈液（Η-7) c 314657 24 200400222 附有硬質覆膜之基材（F-7)之製造在實施例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-7-1)及（F-7-2)。此時之硬質覆膜之厚度為 5 // m 及 0.3 // m。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1。比較合j 1 硬質覆膜形成用塗佈液（RH-1)之調製混合紫外線固化樹脂（大曰本油墨（股）製··優尼得克 V5500)200g與乙基溶纖素800g，以調製硬質覆膜形成用塗佈液（RH-1)。附有硬質覆膜之基材（RF-1)之製造在實施例1中，除使用硬質覆膜形成用塗佈液（RH-1) 以外，其餘則按與實施例1同樣方式，以調製附有硬質覆膜之基材（RF-1-1)及（RF-1-2)。此時之硬質覆膜之厚度為 5 从 m 及 0.3 // m。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，其結杲示於表]。比較 <歹1j 2 硬質覆膜形成用塗佈液（RH-2)之調製混合丙烯酸樹脂（希他羅伊土 ] 007，日立化成（股）製）200g及乙基溶纖素800g，以調製硬質覆膜形成用塗佈液（RH-2)。 314657 200400222 之基材 niF-2U f ;告在貫施例1中，除使用硬質覆膜形成用塗佈液（RH_2) 以外’其餘則按與實施例1同樣方式，以調製2片附有硬貝覆朕之基材（RH1：^(RF_2_2)。此時之硬質覆膜之厚度為 5 // m 及〇. 3 # m。一所传的硬貝覆膜评估表面電卩且、全光線穿透率、濁度 I筆硬度、抗擦傷性以及密貼性，其結果示於表1。 W比較」^ 3In a dispersion of antimony pentoxide particles (made by Catalytic Chemical Industries, Ltd .: ELCOM PCM4, average particle size 20 nm, sb205 concentration 20% by weight, dispersion medium: ethyl lysin / ethanol weight ratio = 94/66) 200g of ultraviolet curable resin (made by Daibonbon Ink Co., Ltd .: Unidek V5500) and 782.9g of ethylcellulysin are mixed to prepare a coating solution for hard film formation (H-4 ). 22 314657 200400222 Manufacture of base material (F-4) with hard film In Example 1, except that the coating liquid (H-4) for hard film formation was used, the rest were the same as in Example 1. To prepare 2 pieces of base material (F-4-1) and (F-4-2) with hard film. The thickness of the hard film at this time is 5 // m and 0.3 // m. The obtained hard film was evaluated for surface resistance, total light transmittance, turbidity, pencil hardness, abrasion resistance, and adhesion. The results are shown in Table 1. Example 5 Preparation of a coating solution (H-5) for forming a hard film was prepared in a dispersion of antimony pentoxide particles (manufactured by Catalytic Chemical Industries, Ltd .: ELCOM PC-14, average particle diameter 20 nm, Sb205 concentration 20 weight) 0 / 〇, dispersing medium: ethyl lysinolysin / ethanol weight ratio = 94/66) 200 g of acrylic resin (Hitaroy soil 1 007, manufactured by Rihwa Kasei Co., Ltd.) and ethyl lysin 760 g to prepare a coating solution (H-5) for forming a hard film. Production of the substrate (F-5) with a hard coating film In Example 1, except that the coating liquid (H-5) for forming a hard coating film was used, the rest were prepared in the same manner as in Example 1. 2 pieces with hard film (F-5-1) and (F-5-2). The thickness of the hard coating at this time is 5 / zm and 0.3 " m. The obtained hard film was evaluated for surface resistance, total light transmittance, turbidity, pencil hardness, abrasion resistance, and adhesion. The results are shown in Table 1. Example 6 Preparation of a coating solution (H-6) for forming a hard film A colloidal solution of antimony pentoxide (manufactured by Catalytic Chemical Industries, Ltd .: RSB-23 314657 200400222 KU, average particle diameter 10 nm, Sb205) Concentration: 1% by weight) Concentrate while displacing the solvent in a rotary evaporator to prepare an antimony pentoxide particle dispersion (Sb205 concentration 20% by weight, dispersion medium: ethyl lysin / ethanol weight ratio = 94 / 66). To this dispersion 200 g, 40 g of an ultraviolet curable resin (manufactured by Dainippon Ink Co., Ltd .: Unidek V5500) and 760 g of ethylcellulysin were mixed to prepare a coating solution for forming a hard film (H -6). The substrate was made in Example 1, except that the coating liquid (H-6) for forming a hard film was used, and the rest was prepared in the same manner as in Example 1 to prepare two pieces of the substrate with a hard film ( F-Π) and (F-6_2). The thickness of the hard coating at this time is 5 // m and 〇.3 # ηι. The obtained hard film was evaluated for surface resistance, total light transmittance, turbidity, oblique pen hardness, abrasion resistance, and adhesion. The results are shown in Table i. Example 7 Preparation of a coating solution (H-7) for use in an antimony pentoxide colloid solution (manufactured by Catalytic Chemical Industries, Ltd., rsB_κυ, average particle size 10 nm, Sb205 concentration i wt%) 4 In the second, add the glycidyloxypropyltrimethoxide sintered shixikeng coupling agent two, and mix for 1 hour at 60%. Next, ㈣W was replaced in the rotary steam m to condense 'to prepare a dispersion