201026508 六、發明說明： 【發明所屬之技術領域】 本發明係關於防眩性硬被覆膜及使用它之偏光板。更 詳細而言，本發明係關於其爲設置包含有機微粒之硬被覆 層的防眩性硬被覆膜，其係可控制外部霧度値及60°光澤 値於所希望之値，同時因膜厚所致之外部霧度値的變動 少、且可穩定生產之表面硬度優異的防眩性硬被覆膜；以 及使用該防眩性硬被覆膜的偏光板。 〇 【先前技術】 在映像管（CRT)或液晶顯示器（LCD)、電槳顯示器（PDP) 等之顯示器中，光從外部入射至畫面，該光反射而使顯示 畫面模糊，特別是近年來隨著顯示器的大型化，解決上述 問題成爲愈來愈重要的課題。舉出有使用具有防眩性硬被 覆層之構件作爲解決該問題的手段之一。然後該防眩性硬 被覆層的形成方法，可大致分類爲（1)在用於形成硬被覆層 之硬化時以物理方法使表面粗糙化的方法；（2)在硬被覆層 ® 形成用之硬被覆劑中混入塡料的方法；（3)在硬被覆層形成 用之硬被覆劑中混入非相溶的2成分，利用彼等之相分離 的方法等 3種。彼等任一者均藉由在表面上形成細微凹 凸，抑制外光之規則反射，並防止螢光燈等之外光的映現。 於彼等之中，以（2)之在硬被覆劑中混入塡料的方法爲主 流。塡料方面一般使用原本以氧化矽爲代表的無機微粒。 使用氧化矽粒子的理由方面，除了可抑制低的所得硬被覆 膜的白色度以外，還可以舉出有未造成因硬化不足所致之 -4 - 201026508 耐擦傷性降低等。 另外，提案有在透明基板上，形成由折射率1.40至1.60 之樹脂粒與電離放射線硬化型組成物所構成之防眩層的防 眩性膜。例如，在專利文獻1中，爲了形成顯現防眩性之 凹凸，而提案有藉由塗膜之膜厚以上之粒徑的有機塡料而 得的防眩性膜，但爲了提高防眩性而增大凹凸時則霧度値 上升，而有所謂透過鮮明度下降的問題。爲了改善該點， 在專利文獻2中，提案有藉由減低用以顯現防眩性之凹凸 ® 形成用的塗膜膜厚以上之粒徑的有機塡充劑添加量，而添 加塗膜膜厚以下之粒徑的有機添加劑，製作平衡佳之防眩 性膜。 然而，實際上，以如上述之方法，即使可取得光學物 性的平衡，由於使用微粒之粒徑的不均勻，出現不存在凹 凸的地方，亦得不到全面的防眩性。又，有所謂因由膜厚 所致之外部霧度値變動大而使穩定生產性變差的問題。 又，該等系列係以微粒尺寸來決定膜厚，如表面硬度之隨 ® 膜厚來改變其性能之物性的調整變困難。 專利文獻1:特開平6-18706號公報 專利文獻2:專利第3515401號公報 【發明說明】 本發明係因該等狀況下，以提供一種防眩性硬被覆 膜’其爲設置包含有機微粒之硬被覆層的防眩性硬被覆 膜，其可控制外部霧度値及60°光澤値於所希望之値，同 時因膜厚所致之外部霧度値的變動少，且可穩定生產之表 201026508 面硬度優異；以及使用該防眩性硬被覆膜之偏光板爲目的。 本發明者等，爲了達成前述目的而重複專心一志硏究 的結果，發現藉由使用含有活性能量射線感應型組成物、 較佳爲包含氧化矽系微粒之活性能量射線感應型組成物， 與對於該組成物具有特定之比重差的有機微粒的硬被覆層 形成材料而形成硬被覆層，而且該厚度較前述有機微粒之 平均粒徑大所構成的防眩性硬被覆膜，可達成該目的。本 發明係基於相關之發現知識而完成者。 Ο 即，本發明爲提供 [1] —種防眩性硬被覆膜，其特徵爲在透明塑膠膜的表面 上，具有使用（A)活性能量射線感應型組成物、及（B)含 有有機微粒之硬被覆層形成材料所形成的硬被覆層，在 溫度25 °C下，前述（A)成分之比重較（B)成分之比重大 0.25以上，而且前述硬被覆層之厚度較前述（B)有機微 粒之平均粒徑大； [2] 如上述記載於[1]項之防眩性硬被覆膜，其中（A)成分爲 ® (a)多官能性（甲基）丙烯酸酯單體及/或（甲基）丙烯酸酯 預聚物，與（b)包含氧化矽系微粒之活性能量射線感應型 組成物； [3] 如上述記載於[1]或[2]項之防眩性硬被覆膜’其中（b)氧 化矽系微粒爲具有包含（甲基）丙烯醯基之官能基做爲表 面官能基的氧化砂微粒；及 [4] 一種偏光板，其係由將記載於上述Π]至[3]項中任一項 之防眩性硬被覆膜之硬被覆層形成面的反側表面貼合 201026508 於偏光鏡所構成。 根據本發明，可提供一種防眩性硬被覆膜，其爲設置 包含有機微粒之硬被覆層的防眩性硬被覆膜，其可控制外 部霧度値及60°光澤値於所希望的値，同時因膜厚所致之 外部霧度値的'變動少；以及可穩定生產之表面硬度優異； 以及使用該防眩性硬被覆膜的偏光板》 【實施方式】 在本發明之防眩性硬被覆膜上，在設置於透明塑膠膜 0 至少單面之硬被覆層的形成中，使用具有下述之組成的硬 被覆層形成材料。 [硬被覆層形成材料] 本發明中之硬被覆層形成材料，含有（A)活性能量射線 感應型組成物、及（B)有機微粒。 ((A)活性能量射線感應型組成物） 在前述硬被覆層形成材料中，使用做爲（A)成分之活性 能量射線感應型組成物方面，可較佳地使用包含（a)多官能 ® 性（甲基）丙烯酸酯單體及/或（甲基）丙烯酸酯預聚物，與（b) 氧化矽系微粒。 還有，在本發明中，所謂活性能量射線，係指在電磁 波或帶電粒子射線中具有能量量子者，即紫外線或電子射 線等。 <(a)多官能性（甲基）丙烯酸酯單體及/或（甲基）丙烯酸酯預聚物> 在本發明中，使用多官能性（甲基）丙烯酸酯單體及/或 (甲基）丙烯酸酯預聚物，做爲（A)活性能量射線感應型組成 201026508 物。 前述多官能性（甲基）丙烯酸酯單體方面，舉例有1>4-丁二醇二（甲基）丙烯酸酯、1，6_己二醇二（甲基）丙烯酸酯、 新戊二醇二（甲基）丙烯酸酯、多乙二醇二（甲基）丙烯酸酯、 羥基三甲基乙酸新戊二醇二（甲基）丙烯酸酯、二（甲基）丙烯 酸二環戊酯、己內酯改質二（甲基）丙烯酸二環戊烯酯、環 氧乙烷改質磷酸二（甲基）丙烯酸酯、烯丙化二（甲基）丙烯酸 環己酯、異氰酸酯二（甲基）丙烯酸酯、三（甲基）丙烯酸三羥 ^ 丙酯、二新戊四醇三（甲基）丙烯酸酯、丙酸改質二新戊四 醇三（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、環氧丙 烷改質三（甲基）丙烯酸三羥丙酯、三（丙烯酸氧乙基）異氰酸 酯、丙酸改質二新戊四醇五（甲基）丙烯酸酯、二新戊四醇 六（甲基）丙烯酸酯、己內酯改質二新戊四醇六（甲基）丙烯酸 酯等之多官能基（甲基）丙烯酸酯。彼等之單體可使用1種 或組合2種以上來使用均可》 另外，前述（甲基）丙烯酸酯系預聚物方面，舉例有聚 酯丙烯酸酯系、環氧基丙烯酸酯系、胺甲酸酯丙烯酸酯系、 聚醇丙烯酸酯系等。其中，聚酯丙烯酸酯系預聚物方面， 例如可藉由以（甲基）丙烯酸，酯化多元羧酸與多元醇之縮 合所得之二終端上具有羥基的聚酯寡聚物的羥基，或者藉 由以（甲基）丙烯酸，將在多元羧酸上加成環氧烷烴而得之 寡聚物終端的羥基予以酯化而得者。 環氧基丙烯酸酯系預聚物’例如可藉由在較低分子量 之雙酚型環氧樹脂或酚醛清漆型環氧樹脂的環氧乙烷環 201026508 上，使（甲基）丙烯酸反應並酯化而得。胺酯丙烯酸酯系預 聚物，例如可藉由以（甲基）丙烯酸，酯化以聚醚聚醇或聚 酯聚醇，和聚異氰酸酯之反應而得的聚胺酯寡聚物而得。 再者，聚醇丙烯酸酯系預聚物，可藉由以（甲基）丙烯酸， 酯化聚醚聚醇之羥基而得。彼等預聚物可使用1種或組合 2種以上來使用均可，又，亦可與前述多官能性（甲基）丙烯 酸酯系單體倂用。 <(b)氧化矽系微粒> β 在本發明中，可使用膠體狀氧化矽微粒及/或具有表面 官能基之氧化矽微粒做爲（b)氧化矽系微粒。 膠體狀氧化矽微粒係平均粒徑爲1至40 0nm左右者， 又具有表面官能基之氧化矽微粒方面，可舉例有具有包含 (甲基）丙烯醯基之官能基做爲表面官能基的氧化矽微粒（以 下，稱爲反應性氧化矽微粒。）。 上述反應性氧化矽微粒，例如可藉由在平均粒徑0.005 至Ιμπι左右之氧化矽微粒表面的矽烷醇基上，使具有可與 ® 該矽烷醇基反應之官能基的含聚合性不飽和基的有機化合 物反應而得。聚合性不飽和基方面，舉例有自由基聚合性 之（甲基）丙烯醯基等。 具有可與前述矽烷醇基反應之官能基的含聚合性不飽 和基之有機化合物方面，較佳爲使用例如以通式（I)表示 的化合物等。 R1201026508 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to an antiglare hard coating film and a polarizing plate using the same. More specifically, the present invention relates to an anti-glare hard coating film provided with a hard coating layer containing organic fine particles, which can control the external haze and the 60° gloss to the desired flaw, and at the same time, the film An anti-glare hard coating film having a small variation in external haze 厚 due to thickness and having excellent surface hardness which can be stably produced, and a polarizing plate using the anti-glare hard coating film. 