of pentoxide particles (sb, 05 roll this eight :, / °' dispersion medium θ ethyl lysin / ethanol weight ratio rhyme 6). In the second :; night: Guangzhong mixed with ultraviolet curing resin (Da Yueben Ink (stock) Fu Ke :), and hard shellfish with ethyl cellulose-solubilizing agent < coating solution (Η-7) for family formation c 314657 24 200400222 Manufacture of the substrate (F-7) with a hard film In Example 1, except that the coating liquid (H-7) for forming a hard film was used, the rest of the procedure was the same as in Example 1. Two substrates (F-7-1) and (F-7-2) with a hard film are prepared. The thickness of the hard film at this time is 5 // m and 0.3 // m. The obtained hard film was evaluated for surface resistance, total light transmittance, turbidity, pencil hardness, abrasion resistance, and adhesion. The results are shown in Table 1. Compare 200 g of the mixed mixed UV curing resin for the coating liquid (RH-1) for hard film formation (manufactured by Daiichi Ink Co., Ltd. ···············) with 800 g of ethyl fibrinolysin. A coating solution for forming a hard film (RH-1) was prepared. Production of the substrate (RF-1) with a hard coating film In Example 1, except that the coating liquid (RH-1) for forming a hard coating film was used, the rest were prepared in the same manner as in Example 1. Substrates (RF-1-1) and (RF-1-2) with hard coating. The thickness of the hard coating at this time is 5 from m and 0.3 // m. The obtained hard coating was evaluated for surface resistance, total light transmittance, turbidity, pencil hardness, abrasion resistance, and adhesion, and the results are shown in Table]. <200 g of mixed acrylic resin (Hitaroite) 007 prepared by < 歹 1j 2 coating film (RH-2) for hard coating formation, 800 g of ethyl fibrinolysin were compared with A coating liquid (RH-2) for forming a hard film was prepared. 314657 200400222 substrate niF-2U f; in Example 1, except that a coating film (RH_2) for forming a hard film is used, the rest is prepared in the same manner as in Example 1, with 2 pieces of hardened The base material of the shell coating (RH1: ^ (RF_2_2). The thickness of the hard coating at this time is 5 // m and 0.3 # m. A hard shell coating has been evaluated to evaluate the surface voltage and full light. The penetrability and turbidity I pen hardness, abrasion resistance, and adhesion are shown in Table 1. W Comparison "^ 3

在一氧化石夕有機凝膠（觸媒化成工業（股）製；〇SCal_ ，平均粒徑l2nm，Si〇2濃度2〇重量％ 5分散媒：異丙知）2〇〇g中混合紫外線固化樹脂（大曰本油墨（股）製··優尼仔克V55〇〇)4〇g與乙基溶纖素了6“，以調製硬質覆膜形成用塗佈液（RH-3)。UV curable was mixed in 2000 g of monolithic oxide gel (manufactured by Catalytic Chemical Industries, Ltd .; 〇SCal_, average particle diameter 12 nm, SiO 2 concentration 20% by weight) 5 dispersant: isopropyl) 40 g of resin (made by Dainippon Ink Co., Ltd., ·················, 5 ~) with ethyl fibrinolysin to prepare a coating solution (RH-3) for forming a hard film.

、在實施例1中，除使用硬質覆膜形成用塗佈液（Rh_ ^卜，其餘則按與實施例1同樣方式，以調製1片附有石質覆膜之基材（RFdd)、（RF_3_2)以及（κρ3·3)。此日士硬質覆膜之厚度為5 // m、1 " m以及〇·3 " m。了之硬就所得的硬質覆膜評估表面電阻、全光線穿透率、、度、鉛筆硬度、抗擦傷性以及密貼性，其結果示於濁比車避』 1 0 形成用塗佈液（RH-4)之私二氧化二銻粒子（平均粒徑1$〇 # m)按能成 26 1 ^657 200400222 3 0重量°〆。之方式分散在異丙醇中’使用碾砂機（s an d mi 11) 在3 〇°C下粉碎5小時。對此添加異丙醇以調製濃度20重量％之三氧化二銻微粒分散液（平均粒徑50nm)。在此分散浪2〇〇g中混合紫外線固化樹脂（大曰本油墨（股）製：優尼得克V55⑽）4〇g與乙基溶纖素760g，以調製硬質覆膜形成用塗佈液（RH-4)。硬質覆膜之基材（RF-4)之製造_ 在實施例1中，除使用硬質覆膜形成用塗佈液（rh_4) 以外，其餘則按與實施例1同樣方式，以調製2片附有硬質覆膜之基材(RF-4- i)及(RF_4_2)。此時之硬質覆膜之厚度為 5 // m 及 0 · 3 // m。就所得的硬質覆膜評估表面φ κ \ ^ &七 τ ®兔阻、全光線穿透率、濁度、錯筆硬度、抗擦傷性以及穷及么貼性，其結果示於表1。 314657 27 200400222 表1 削有硬t獲膜之基材硬質覆膜基材種類五氧化二銻粒子基贺全先線穿透率濁度鉛筆硬度’ 抗擦傷性表面電阻平均粒徑含量種類含量膜厚密貼性 Q/D nm 重t% 重量％ U m % S X108 實施例1 PET 20 on 紫外線El· 80 5 91.9 1.1 3H 〇 ◎ 10 化糊脂 0.3 92.1 1.2 2H 〇 ◎ B0 實施例2 PET 20 on 紫外線固 70 5 91.6 1.2 3H ◎ ◎ 6 OU 化樹脂 0.3 91.8 1.2 2H 〇 ◎ 12 紫外線固化掏脂 5 91.1 1.7 3H ◎ @ 2 實施例3 PET 20 50 50 1 91.4 1.7 2H ◎ ◎ 3 0.3 91.5 1.7 2H 〇 ◎ 4 實施例4 PET 20 70 紫外線固 30 5 91.0 1.9 3H 〇 ◎ 5 化樹脂 0.3 91.3 2.0 2H 〇 ◎ 8 實施例5 PET 20 50 丙烯酸 50 5 : 91.3 1.8 2H ◎ ◎ 1 樹脂 0.3 91.5 1.8 2H 〇 ◎ 3 實施例6 PET 10 50 紫外線固 50 5 91,7 1.5 3H ◎ © 3 化樹脂 0.3 91.8 1.6 2H 〇 ◎ 7 實施例7 PET 10*7 50 紫外線0 50 5 91.8 1.4 4H ◎ ◎ 5 化樹脂 0.3 91.9 1.5 2H 〇 ◎ 10 比較例】 PET η 紫外線固 1ΠΠ 5 92.0 1.1 2H △ △ 10000以上化樹脂 1 UU 0.3 92.0 1.1 2B X △ 10000以上比較例2 PET 0 丙烯酸 1ΛΠ 5 91.9 1.1 1H X △ 10000以上构脂 1UU 0.3 92.0 1.3 B X Δ 10D00以上比較例3 (SiOj)*2 紫外線0 化樹脂 5 91.0 1.6 2H X Δ 10000以上 PET 50 50 1 91.4 1.8 2B X △ 10000以上 0.3 91.6 2.0 3B X △ 10000以上比較例4 PET (Sbj〇3) 50 紫外線固 50 5 卜91.0 1.6 2H △ △ 10000以上化樹脂 0.3 卜91.5 2.2 B X △ 10000以上 * 1:賁施例7係經矽烷偶合劑處理者。 * 2:比較例3係不用五氧化二銻而使用二氧化矽者。 * 3.:比較例4係不用五氧化二銻而使用三氧化二銻者〇實施例8 中間膜形成用之塗佈液（M-Π之調製將作為高折射率粒子的氧化鈦膠體（觸媒化成工業（股）製；歐布多雷克1130Z，折射率2.2，平均粒徑20nm，濃度20重量％)20g，與紫外線固化樹脂（大曰本油墨（股）製；優尼得克V5 5 00)0.44g以及異丙醇6.7g充份混合以調製中間被膜形成用塗佈液（M-1)。防止反射膜形成用塗佈液（R-1)之調製 [低折射率複合氧化物微粒分散凝膠之製造] 將曱基曱氧矽烷27.4g混合在濃度0.65重量％之氫氧化鈉水溶液872.6g中，在室溫下攪拌1小時，以調製作 28 514657 200400222 為CHsSiC»3/2的ι·5重量％之無色透明的部份加水分解物。 ^接著，將作為籽粒（seed particle)的平均粒徑5nm，Si〇2 派度20重之二氧化矽凝膠2〇g與純水3⑼㊂的混合物加溫至阶。此反應母液之PH為10.5，並對該母液中耗費6小時同時添加作為Si〇2的濃度15重量％之矽酸鈉水 /令液90〇g與上述部份加水分解物之水溶液$⑻㊂以及作為 A!2〇3的濃度〇·5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8〇r。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 fi]ter)洗淨，以製得固體成份濃度20重量％之含有曱基之Si〇2 . A】2〇3複合氧化物微粒 (A-1)之分散液。對所得的複合氧化物微粒（A])之分散液250g中添加純水550g並加溫至98°C，在維持此溫度之下，耗費5小時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石夕酸液（S i〇2濃度3 ·5重量％) 1 〇〇 g，以製得由一 ^ 化矽所被覆的含有曱基的Si〇2· Al2〇3複合氧化物微粒（B」）之分散液。接著，使用超濾膜洗淨，並對作成固體成份、、穿度13重量％的分散液500g添加純水i，125g，再滴下灌趟酸（濃度35.5重量％)而作成ΡΗ1·0以實施從微粒去除銘的處理。接著，在添加ρΗ3 ·0之鹽酸水溶液1 〇公升及純水^ 公升之下，使用超濾膜以洗淨去除所溶解的鋁鹽之同曰士進行濃縮以製付由固體成份濃度I 3重量％之二^j y μ 年L IC _戶f 3j4657 29 200400222 被覆的含有甲基之Si〇2. A】2〇3#合氧化物微粒（C⑴之分散液。將所得複合氧化物微粒（cq)之分散液，與純水5〇〇g、乙醇17,以及濃度2δ重量％之氨水6心的混合液加溫為35。〇後，添加石夕酸乙基鹽（肌濃度μ重量❶/錢，ϋ使用前述二氧化石夕加以被覆。使用蒸發器將此濃縮至固體成份濃度5重量％後，添加濃度15重量 %之氨水以作成ΡΗ10,在18〇。口之高壓鍋内加熱處理2 小時’接著’ I用超濾膜進行濃縮，製得經以固體成份濃度ίο重量％之二氧化矽所完全被覆的含有甲基之si〇2. Α】2〇3複合氧化物微粒（D-1)之分散液。 “該二氧化石夕被覆複合氧化物微粒⑴⑴之Si02/A1203 旲耳比為278，平均粒徑為34nm，折射率為i 36。在此，粒子之折射率係依下射式進行測定者。複綠物微粒㈣之分散液置入蒸發器中，使分月文 >谷媒洛發。 (2) 將此在12(TC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2、3滴，並對此混合上述粉末。 (4) 使用各種標準折射液實施上述（3)之操作，當混合液（多 2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])之分散液經過超濾挺’亚將分散媒之水取代為乙醇。 314657 30 200400222 充份混合該乙醇凝膠（固體成份濃度5重量％)5〇g，與 I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in(重量比）混合溶媒47g，以調製防止反射膜形成用塗佈液丨）。 Μ有硬質覆膜之某j 製造在按共κ %例1同樣方式所調製的硬質覆膜之基材 ()上&鑲铫塗佈法塗佈上述所調製的中間被膜形成=塗佈液（M])，在贼下乾燥i分鐘。此時之中間膜之厚度為80nm，折射率為18〇。接者，依鐵條塗佈 --- 丨㈣衣的P万JL汉射膜形成用塗佈液°1·1)，在8(rc下乾燥1分鐘後，照射高銀燈（80W/cm)l分鐘以使豆固化，以调製附有硬質覆膜之土材㈣此時之防止反射薄膜之厚度為8〇]這。在此，表中所示的硬質覆膜、防止反射膜 ::系切晶圓上個別將上述各塗佈液按與上述方法：公佈、乾燥以及固化處理，並使用橢圓對稱計進仃 (e】lips〇meter)(ULVAC 社製，EMS i)加以測定者。所得的附有硬質覆膜之基材評估表面電阻。、全牙处半、濁度、鉛筆硬度、抗擦傷性示於表2。及山貼性，其結杲敗直(f-ji之製立硬質覆膜之基間膜及防止在按與實施例2同樣方式所調製的附有才（〜1)上，牧與貫施例8同樣方式形成中 314657 200400222 反射月笪 $ ’以調製附有硬質覆膜之基材（F-9-i)C) *尤所得的附有硬質覆膜之基材評估表面命穿透率吧、、濁度、鉛筆硬度、抗擦傷性及密貼今於表2。實施11 〇 ---^ 之基材（f-io)之舉；告按與實施例3同樣方式所調製的附右材（F、3、i、 1 )、（F-3-2)以及（F-3-3)上，按與實施命工成中間膜及防止反射膜，以調製 a (F-l〇.n ^ ^ ^ μ )、（F、l〇-2)以及（F-10-3)。穿透ΐ所得的附有硬質覆膜之基材評估表面1 二表2。、濁度、鉛筆硬度、抗擦傷性及密貼七 f施息附有石承暂窄材(F==實施例4同樣方式所調製的附有, 反射嗅，以=與實施例8同樣方式形成h 周衣附有硬質覆膜之基材（F_1Kn h所得的附有硬質覆穿透率、：巧由丞w汁估表面謂示於表2〜1筆硬度、抗擦傷性以及密點在按與實:^77^^ )门知方式所調製的附阻、全光線 ’其結果不質覆膜之基 8同樣方覆膜之基材阻、全光線 ? 其結果示質覆膜之基膜及防止 ) 阻、全光線性，其結果覆膜之基 314657 32 200400222 材（F-5、i)上，反射膜，以調就所得的穿透率、濁度示於表2。實施例]1 在按與實材（F-6 4)上，反射膜，以調就所得的穿透率、濁度示於表2。之按與實施例8同樣方式形成中製附有硬質覆膜之基材。果及防止附有硬質覆膜之基材評估表4阻、、紐筆硬度、抗擦傷性以及密％ &，其結果、盖材（F-13)之f i告施例6同樣方式所調製的附 z 有更質覆膜之基按與貫施例8同樣方式形成中 τ间及防止製附有硬質覆膜之基材（F> 1 3、^ 附有硬質覆膜之基材評估表面叫兔阻、全光線、鉛筆硬度、抗擦傷性以及宓在貼性，其結果實施Μ 之基材（F-14)之製造在按與實施例7同樣方式所調製的附材（F- 7、i、l 、， )上’按與實施例8同樣方式形成身才餐In Example 1, except that a coating film for forming a hard film (Rh_ ^ b) was used, the rest was prepared in the same manner as in Example 1 to prepare a substrate (RFdd) with a stone film, ( RF_3_2) and (κρ3 · 3). The thickness of the Japanese hard coating is 5 // m, 1 " m, and 〇 · 3 " m. The hard coating obtained after evaluation is hard to evaluate the surface resistance and full light The results of the transmittance, hardness, pencil hardness, abrasion resistance, and adhesion are shown in Turbidity Avoidance. 1 10 Private antimony dioxide particles (average particle size) of the coating liquid (RH-4) for formation 1 $ 〇 # m) disperse in isopropanol in a manner capable of 26 1 ^ 657 200400222 30 0 °° C. 'using a sand mill (sandmi 11) and crushed at 30 ° C for 5 hours. Isopropyl alcohol was added to prepare a 20% by weight antimony trioxide fine particle dispersion (average particle size: 50 nm). 