〇[Prior Art] In a display tube (CRT), a liquid crystal display (LCD), a paddle display (PDP), etc., light is incident from the outside to the screen, and the light is reflected to blur the display, especially in recent years. With the increase in the size of the display, solving the above problems has become an increasingly important issue. One of the means for solving this problem is to use a member having an anti-glare hard coating layer. Then, the method for forming the antiglare hard coating layer can be roughly classified into (1) a method of physically roughening the surface when hardening the hard coating layer is formed; and (2) forming the hard coating layer®. (3) A method in which a binder is mixed in a hard coating agent; (3) three kinds of incompatible two components are mixed in a hard coating for forming a hard coating layer, and three methods such as phase separation are used. Either of them suppresses the regular reflection of external light by forming fine concavities on the surface, and prevents the reflection of light other than fluorescent lamps. Among them, the method of mixing the dip in the hard coating agent in (2) is the main flow. In the case of dip, inorganic particles originally represented by ruthenium oxide are generally used. In addition to the whiteness of the obtained hard coating film, the reason for the use of the cerium oxide particles is not limited, but also the abrasion resistance is not caused by the insufficient hardening of -4 - 201026508. Further, an antiglare film having an antiglare layer composed of a resin particle having a refractive index of 1.40 to 1.60 and an ionizing radiation curable composition is formed on a transparent substrate. For example, in the case of forming the anti-glare unevenness, an anti-glare film obtained by using an organic material having a particle diameter equal to or larger than the film thickness of the coating film is proposed, but in order to improve the anti-glare property, When the unevenness is increased, the haze is increased, and there is a problem that the sharpness is lowered. In order to improve this, in Patent Document 2, it is proposed to increase the amount of the organic ruthenium added by reducing the particle size of the coating film thickness for forming the anti-glare property. The following organic additives of the particle size are used to produce a well-balanced anti-glare film. However, in actuality, even in the above-described method, even if the balance of the optical properties can be obtained, the unevenness of the particle diameter of the particles is used, and there is no place where the concavities are present, and comprehensive anti-glare properties are not obtained. Further, there is a problem that the external haze 値 varies greatly due to the film thickness, and the stable productivity is deteriorated. Moreover, these series determine the film thickness by the particle size, and it is difficult to adjust the physical properties such as the surface hardness depending on the film thickness. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The anti-glare hard coating film of the hard coating layer can control the external haze and the 60° gloss to the desired crucible, and the external haze fluctuation due to the film thickness is small, and the production can be stably performed. Table 201026508 is excellent in surface hardness; and the polarizing plate using the anti-glare hard coating is intended. The inventors of the present invention have found that by using an active energy ray-sensitive composition containing an active energy ray-sensitive composition, preferably an oxidized cerium-based fine particle, and the like, in order to achieve the above object, it is found that The composition has a hard coating layer forming material of organic fine particles having a specific specific gravity difference to form a hard coating layer, and the anti-glare hard coating film having a thickness larger than an average particle diameter of the organic fine particles can achieve the object. . The present invention has been completed based