200 g of this dispersion was mixed with an ultraviolet curable resin (made by Daiichi Ink (stock): excellent Nidec V55⑽) 40g and ethyl lysinolysin 760g to prepare a coating film (RH-4) for the formation of a hard coating. Manufacture of a base material (RF-4) for a hard coating_ In Example 1, except that a coating film (rh_4) for forming a hard film was used, the same procedure as in Example 1 was used to prepare two substrates (RF-4-i) with a hard film. And (RF_4_2). The thickness of the hard film at this time is 5 // m and 0 · 3 // m. The surface of the hard film obtained is evaluated φ κ \ ^ & Seven τ ® rabbit resistance, full light transmission Rate, turbidity, stiff pen hardness, abrasion resistance, and poor adhesion, and the results are shown in Table 1. 314657 27 200400222 Table 1 Substrates with hardened film and hard film substrate type Antimony pentoxide Particles based on the first line transmittance turbidity pencil hardness' scratch resistance surface resistance average particle size content type content film thickness adhesion Q / D nm weight t% weight% U m% S X108 Example 1 PET 20 on UV El 80 5 91.9 1.1 3H 〇 ◎ 10 chemical paste 0.3 92.1 1.2 2H ○ ◎ B0 Example 2 PET 20 on UV curing 70 5 91.6 1.2 3H ◎ ◎ 6 OU resin 0.3 91.8 1.2 2H 〇 ◎ 12 UV curing liposuction 5 91.1 1.7 3H ◎ @ 2 Example 3 PET 20 50 50 1 91.4 1.7 2H ◎ ◎ 3 0.3 91.5 1.7 2H 〇 ◎ 4 Example 4 PET 20 70 UV curing 30 5 91.0 1.9 3H 〇 ◎ 5 resin 0.3 91.3 2.0 2H ○ ◎ 8 Example 5 PET 20 50 acrylic 50 5: 91.3 1.8 2H ◎ ◎ 1 resin 0.3 91.5 1.8 2H ○ ◎ 3 Example 6 PET 10 50 UV curing 50 5 91,7 1.5 3H ◎ © 3 Chemical resin 0.3 91.8 1.6 2H 〇 ◎ 7 Example 7 PET 10 * 7 50 UV 0 50 5 91.8 1.4 4H ◎ ◎ Chemical resin 0.3 91.9 1.5 2H 〇 ◎ 10 Comparative Example] PET η UV curing 1ΠΠ 5 92.0 1.1 2H △ △ 10,000 or more resin 1 UU 0.3 92.0 1.1 2B X △ 10000 or more Comparative Example 2 PET 0 Acrylic acid 1ΛΠ 5 91.9 1.1 1H X △ 10,000 or more 1UU 0.3 92.0 1.3 BX Δ 10D00 or more Comparative Example 3 (SiOj) * 2 UV resin 5 91.0 1.6 2H X Δ 10000 or more PET 50 50 1 91.4 1.8 2B X △ 10000 or more 0.3 91.6 2.0 3B X △ 10000 or more Comparative Example 4 PET (Sbj0) 50 UV curing 50 5 Bu 91.0 1.6 2H △ △ 10000 or more resin 0.3 Bu 91.5 2.2 BX △ 10000 or more * 1: Example 7 is treated with a silane coupling agent* 2: Comparative Example 3 is a case where silicon dioxide is used instead of antimony pentoxide. * 3 .: Comparative Example 4 is the one in which antimony trioxide is used instead of antimony pentoxide. Example 8 Coating solution for the formation of an intermediate film (M-Π is prepared as titanium oxide colloid with high refractive index particles (contact Medium chemical industry (stock) system; Obutorek 1130Z, refractive index 2.2, average particle size 20nm, concentration 20% by weight) 20g, and UV curing resin (made by Daiyoku Ink (stock); Unedek V5 5 00) 0.44 g and 6.7 g of isopropyl alcohol were sufficiently mixed to prepare a coating liquid (M-1) for forming an intermediate film. Preparation of a coating liquid (R-1) for forming an antireflection film [low refractive index composite oxidation Of fine particle dispersion gel] 27.4 g of fluorenyl alkoxysilane was mixed with 872.6 g of a 0.65% by weight sodium hydroxide aqueous solution and stirred at room temperature for 1 hour to prepare 28 514657 200400222 as CHsSiC »3 / 2 ％ · 5% by weight of a colorless and transparent partially hydrolyzed product. ^ Next, 20 g of a silica gel having an average particle size of 5 nm as a seed particle and 20 weight of SiO 2 and The mixture of pure water 3⑼㊂ is warmed to the stage. The pH of this reaction mother liquor is 10.5, and it takes 6 hours for the mother liquor. At the same time, 90% of 15% by weight sodium silicate water / reagent solution with a concentration of SiO2 and an aqueous solution of the above-mentioned partially hydrolyzed product $ ⑻㊂ and aluminum with a concentration of 0.5% by weight as A! Sodium hydroxide aqueous solution was 180 g. Meanwhile, the temperature of the reaction mother liquor was maintained at 80 r. The pH of the reaction mother liquor rose to 12.7 immediately after the addition, and thereafter there was no change. After the addition was completed, the reaction solution was cooled to a temperature. It was washed with an ultra-filtration membrane (Ultra fi] ter) to obtain a dispersion of 20% by weight solid content of sulfonium-containing SiO2. A] 203 composite oxide particles (A-1). 550 g of pure water was added to 250 g of the obtained dispersion liquid of the complex oxide fine particles (A)), and the temperature was increased to 98 ° C, and the sodium silicate aqueous solution was added with a cation exchange resin while maintaining the temperature for 5 hours. 