on relevant discovery knowledge. That is, the present invention provides [1] an anti-glare hard coating film characterized in that (A) an active energy ray-sensitive composition is used on a surface of a transparent plastic film, and (B) contains an organic In the hard coating layer formed of the hard coating layer forming material of the fine particles, the ratio of the specific gravity of the component (A) to the component (B) is 0.25 or more at a temperature of 25 ° C, and the thickness of the hard coating layer is higher than the above (B The organic fine particles have a large average particle diameter; [2] The antiglare hard coating film according to [1] above, wherein the component (A) is a (a) polyfunctional (meth) acrylate monomer And/or a (meth) acrylate prepolymer, and (b) an active energy ray-sensitive composition comprising cerium oxide-based fine particles; [3] an anti-glare property as described in [1] or [2] above. a hard coating film in which (b) cerium oxide-based fine particles are oxide sand particles having a functional group containing a (meth)acryl fluorenyl group as a surface functional group; and [4] a polarizing plate, which is described in The opposite surface of the hard coating layer forming surface of the antiglare hard coating film of any one of the above items [3] to [3] is attached to 20102650 8 is composed of a polarizer. According to the present invention, it is possible to provide an antiglare hard coating film which is an antiglare hard coating film provided with a hard coating layer containing organic fine particles, which can control external haze and 60° gloss to be desired.値, at the same time, the variation of the external haze 因 due to the film thickness is small; and the surface hardness which can be stably produced is excellent; and the polarizing plate using the anti-glare hard coating film. [Embodiment] On the glare hard coating film, a hard coating layer forming material having the following composition is used for forming a hard coating layer provided on at least one side of the transparent plastic film 0. [Hard coating layer forming material] The hard coating layer forming material of the present invention contains (A) an active energy ray-sensitive composition and (B) organic fine particles. ((A) Active Energy Ray-Inductive Composition) In the hard coating layer forming material, the active energy ray-sensitive composition as the component (A) can be preferably used. (a) Multifunctional® is preferably used. (Meth) acrylate monomer and / or (meth) acrylate prepolymer, and (b) cerium oxide based particles. Further, in the present invention, the term "active energy ray" means an energy quantum which is an electromagnetic wave or a charged particle beam, that is, an ultraviolet ray or an electron ray. <(a) Polyfunctional (meth) acrylate monomer and/or (meth) acrylate prepolymer > In the present invention, a polyfunctional (meth) acrylate monomer and/or (Meth) acrylate prepolymer as (A) active energy ray-sensitive composition 201026508. Examples of the above polyfunctional (meth) acrylate monomer include 1 > 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol. Di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl (meth)acrylate, Ester-modified dicyclopentenyl (meth)acrylate, ethylene oxide modified di(meth)acrylate, allylic dicyclohexyl (meth)acrylate, isocyanate di(meth)acrylate Ester, trishydroxypropyl tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, neopentyl alcohol three ( Methyl) acrylate, propylene oxide modified tris (tri) propyl (meth) acrylate, tris (oxyethyl acrylate) isocyanate, propionic acid modified di pentaerythritol penta (meth) acrylate, two new Pentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, etc. Polyfunctional (meth) acrylate. The monomer may be used alone or in combination of two or more. In addition, examples of the (meth)acrylate prepolymer include a polyester acrylate type, an epoxy acrylate type, and an amine. Formate acrylate type, polyalcohol acrylate type, and the like. Wherein, in terms of the polyester acrylate-based