100 g of shixi acid solution (Sio2 concentration 3.5% by weight) obtained by de-testing to obtain a silicon oxide-containing SiO2 · Al2O3 composite oxide coated with silicon oxide Dispersion of fine particles (B ″). Next, it was washed with an ultrafiltration membrane and made into a solid component with a penetration of 13% by weight. 500 g of the dispersion was added with 125 g of pure water i, and then dipped in acid (concentration 35.5% by weight) to form PQ1.0 to perform a process of removing the particles from the particles. Next, a hydrochloric acid aqueous solution of pH 3.0 was added to 10 liters and purified water. Under water ^ liters, the ultra-filtration membrane was used to wash and remove the dissolved aluminum salt, and the concentrate was concentrated to produce a solid content concentration of I 3% by weight ^ jy μ year L IC _ 户 f 3j4657 29 200400222 Coated SiO2. A] 2 # 3 # complex oxide particles containing a methyl group (a dispersion of C⑴. The mixed liquid of the obtained complex oxide fine particles (cq), 500 g of pure water, 17 ethanol, and 6 cores of ammonia water having a concentration of 2δ% by weight was heated to 35. 〇 After that, add ethyl oxalate (muscle concentration μ weight 钱 / money, ϋ) and cover it with the aforementioned dioxide. Use an evaporator to concentrate this to a solid content concentration of 5% by weight, and then add 15% by weight. Ammonia was prepared into pH 10 and heat-treated in a pressure cooker at 180 ° C for 2 hours. 'Next' I was concentrated with an ultrafiltration membrane to obtain a methyl group-containing solution that was completely coated with silicon dioxide at a solid content concentration of 6% by weight. SiO2. A] A dispersion of 203 composite oxide particles (D-1). "The SiO2 / A1203 ratio of the SiO2 coated composite oxide particles is 278, and the average particle diameter is 34nm. The refractive index is i 36. Here, the refractive index of the particles is measured according to the down-shooting method. The dispersion of the chlorophyll fine particles ㈣ is placed in an evaporator, and the moonlight > Gu media Luofa. (2) This was dried at 12 ° C and made into a powder. (3) Two or three drops of a standard refracting liquid of known refractive index was dropped on a glass plate, and the above powders were mixed. (4) Various standard refracting liquids were used. When the operation (3) above is carried out, when the mixed solution (mostly 2) is transparent The refractive index of the quasi-refractive solution is taken as the refractive index of the microparticles. The dispersion of the composite oxide microparticles (D) obtained above is subjected to ultrafiltration to replace the water of the dispersion medium with ethanol. 314657 30 200400222 Mix the ethanol thoroughly 50 g of gel (solid content concentration: 5% by weight), 3 g of I-line curing resin (made by Daiichi Ink (stock); Unideck v5500), and in (weight of isopropanol and n-butanol) Ratio) 47g of mixed solvent to prepare a coating solution for forming an antireflection film 丨). Someone with a hard coating is manufactured on the base material () of the hard coating prepared in the same manner as in Example 1 in total κ% & The inlay coating method is applied to form the above-prepared intermediate film = coating solution (M)), and dried under a thief for i minutes. At this time, the thickness of the intermediate film is 80 nm and the refractive index is 180. Then, Coating with iron strips --- 丨 Yiyi's Pwan JL Han film-forming coating solution ° 1 · 1), dried at 8 (rc for 1 minute, and then irradiated with a high silver lamp (80W / cm) for 1 minute to make The beans are cured to prepare a soil material with a hard coating. The thickness of the antireflection film at this time is 80.] Here, the table shows Quality coating, anti-reflection coating :: each of the above coating solutions is individually cut on a wafer according to the above method: published, dried, and cured, and (e) lipsmeter (ULVAC) And EMS i) were measured. The obtained substrate with a hard film was evaluated for surface resistance. The full tooth half, turbidity, pencil hardness, and abrasion resistance are shown in Table 2. Straight down (f-ji's rigid basement interlayer membrane and prevention of the attached talent (~ 1) prepared in the