prepolymer, for example, a hydroxyl group of a polyester oligomer having a hydroxyl group at the terminal end obtained by condensation of a (meth)acrylic acid, an esterified polycarboxylic acid and a polyhydric alcohol, or The hydroxyl group at the terminal of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid is esterified with (meth)acrylic acid. The epoxy acrylate-based prepolymer can be reacted and esterified, for example, by epoxide ring 201026508 of a lower molecular weight bisphenol type epoxy resin or a novolac type epoxy resin. Get it. The urethane acrylate-based prepolymer can be obtained, for example, by a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate by esterification with (meth)acrylic acid. Further, the polyalcohol acrylate prepolymer can be obtained by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid. These prepolymers may be used singly or in combination of two or more kinds, or may be used in combination with the above-mentioned polyfunctional (meth) acrylate monomer. <(b) Cerium oxide-based fine particles> β In the present invention, colloidal cerium oxide microparticles and/or cerium oxide microparticles having a surface functional group can be used as (b) cerium oxide-based fine particles. The colloidal cerium oxide microparticles having an average particle diameter of about 1 to 40 nm and having surface functional groups of cerium oxide microparticles can be exemplified by having a functional group having a (meth)acryl fluorenyl group as a surface functional group. Antimony particles (hereinafter referred to as reactive cerium oxide particles). The above reactive cerium oxide microparticles may, for example, be a polymerizable unsaturated group having a functional group reactive with the stanol group by a stanol group on the surface of the cerium oxide microparticles having an average particle diameter of about 0.005 to Ιμπι. The organic compound is obtained by reaction. The polymerizable unsaturated group is exemplified by a radically polymerizable (meth) acrylonitrile group. For the organic compound having a polymerizable unsaturated group having a functional group reactive with the aforementioned stanol group, for example, a compound represented by the formula (I) or the like is preferably used. R1
I CH2 ^ 〇 一 COR^ · · (1) 201026508 (式中，R1爲氫原子或甲基，R2爲鹵素原子或 OCHaGHaNGO、一OCHaCH-CHa. — OCHaCH^CHa、 \/ \/I CH2 ^ 〇 a COR^ · · (1) 201026508 (wherein R1 is a hydrogen atom or a methyl group, R2 is a halogen atom or OCHaGHaNGO, an OCHaCH-CHa. - OCHaCH^CHa, \/ \/
Ο N Η -OCH2CH2OH、-OH、-0(CH2)30、-Si(OCH3)3 所示之官能基。）官能 N Η -OCH2CH2OH, -OH, -0(CH2)30, -Si(OCH3)3. )
該等化合物方面，可使用例如丙烯酸、氯化丙烯酸、 丙烯酸-2-異氰酸乙酯、丙烯酸環氧丙酯、丙烯酸-2,3-醯亞 胺丙酯、丙烯酸-2-羥乙酯、丙烯醯氧丙基三甲氧基矽烷等 及對應於彼等丙烯酸衍生物的甲基丙烯酸衍生物。彼等丙 烯酸衍生物或甲基丙烯衍生物，係單獨使用或組合2種以 上來使用均可。 鍵結如此所得之含聚合性不飽和基之有機化合物的氧 化矽微粒，係藉由活性能量射線之照射來交聯、硬化做爲 活性能量射線硬化成分。 該反應性氧化矽微粒具有提升所得硬被覆膜之耐擦傷 .性的效果。 包含在該等氧化矽微粒上鍵結具有聚合性不飽和基之 有機化合物而形成之化合物的活性能量射線感應型組成物 (A)方面，則上市有例如JSR股份有限公司製、商品名「歐 普斯塔Z7 530」、「歐普斯塔Z7 524」、「歐普斯塔（〇P STAR) TU4086」等》 在本發明中，該（b)成分之氧化矽系微粒的含量，在（A) 成分之活性能量射線感應型組成物的固體成份中，通常爲 10- 201026508 5至90質量％左右，較佳爲10至70質量％ 。 還有，在該（b)成分之氧化矽系微粒中之氧化矽粒子的 平均粒徑，可由雷射繞折•散射法來測定。在該方法中， 藉由在分散粒子之液體中將當時繞射•散射雷射光的光強 度變化，測定平均粒徑》 ((B)有機微粒） 在本發明之硬被覆層形成材料中，使用做爲（B)成分的 有機微粒方面，舉例有聚矽氧系微粒、三聚氰胺系樹脂微 ® 粒、丙烯酸系樹脂微粒（舉例有聚甲基丙烯酸甲酯系微粒 (以下稱爲PMMA系微粒）等）、丙烯酸-苯乙烯系共聚物微 粒、聚碳酸酯系微粒、聚乙烯系微粒、聚苯乙烯系微粒、 笨胍阱系樹脂微粒等。又，用於本發明之有機微粒的形狀 雖無任何制限，但從提升防眩性能之再現性的觀點來看， 因球狀者可使光之散射狀態均質化而佳。再者從同樣之觀 點來看，有機微粒特佳爲粒度分佈狹窄者。該有機微粒之 平均粒徑，從防眩性能的觀點來看，較佳爲1至ΙΟμπί，特 ® 佳爲2至5jim，又從同樣的觀點來看，粒度分佈較佳爲以 庫爾特計數器（Coulter Counter)法所測定之最尖峰値的粒 徑±5 0%以上粒徑的質量分率爲全體之70%以上者。 在本發明中，該（B)成分之有機微粒係單獨使用1種或 組合2種以上來使用均可，又，該配合量從防眩性能的觀 點來看，相對於其爲前述（A)成分之活性能量射線感應型組 成物的固體成份100質量份，較佳爲0.1至30質量份，更 佳爲1至20質量份》 • 11- 201026508 在本發明中，爲了使前述（B)成分之有機微粒偏存於硬 被覆層表面附近而提升防眩性能，在溫度25°C，前述（A) 成分之活性能量射線感應型組成物的比重必須較前述（B) 成分之有機微粒的比重大 0.25以上。若該比重差未滿 0·25，則該有機微粒存在於硬被覆層表面附近的比例變 低，得不到所希望的防眩性能。該比重差較佳爲0.3 0以上， 更佳爲0.40以上。又，該比重差過大時，存在於硬被覆層 表面附近的有機微粒量變得過多，恐發生硬被覆層之耐擦 © 傷性降低。因而該比重差以1以下爲佳，較佳爲0.80以下， 更佳爲0.7 0以下。 還有，在溫度25 °C之（Α)活性能量射線感應型組成物的 比重，係藉由能量射線照射以進行硬化之前者，爲依照以 JIS Z 8 804之比重瓶的比重測定方法所測定之値。又，在 溫度25 °C之（B)有機微粒的比重爲藉由JIS Z 8807- 1 976之 比重瓶的比重測定方法所測定之値。 (光聚合起始劑） ® 在本發明中之硬被覆層形成材料中，隨所希望可含有 光聚合起始劑°該光聚合起始劑方面，舉例有苯偶姻、苯 偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻正 丁基醚、苯偶姻異丁基醚、苯乙酮、二甲胺基苯乙酮、2，2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-羥環己基苯基酮、2-甲基 -l-[4-甲硫]苯基]-2-嗎福林-丙-1-酮、4-(2-羥乙氧基）苯基 -2-(羥-2-丙基）酮、二苯基酮、對苯基二苯基酮、4,4’-二乙 -12- 201026508 胺基二苯基酮、二氯二苯基酮、2_甲基蒽醌、2_乙基蒽醌、 2_第一·丁基恵酿、2 -胺基恵醒、2 -甲基-9 -氧硫卩山哩、2 -乙 基-9-氧硫岫唱、2 -氯9 -氧硫卩山卩星、2,4 -二甲基-9-氧硫灿喔、 2,4 -二乙基-9-氧硫灿嗶、苄基二甲基縮酮、苯乙酮二甲基 縮酮、對二甲胺基苯偶姻酸酯等。 彼等係使用1種或組合2種以上來使用均可，又其配 合量係相對於全部活性能量射線感應型化合物1〇〇質量 份’通常在0.2至10質量份範圍中選擇。還有，其中所謂 ® 全體活性量射線硬化型化合物，係表示在使用反應性氧化 矽微粒做爲（b)氧化矽系微粒的情況下，包含它者。 (硬被覆層形成材料之調製） 在本發明中所用的硬被覆層形成材料，必要時在適當 的溶劑中，以個別既定之比例添加前述之（A)成分的活性 能量射線感應型組成物、（B)成分的有機微粒、及隨所希望 而用的光聚合起始劑或各種添加成分，例如抗氧化劑、紫 外線吸收劑、砂院系偶合劑、光安定劑、勻塗劑、消泡劑 ® 等，可藉由溶解或分散來調製。 此時所用的溶劑方面，舉例有己烷、庚烷等之脂肪族 烴；甲苯、二甲苯等之芳香族烴；二氯甲烷二氯乙烷等 之鹵化烴；甲醇、乙醇、丙醇、丁醇、丙二醇單甲基醚等 之醇類；丙酮' 甲基乙基酮、2-戊酮、異佛酮、環己酮等 之酮類；乙酸乙酯、乙酸丁酯等之酯類；乙基賽珞蘇等之 賽珞蘇系溶劑等。 如此所調製之硬被覆層形成材料的濃度、黏度方面， 13. 201026508 只要爲可被覆者即可，並無特別限制，可 選定。 [透明塑膠膜] 在本發明之防眩性硬被覆膜中，在透 單面上，使用如前述所調製之硬被覆層形 被覆層。 針對前述之透明塑膠膜則無特別限制 認之塑膠膜之中選擇做爲習知之光學用硬 © 該等塑膠膜方面，可舉例有聚對苯二甲酸 二甲酸丁二酯、聚萘酸乙二酯等之聚酯膜 丙烯膜、玻璃紙、二乙酸纖維素膜、三乙 酸纖維素丁酸酯膜、聚氯乙烯膜、聚偏二 烯醇膜、乙烯-乙酸乙烯酯共聚物膜、聚苯 酯膜、聚甲基戊烯膜、聚碾膜、聚醚基醚国 聚醚醯亞胺膜、聚醯亞胺膜、氟樹脂膜、 酸樹脂膜、降莰烯系樹脂膜、環烯烴樹脂 ® 彼等塑膠膜可爲透明、半透明均可， 或無著色者，可隨著用途來適宜選擇。例 晶顯示體之保護用的情況下，適合無色透 彼等塑膠膜厚度雖無特別限制，隨丨 定，但通常爲15至300 μιη，較佳爲30至 又，該塑膠膜係以提升與設置於其表面之 的，可隨所希望而在單面或雙面上，藉由 法等實施表面處理。上述氧化法方面，舉 隨狀況來適宜地 明塑膠膜之至少 成材料，形成硬 ，可適宜地從公 被覆膜的基材。 乙二酯、聚對苯 ;聚乙烯膜、聚 酸纖維素膜、乙 氯乙烯膜、聚乙 乙烯膜、聚碳酸 Ϊ膜、聚醚砸膜、 聚醯胺膜、丙烯 膜等的塑膠膜。 又亦可爲已著色 如在使用做爲液 明膜。 伏況來適宜地選 200μιη的範圍。 層的密著性爲目 氧化法或凹凸化 例有電暈放電處 14-As such compounds, for example, acrylic acid, chlorinated acrylic acid, ethyl 2-isocyanate, glycidyl acrylate, 2,3-indolyl propyl acrylate, 2-hydroxyethyl acrylate, Acryloxypropyltrimethoxydecane, and the like, and methacrylic acid derivatives corresponding to the acrylic acid derivatives thereof. These acrylic acid derivatives or methyl propylene derivatives may be used singly or in combination of two or more. The cerium oxide microparticles bonded to the polymerizable unsaturated group-containing organic compound thus obtained are crosslinked and hardened by irradiation with an active energy ray to be an active energy ray hardening component. The reactive cerium oxide microparticles have an effect of improving the scratch resistance of the obtained hard coating film. An active energy ray-sensitive composition (A) containing a compound formed by bonding an organic compound having a polymerizable unsaturated group to the cerium oxide microparticles is commercially available, for example, as manufactured by JSR Co., Ltd. under the trade name "Op". "Star Z7 530", "Opsta Z7 524", "Opta STA STA 408408", etc. In the present invention, the content of the cerium oxide-based fine particles of the component (b) is (A) The solid content of the active energy ray-sensitive composition is usually from 10 to 201026508 5 to 90% by mass, preferably from 10 to 70% by mass. Further, the average particle diameter of the cerium oxide particles in the cerium oxide-based fine particles of the component (b) can be measured by a laser diffraction/scattering method. In this method, the average particle diameter is determined by changing the light intensity of the diffused/scattered laser light in the liquid of the dispersed particles ((B) organic fine particles) in the hard coating layer forming material of the present invention, Examples of the organic fine particles of the component (B) include polyfluorene-based fine particles, melamine-based resin micro-particles, and acrylic resin fine particles (for example, polymethyl methacrylate-based fine particles (hereinafter referred to as PMMA-based fine particles). ), acrylic acid-styrene copolymer fine particles, polycarbonate fine particles, polyethylene fine particles, polystyrene fine particles, awkward trap resin fine particles, and the like. Further, the shape of the organic fine particles used in the present invention is not limited, but from the viewpoint of improving the reproducibility of the antiglare property, it is preferable that the spherical shape can homogenize the