same manner as in Example 2) 200400222 Reflective Moonlight $ 'to prepare a substrate with a hard coating (F-9-i) C) * Evaluate the surface penetration rate of the substrate with a hard coating, especially the turbidity, pencil The hardness, abrasion resistance and adhesion are shown in Table 2. Implementation of 11 〇 --- ^ substrate (f-io); report with the right material (F, 3, i, 1), (F-3-2) and (F-3-3), the intermediate film and the anti-reflection film are prepared according to the order of implementation to modulate a (F10.n ^^^^), (F, 10-2), and (F-10- 3). Evaluation surface of the substrate with hard coating obtained by penetrating the concrete 1 2 Table 2. , Turbidity, pencil hardness, abrasion resistance, and close adhesion. F is attached with a temporary narrow stone material (F == Modified in the same manner as in Example 4, with reflection and odor, in the same manner as in Example 8. Form a substrate with a hard coating on the h-shirt (F_1Kn h with a hard coating on the penetration rate: The surface is estimated by the appearance of the surface hardness shown in Table 2 ~ 1, hardness, abrasion resistance, and dense point. According to the actual method: ^ 77 ^^) Modified resistance, full light, the result is not the same as the base of the coated film. 8 The same resistance of the base film, the full light? The result shows the base of the quality film. The results are shown in Table 2. The results are shown in Table 2 below. The results are shown in Table 2. Example] 1 Table 2 shows the transmittance and turbidity obtained by adjusting the reflection film on the actual material (F-6 4). In the same manner as in Example 8, a substrate made of a hard film was formed. The results are shown in Table 6 of the evaluation of the resistance, the hardness of the pen, the scratch resistance, and the density% of the substrate with a hard film. The results are shown in the same manner as in Example 6 of the cover material (F-13). In the same manner as in Example 8, the substrate with a more quality coating is formed in the same manner as in Example 8 and a substrate with a hard coating is prevented (F > 1 3, ^ Evaluation surface of the substrate with a hard coating) It is called rabbit resistance, full light, pencil hardness, abrasion resistance, and stickiness. As a result, the base material (F-14) that implements M is manufactured in the same manner as in Example 7 (F-7). , I, l,,) on the 'in the same manner as in Example 8

A勝’以調製附有硬質覆膜之基材（F VC所得的附有硬質覆膜之基材評估表牙透率、濁度、鉛筆硬度、抗擦傷性以及示於表2。比較故上之基材在按與比較例1同樣方式所調製 #硬質覆膜之基中間膜及防止、14])。面電阻、全光線密貼性，其結果的p付有硬質覆膜之基 314657 200400222 材（RF-W)上，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。就所得的附有硬質覆膜之基材評估表面電阻、全光線穿透率、濁度、斜筆硬度、抗擦傷性以及密貼性，早一丄人士 /、〆口 f 不於表2。比較例j 置覆膜之某封fRF-ή^製造鼸纟按與比較例2同樣方式所調製的附有硬f覆膜之基，材，按與實施例8同樣方式形成中間膜及防: 反射膜，以調製附有硬質覆膜之基材（RF_6q )。就所得的附有硬質覆膜之基材評估表面電阻、全光線穿透率、濁度、鉛筆硬度、抗擦傷性以及密貼性，其結示於表2。實施例1 5 土威用之重液（M-2)之調製 ^ 調製將硝酸銦79.9g溶解在水686g中所得的溶液，A win 'is prepared by preparing a substrate with a hard coating (F VC substrate with a hard coating is used to evaluate the surface permeability, turbidity, pencil hardness, abrasion resistance, and the results are shown in Table 2. Comparison of the reason The base material was prepared in the same manner as in Comparative Example 1. The base intermediate film and prevention of #hard coating, 14]). Surface resistance and full-light adhesion. As a result, p is coated with a hard film base 314657 200400222 material (RF-W), and an intermediate film and an anti-reflection film are formed in the same manner as in Example 8. Laminated substrate. The obtained substrate with a hard film was evaluated for surface resistance, total light transmittance, turbidity, oblique pen hardness, abrasion resistance, and adhesiveness. Table 2 is not available. Comparative Example j Manufacture of a certain fRF-price ^ with a coating film. The base and material with a hard f film prepared in the same manner as in Comparative Example 2 were formed in the same manner as in Example 8 to form an intermediate film and prevent: Reflective film to modulate the substrate (RF_6q) with a hard film. The obtained substrate with a hard coating was evaluated for surface resistance, total light transmittance, haze, pencil hardness, abrasion resistance, and adhesiveness. Table 2 shows the results. Example 1 5 Preparation of heavy liquid (M-2) for Towell ^ Prepare a solution obtained by dissolving 79.9 g of indium nitrate in 686 g of water,

•及將錫酸鉀12.7g溶解在濃度1〇重量％之氫氧化鉀溶液中所得的溶液，並將此等溶液以2小時添加經保持在5〇 C的1〇〇〇g之純水中。在此當中，保持系内之pH為U。從所得的錫摻雜氧化銦水合物分散液中溏別· ί先淨錫摻雜乳化銦水合物後，加以乾燥，接著，在空氣中在3 50°C之 μ度下燒成3小時，再在空氣中以6〇(rc之溫度燒成2小 %，以製得錫推雜氧化銦微粒（Q-3)。將此按濃度能成為 J 〇里I %之方式分散在純水中，再以硝酸水溶液調整pH 34 3】抱7 200400222 ' •後，在保持此混合液為3 〇τ ^ m 、^ C之下使用碾砂機粉碎3 /、寸，以調製凝膠。其次，使丄 ,、；丄八子父換树脂處理此凝膠以去除項酸離子，接著，使用豈旋心制松吨士 ^ "内®子進打溶媒取代，以調衣払鍊有錫的氧化銦（IT〇)微 <刀放液（折射率1 ·9〇，平句粒徨20nm，濃度2〇重量％)。接著，充份混合摻雜有錫的_儿λ 、、存2〇 , 頁錫的虱化銦（ΙΤΟ)微粒之分散液20g ’與紫外線固州〇〇)〇 44^ % ^ 7 本油墨（股）製；優尼得克 .g及兴丙醇6.7g，以調製中n| 液（Mj)。衣中間被肤形成用塗佈在實施例8中，除使用中間外，i从，少风用塗佈液（M-2)以 /、釦則按與實施例8同樣方式膜，以▲田由丨风干間版及防止反射、乂调製附有硬質覆膜之基材（f_15、1}。就所得的附有硬質覆膜之基材穿透率、、巧洽十估表面電阻、全光線濁度、鉛筆硬度、抗擦傷性示於表2。及么貼性，其結果 -實施二^基;6)之製造在’、施例8中，除未形成有中門、實施例δ同_ | Β 、以外，其餘則按與 ^ 以調製附有硬f覆膜之基材〇Μ6_η。、所得的附有硬質覆膜之基材穿透率、屬声a 十怙表面電阻、全光線示於表2。 &抗^^生以及密貼性，其結果比較1 314657 200400222 附有硬質覆藍之基材（RF-7J^製逵^ 在按與比較例3同樣方式所調製的附有硬質覆膜之基材（RF-3-1)、（rf-3-2)以及（RF-3-3)上，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（RF-7~1)、（RF_7_2)以及（RF-'3)。就所得的附有硬質覆膜之基材評估表面電阻、全光線And a solution obtained by dissolving 12.7 g of potassium stannate in a 10% strength potassium hydroxide solution, and adding these solutions to 2 000 g of pure water maintained at 50 C over 2 hours . During this time, the pH in the system was kept at U. From the obtained tin-doped indium oxide hydrate dispersion, 先 first, clean the tin-doped emulsified indium hydrate, dry it, and then sinter it in air at μ 50 ° C for 3 hours. Then, it is fired in air at 2 ° C (2%) to obtain tin doped indium oxide particles (Q-3). This is dispersed in pure water in such a way that the concentration becomes J ° 0%. Then, adjust the pH 34 with a nitric acid aqueous solution. 3] Hold 7 200400222 '• After keeping this mixed solution at 3 〇 ^ m, ^ C, use a sand mill to pulverize 3 /, inch to adjust the gel. Second, The gelatin was replaced with a resin to treat the gel to remove acid ions. Then, it was replaced with a pine cone made of Xuanxin ^ " Inner® Zijin solvent, to adjust the oxidation of tin with a tin chain. Indium (IT0) micro < knife discharge solution (refractive index 1.90, Pinggu particle size 20nm, concentration 20% by weight). Next, tin-doped λ, λ, and 2% were mixed well. , 20g of dispersion of indium lice indium (ΙΤΟ) particles' and UV Guzhou 〇〇) 〇44 ^% ^ 7 Made by this ink (stock); Unedek.g and 6.7g of propanol Prepared in n | liquid (Mj). In the middle of the clothing, the coating for skin formation was applied in Example 8. Except that the middle was used, the coating solution for low wind (M-2) was used, and the buckle was filmed in the same manner as in Example 8. The substrate with a hard film (f_15, 1} is prepared by air-drying the interlayer plate and preventing reflection, and the surface transmittance of the substrate with a hard film is calculated. The light turbidity, pencil hardness, and abrasion resistance are shown in Table 2. The results are shown in Table 2. The results are shown in Table 2. 6) The manufacturing method is described in Example 8 except that the middle door is not formed. Example δ Same as _ | Β, except for the rest, press and ^ to modulate the substrate OM6_η with a hard f film. Table 2 shows the transmittance, surface acoustic resistance, and full light of the obtained substrate with a hard coating. & Resistance to health and adhesion, the results are compared 1 314657 200400222 substrate with a hard blue coating (manufactured by RF-7J ^ 逵) In the case where a hard coating is prepared in the same manner as in Comparative Example 3 On the substrates (RF-3-1), (rf-3-2), and (RF-3-3), an intermediate film and an anti-reflection film were formed in the same manner as in Example 8 to prepare a film with a hard film. Substrates (RF-7 ~ 1), (RF_7_2), and (RF-'3). Assess the surface resistance and full light of the obtained substrate with a hard coating