light scattering state. From the same point of view, organic particles are particularly preferred for those with a narrow particle size distribution. The average particle diameter of the organic fine particles is preferably from 1 to ΙΟμπί, particularly preferably from 2 to 5 μm from the viewpoint of antiglare performance, and from the same viewpoint, the particle size distribution is preferably a Coulter counter. The particle diameter of the most peak 値 measured by the (Coulter Counter) method is ±50% or more, and the mass fraction of the particle diameter is 70% or more of the total. In the present invention, the organic fine particles of the component (B) may be used singly or in combination of two or more. The blending amount is the aforementioned (A) from the viewpoint of antiglare performance. 100 parts by mass of the solid component of the active energy ray-sensitive composition of the component, preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. 11 - 201026508 In the present invention, in order to make the above component (B) The organic particles are concentrated in the vicinity of the surface of the hard coating layer to enhance the anti-glare property. At a temperature of 25 ° C, the specific gravity of the active energy ray-sensitive composition of the above component (A) must be greater than the specific gravity of the organic particles of the above (B) component. Larger than 0.25. If the specific gravity difference is less than 0·25, the ratio of the organic fine particles existing in the vicinity of the surface of the hard coating layer becomes low, and the desired antiglare performance cannot be obtained. The specific gravity difference is preferably 0.30 or more, more preferably 0.40 or more. When the difference in specific gravity is too large, the amount of organic fine particles existing in the vicinity of the surface of the hard coating layer is excessively increased, and the scratch resistance of the hard coating layer may be lowered. Therefore, the specific gravity difference is preferably 1 or less, preferably 0.80 or less, more preferably 0.70 or less. In addition, the specific gravity of the active energy ray-sensitive composition at a temperature of 25 ° C is determined by the specific gravity measuring method of the pycnometer according to JIS Z 8 804 before being hardened by irradiation with energy rays. After that. Further, the specific gravity of the (B) organic fine particles at a temperature of 25 °C is measured by a specific gravity measuring method of a pycnometer of JIS Z 8807-1 976. (Photopolymerization initiator) In the hard coating layer forming material of the present invention, a photopolymerization initiator may be contained as desired. Examples of the photopolymerization initiator include benzoin and benzoin methyl. Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2-two Methoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-l-[4-methyl thio] phenyl]-2-morphine-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2 -(hydroxy-2-propyl)one, diphenyl ketone, p-phenyldiphenyl ketone, 4,4'-diethyl-12- 201026508 aminodiphenyl ketone, dichlorodiphenyl ketone, 2 _Methyl hydrazine, 2_ethyl hydrazine, 2_first butyl broth, 2-amino group awake, 2-methyl-9-oxosulfonium, 2 -ethyl-9-oxygen Singing, 2-chloro 9-oxosulfonate, comet, 2,4-dimethyl-9-oxosulfanthine, 2,4-diethyl-9-oxosulfanthene, benzyldimethyl A ketal, an acetophenone dimethyl ketal, a p-dimethylamino benzoate ester, and the like. These may be used singly or in combination of two or more kinds, and the compounding amount thereof is usually selected in the range of 0.2 to 10 parts by mass based on the total mass of the active energy ray-sensitive compound. In addition, the term "all active amount ray-curable compound" refers to a case where the reactive cerium oxide microparticles are used as (b) cerium oxide-based fine particles. (Preparation of hard coating layer forming material) The hard coating layer forming material used in the present invention, if necessary, the active energy ray-sensitive composition of the above component (A) is added in an appropriate ratio in an appropriate solvent. The organic fine particles of the component (B), and the photopolymerization initiator or various added components used as desired, such as an antioxidant, an ultraviolet absorber, a sand system coupling agent, a light stabilizer, a leveling agent, and an antifoaming agent. ® , etc., can be prepared by dissolving or dispersing. Examples of the solvent to be used in this case include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane dichloroethane; methanol, ethanol, propanol and butanol. Alcohols such as propylene glycol monomethyl ether; ketones such as acetone 'methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone; esters of ethyl acetate and butyl acetate; ethyl Sai Su and other competitions, such as solvent, etc. In terms of the concentration and viscosity of the hard coating layer forming material thus prepared, 13. 201026508 is not particularly limited as long as it can be covered, and can be selected. [Transparent plastic film] In the antiglare hard coating film of the present invention, the hard coating layer coating layer prepared as described above is used on the single-sided surface. For the above-mentioned transparent plastic film, there is no particular limitation on the plastic film selected as the optical hardening of the conventional one. For the plastic film, for example, polybutylene terephthalate or polybutylene naphthalate can be exemplified. Polyester film acryl film such as ester, cellophane, cellulose diacetate film, cellulose acetate triacetate film, polyvinyl chloride film, polyvinylidene alcohol film, ethylene-vinyl acetate copolymer film, polyphenyl ester Membrane, polymethylpentene film, polycrystalline film, polyetheretherene polyether phthalimide film, polyimide film, fluororesin film, acid resin film, norbornene resin film, cycloolefin resin® These plastic films can be transparent, translucent or non-staining, and can be selected according to the application. In the case of the protection of the crystal display body, the thickness of the plastic film which is suitable for colorlessness is not particularly limited, and is usually 15 to 300 μm, preferably 30 to 30, and the plastic film is improved. The surface treatment may be carried out by a method or the like on one or both sides as desired. In the above oxidation method, it is preferable to form at least a material of the plastic film in accordance with the condition to form a substrate which is hard and can be suitably coated from the film. Ethylene glycol, polyparaphenylene; plastic film of polyethylene film, cellulose cellulose film, vinyl chloride film, polyethylene film, polycarbonate film, polyether film, polyamide film, acrylic film, etc. It can also be colored as used in the liquid film. The condition is suitably selected to be in the range of 200 μm. The adhesion of the layer is the result of oxidation or embossing.
201026508 理、電漿處理、鉻酸處理（濕式）、火焰處理、熱空氣 臭氧·紫外線照射處理等；又，凹凸化法方面，舉例 法、溶劑處理法等。彼等之表面處理法雖隨塑膠膜種 適宜地選擇，但一般從效果及操作性等方面來看，較 使用電暈放電處理法。又，亦可設置底層。 [硬被覆層之形成] 在前述透明塑膠膜之至少單面上，使用習知公 法，例如刮條塗布法、刮刀塗布法、輥塗法、刮板塗 ® 口模式塗布法、凹槽輥塗布法等，進行被覆前述硬 形成材料而形成塗膜，於乾燥後，藉由在其上照射 量射線而硬化該塗膜，形成硬被覆層。 活性能量射線方面，舉例有紫外線或電子射線等 述紫外線係以高壓水銀燈、無電極燈、鹵化金屬燈、 等而得，照射量通常爲100至500 mjr/cm2，另外電3 係藉由電子射線加速器等而得，照射量通常爲150 3 kV。在該活性能量射線之中，特別適合爲紫外線。還 在使用電子射線的情況下，可由不添加光聚合起始齊 式，得到硬化膜。 如此所形成之硬被覆層的厚度，在本發明中必須 使用之有機微粒的平均粒徑大，因而下限爲2 μιη左；έ 藉由硬被覆層之硬化收縮來防止硬被覆膜捲縮的】 看，上限爲20 μιη左右。較佳之厚度爲5至15 μηι的 特佳之厚度爲8至12μπι。 [防眩性硬被覆膜] 理、 磨砂 類來 佳爲 之方 法、 覆層 性能 。上 氣燈 射線 350 有， 的方 較所 ，從 點來 5圍， -15- 201026508 (光學特性） 如此所形成之本發明的防眩性硬被覆的光學特性，隨 其類型而有較佳値不同的情況。 在高對比型的情況下，通常內部霧度値爲〇至10% 。 即使內部霧度値在該範圍中發生不均勻，因可達成高對比 而亦可隨顯示器種類（設計構想）中充分適用。內部霧度値 超過1 0%時則得不到高對比（成爲泛用型）。又，在泛用型 的情況下，通常內部霧度値爲5至40% 。內部霧度値未滿 Φ 5%則抑制不均勻之性能不足，超過40%時則辨識性降低。 泛用型防眩性硬被覆膜之較佳的內部霧度値，通常爲10至 3 0% ，較佳爲15至25% 。 又，外部霧度値從高對比型、泛用型與辨識性的觀點 來看，較佳爲20%以下，從防眩性的觀點來看較佳爲5% 以上。外部霧度値係測定防眩性硬被覆膜之總霧度値與內 部霧度値，藉由總霧度値減去內部霧度値之差所得的値。 再者，60°光澤値係高對比型、泛用型一起較佳爲20 ® 至120，更佳爲20至80。60°光澤値超過120時則表面光 澤度大（光之反射大），對防眩性造成不良影響。60°光澤値 未滿20則容易發生褪成淡褐色。又，防眩性硬被覆膜之全 體光線透過率較佳爲8 8%以上，更佳爲90%以上。全體光 線透過率未滿88%則恐怕透明性變不足。 