穿透率、濁度、鉛筆硬度、抗擦傷性以及密貼性，其結示於表2。 ' ° 比較基材（RF-8)之製造从只％敉例4同樣方式所調製的附有硒材⑽+1}上，按與實施例8 〜、讀之基反射膜，以調製附有硬質覆膜之基材⑽=間膜及防止 —就所得的附有硬質覆膜之基材評估表牙透率、濁度、鉛筆硬度、^ 电且、全光線示於表2。以“性以及密貼性，其結果 31465? 36 200400222 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 S 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 SO 3 94.6 1.6 0.48 4H ◎ ◎ 實施例10 貫施例3 5 1.80 80 1.44 80 1 94.6 1.9 0.48 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 〇〇實施例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 1.44 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16 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 △ 比較例6 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 0.3 1.B0 80 1.39 80 10000以上 94,7 1.7 0.55 2B △ Δ 比較例8 比較例4 5 1,80 80 1.39 80 10000以上 94.4 1.5 0.50 2H Δ Δ 314657The transmittance, turbidity, pencil hardness, abrasion resistance and adhesion are shown in Table 2. '° Comparative substrate (RF-8) is manufactured from selenium material with a modulation method of + 1% in the same manner as in Example 4 (+1), and the base reflection film is read in accordance with Examples 8 to, to prepare the The substrate of the hard coating ⑽ = interlayer and prevention—The obtained substrates with the hard coating were evaluated for tooth permeability, turbidity, pencil hardness, electrical conductivity, and full light. Based on the "sex and adhesion" results, 31465? 36 200400222 substrate with a hard coating, hard coating, intermediate film, anti-reflection film thickness " m refractive index thickness nm refractive index film thickness nm surface resistance Q / D X10 ® Total Light Transmission Turbidity S Reflectance \ Pencil Hardness Scratch Resistance Adhesiveness 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 SO 3 94.6 1.6 0.48 4H ◎ ◎ Example 10 Example 3 5 1.80 80 1.44 80 1 94.6 1.9 0.48 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 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 1.44 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 16 Implementation Example 1 5-1.39 80 8 94.6 1.5 0.90 4H ◎ Comparative example 5 Comparative example 1 5 1.80 80 1.44 80 10,000 or more 94.5 1,5 0.50 2H Δ △ Comparative example 6 Comparative example 2 5 1,80 80 1.44 80 10,000 or more 94.3 1.5 0.49 2H Δ Δ Comparative example 7 Comparative example 3 5 1.80 80 1.39 80 10,000 or more 94,5 1,5 0.51 2H Δ Δ 1 1.80 80 1.39 80 10,000 or more 94.6 1.6 0.54 B △ Δ 0.3 1.B0 80 1.39 80 10,000 or more 94,7 1.7 0.55 2B △ Δ Comparative Example 8 Comparison Example 4 5 1,80 80 1.39 80 above 10000 94.4 1.5 0.50 2H Δ Δ 314657

Claims

200400222 拾、申請專利範圍： K 一種附有硬質覆膜之基材，#由基材、及基材上所形成的硬夤覆膜而成，其特徵為： "亥更貝设膜含有基質成份及五氧化二銻（Sb2〇5)粒子，該五氧化二銻粒子之平均粒徑在2至100nm之範圍’而硬質覆膜中之五氧化二銻粒子之含量在5至重量％之範圍。 2·:申請：利範圍f i項之附有硬質覆膜之基材，其中， W述基質成份係熱固化樹脂或紫外線固化樹脂者。申I I利轨圍第1項或第2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:… 4. 如申請專利範圍第覆膜之基材，其中至1 0 // m之範圍。如申请專利範圍第覆膜之基材，其中止反射膜者。200400222 Scope of patent application: K A substrate with a hard film, # is made of a substrate and a hard film formed on the substrate, and is characterized by: " 海更贝 SET film contains a substrate Ingredients and antimony pentoxide (Sb205) particles, the average particle diameter of the antimony pentoxide particles is in the range of 2 to 100nm 'and the content of antimony pentoxide particles in the hard coating is in the range of 5 to wt% . 2: Application: The substrate with a hard film in the scope of item f i, wherein the matrix component is a thermosetting resin or an ultraviolet curing resin. The substrate with a hard film in item II or item 2 of the application II, in which the film thickness of the aforementioned hard film is between 0: ... 4. If the substrate with the film in the scope of the patent application, Where to the range of 1 0 // m. For example, the base material of the film covering the scope of the patent application, including the anti-reflection film.

1項至第3項中任一項之附有硬質，前述硬質覆膜之膜厚，為在q.2 1項至第4項中任一項之附有硬質，在前述硬質覆膜上，再形成有防 6. 如申請專利範在前述硬質覆圍第5項之附有硬質覆膜之基材膜與防止反射膜之間，形成有中 ’其中，間膜者。 38 200400222Any one of items 1 to 3 is attached with hardness, and the film thickness of the aforementioned hard coating is the same as that in any one of q.2 1 to item 4, attached to the aforementioned hard coating, Re-formation 6. If the patent application is between the base film with a hard coating and the anti-reflection film in the aforementioned hard covering item 5, there is a medium, among which an interlayer film. 38 200400222

柒、指定代表圖：本案無代表圖 (一）本案指定代表圖為：第（）圖。 (二）本代表圖之元件代表符號簡單說明：指定 Designated representative map: There is no representative map in this case. (1) The designated representative map in this case is: (). (2) A brief description of the component representative symbols of this representative map:

捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 4 314657捌. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 4 314657