還有，針對前述光學的特性値的測定方法，於後説明。 (效果） 本發明之防眩性硬被覆膜達成下述的效果。 -16- 201026508 (1) 藉由規定活性能量射線感應型組成物與有機微粒的比 重差，有機微粒偏存於硬被覆層的表面附近，發揮所希 望的防眩性能。藉由控制該比重差，可控制外部霧度値 及60°光澤値於所希望之値。 (2) 即使在較有機微粒之平均粒徑大的膜厚中，有機微粒存 在於硬被覆層表面附近，而提升了防眩性，同時亦減低 塗布不勻。又，由於必然地使膜厚變大而與使用同程度 之平均粒徑的有機微粒所製作之習知防眩性硬被覆膜 β 比較，預見鉛筆硬度的提升。 (3) 藉由使用包含氧化矽系微粒之活性能量射線感應型組 成物，可得到硬化收縮度低、捲曲少的防眩性硬被覆 膜。又，使用包含氧化矽系微粒之活性能量射線感應型 組成物時，可進行擴大與有機微粒之比重差的設計。 (其他機能層） 在本發明之防眩性硬被覆膜中，必要時可在最上層， 以賦予抗反射性等爲目的，設置抗反射層，例如矽氧烷系 ® 被覆膜、氟系被覆膜等。在該情況下，該抗反射層之厚度 適當爲0.05至Ιμιη左右。藉由設置該抗反射層，消除由因 太陽光、螢光燈等所致之反射所產生之畫面的反射，又藉 由抑制表面之反射率，提升全體光線透過率，並提升透明 性。還有，隨著抗反射層的種類，則可謀求防靜電性的提 升。 (黏著劑層） 在本發明之防眩性硬被覆膜中，在塑膠膜之與硬被覆 17- 201026508 層反面上，可形成用於貼著於液晶顯示體 黏著劑層。構成該黏著劑層的黏著劑方面 於光學用途之例如丙烯酸系黏著劑、胺酯 氧系黏著劑。該黏著劑層之厚度通常爲5 爲10至60μιη的範圍。 再者，在該黏著劑層上，必要時可設 離片方面，舉例有在聚對苯二甲酸乙二酯 種塑膠膜上，塗布聚矽氧樹脂等之剝離劑 Φ 片的厚度雖無特別之限制，但通常爲20 3 形成該等黏著劑層之防眩性硬被覆膜 CRT、LCD、PDP等之顯示器，賦予防眩性 等的構件，特別適合做爲在LCD等中之的 [偏光板] 又，本發明亦提供將前述之本發明的 貼合於偏光鏡所構成的偏光板。 LCD中之液晶元件係具有將一般形成 ® 明電極基板，以其配向層爲內側，藉由間 定的間隙，密封該週邊以夾住液晶材料於 在上述2片透明電極基板的外側表面上， 層以設置偏光板的構造。 第1圖係顯示上述偏光板之一範例之 如該圖所示，該偏光板10 —般在聚乙烯醇 面上，具有貼合三乙基纖維素（TAC)膜2 的基材，然後，在該單面形成用於貼著於 等之被貼著體的 ，較佳爲使用適 系黏著劑、聚矽 至1 0 Ο μ m、較佳 置剝離片。該剝 、聚丙烯等之各 者。對於該剝離 ί 1 5 Ομιη 左右。 ，適用做爲對於 能或耐擦傷性能 I偏光板貼著用。 防眩性硬被覆膜 配向層之2片透 隔片配置成爲既 該間隙中，同時 分別經由黏著劑 .構成的斜視圖。 :系偏光鏡1的雙 及2’之3層構造 液晶元件等之光 -18- 201026508 學零件的黏著劑層3，再者在該黏著劑層3上，貼著剝離 片4。又，在與該偏光板之該黏著劑層3的反面上，通常 設置著表面保護膜5。 本發明之偏光板係在設置於偏光鏡1之雙面的TAC膜 2、2’之中，在另外TAC膜上設置上述之關於本發明的硬 被覆層者。在偏光板上設置著黏著劑層3、剝離片4及表 面保護膜5的情況下，特別在表面保護膜5側之TAC膜2’ 側上設置有關於本發明的硬被覆層。 製造本發明之偏光板的方法方面，例如可進行以下所 示之操作。還有，第2圖係顯示本發明偏光板之一範例之 構成的截面模式圖。 首先，使用如TAC膜之無光學異向性膜12’做爲基材 的透明塑膠膜，於另一面上形成關於本發明之硬被覆層 13，成爲防眩性硬被覆膜14。其次，在偏光鏡11的單面 上，將未形成硬被覆層13之TAC膜1 2，使用接著劑層1 5、 15’積層前述防眩性硬被覆膜14於反面。在透明塑膠膜上 ® 使用TAC膜的情況下，藉由以接著劑之積層來提升密著性 方面，亦可進行前述之表面處理的其他皂化處理等。 因而，得到防眩性能與耐擦傷性能優異之偏光板20。 偏光板20於必要時，亦可在設置硬被覆層13之面上，設 置前述第1圖所示之可剝離的表面保護膜5，或在其反面 上用於貼著於液晶元件等之光學零件的黏著劑層16或剝 離片17。 本發明之偏光板係起始於LCD中之液晶元件用，可用 -19- 201026508 做爲光量調整用、偏光干涉應用裝置用、光學缺陷檢測器 用等。 實施例 其次，雖藉由實施例進一步說明本發明，但本發明係 不受彼等範例任何限制者。 還有，有機微粒之平均粒徑及比重、活性能量射線感 應型組成物之比重、以及硬被覆膜性能係依照下述方法而 求得。 © <有機微粒> (1) 平均粒徑 藉由庫爾特計數器（Coulter Counter)法測定。 (2) 在溫度25°C之比重 以JIS Z 8807-1976之比重瓶的比重測定。 <活性能量射線感應型組成物> (3) 在溫度25°C之比重 針對活性能量射線照射前之活性能量射線感應型組成 ® 物，以JIS Z 8 804之比重瓶的比重測定。 <硬被覆膜> (4) 全體光線透過率及總霧度値 使用日本電色工業股份有限公司製霧度計 「NDH-2000」，依照JISK7136，針對在實施例及比較例 中所作製的防眩性硬被覆膜，測定全體光線透過率及總霧 度値。還有，總霧度値係表示起因於內部之霧度値（內部霧 度値）與起因於表面之凹凸之外部霧度値的合計値。 -20- 201026508 (5) 內部霧度値及外部霧度値 在丙烯酸系黏著劑[日本碳化物（Carbide)公司製、商品 名「PE-121」]100質量份中，添加異氰酸酯交聯劑[東洋油 墨公司製、商品名「BHS-8515」]2質量份、及甲苯100質 量份以製作黏著劑溶液。在厚度50μιη之聚對苯二甲酸乙 二酯[東洋紡織公司製、商品名「Α4 300」]膜上，塗布黏著 劑溶液成爲乾燥後之厚度爲20μιη，於100 °C乾燥3分鐘以 製作黏著片。將所製作之黏著片貼著於硬被覆膜之硬被覆 Ο 層而成爲內部霧度判定用試料。測定該黏著片與內部霧度 判定用試料之霧度値，從內部霧度判定用試料之霧度値減 去黏著片之霧度値的値，爲硬被覆膜之內部霧度値。還有， 同樣地測定於實施例及比較例中所用之基材薄膜（三乙基 纖維素膜）及聚對苯二甲酸乙二酯的內部霧度値時，未滿 0.01%之値可視爲無。霧度値之測定與上述（4)相同。 (6) 防眩性之評估 在螢光燈下以目視觀察經由丙烯酸系黏著劑將硬被覆 ® 膜貼著於丙烯酸樹脂黑板[住友化學股份有限公司製]的試 樣，由下述之判定基準來評估防眩性。 〇：螢光燈之抗反射性充足，且褪成淡褐色少 X :螢光燈之抗反射性不足，或螢光燈之抗反射性雖 充足，但褪成淡褐色大且辨視性差者 (7) 60°光澤値 使用日本電色工業股份有限公司製光澤計 「VG2000」，依照JIS K 7105來測定。 -21- 201026508 (8) 鉛筆硬度 依照JIS K 5 400，使用安田精機製作所股份有限公司 之鉛筆抓刮塗膜硬度試驗機「No 553-M1」]來測定。 (9) 塗布不句 目視觀察硬被覆層表面，依照下述之判定基準，評估 塗布不勻。 〇：均勻地看見塗布面全體 X :塗布面上混合存在防眩性高的部分與低的部分而 〇 看見全體不均勻。 (10) 膜厚 分別針對於實施例及比較例中所製作之防眩性硬被覆 膜、及其爲該防眩性硬被覆膜之製作中所使用之透明塑膠 膜的 TAC(三乙基纖維素）膜，以定壓厚度計[Nikon公司 製、「MH-15M」]來測定厚度，取其差而計算出硬被覆層 的膜厚。 調製例1 ® 硬被覆層用被覆劑1 均勻混合含有（A)活性能量射線感應型組成物之硬被 覆劑[JSR股份有限公司製、商品名「歐普斯塔Z7 530」： 由反應性氧化矽微粒（42質量％ )、與多官能性（甲基）丙烯 酸酯系單體及（甲基）丙烯酸酯預聚物（28質量％)所構成之 活性能量射線感應型組成物（合計：70質量％、比重1.65)、 光聚合起始劑（3質量％)、及甲基乙基酮（2 7質量％);固體 成分濃度（73質量％ )] 1〇〇質量份、球狀之聚甲基丙烯酸甲 -22- 201026508 酯（PMMA)系微粒[綜硏化學股份有限公司製、平均粒徑 3μηι、比重1.19]3.75質量份作爲（B)有機微粒、以及丙二醇 單甲基醚90質量份做爲稀釋溶劑，調製固體成分濃度約 40質量％之硬被覆層用被覆劑1。該被覆劑之配合顯示於 表1 〇 調製例2 硬被覆層用被覆劑2 除了變更球狀之ΡΜΜΑ系微粒[綜硏化學股份有限公 Ο 司製、平均粒徑3μιη、比重1·19]7·5質量份做爲（Β)有機微 粒以外，與調製例1同樣地調製固體成分濃度約40質量％ 的硬被覆層用被覆劑2。該被覆劑之配合示於表1。 調製例3 硬被覆層用被覆劑3 除了變更球狀之ΡΜΜΑ系微粒[綜硏化學股份有限公 司製、平均粒徑3μιη、比重1.19]11.25質量份做爲（Β)有機 微粒以外，與調製例1同樣地調製固體成分濃度約40質量 ® %的硬被覆層用被覆劑3。該被覆劑之配合示於表1。 調製例4 硬被覆層用被覆劑4 混合含有（Α)活性能量射線感應型組成物之硬被覆劑 [JSR股份有限公司製、商品名「歐普斯塔Ζ7 530」：由反 應性氧化矽微粒（42質量％)、與多官能性（甲基）丙烯酸酯 系單體及（甲基）丙烯酸酯系預聚物（28質量％)所構成之活 性能量射線感應型組成物（合計：70質量％、比重1.65)、 -23- 201026508 光聚合起始劑（3質量％)、及甲基乙基酮（2 7質量％);固體 成分濃度（73質量％ )] 80質量份、及含有不含反應性氧化矽 微粒之活性能量射線感應型組成物的硬塗布劑[大日精化 工業股份有限公司製、商品名「謝伊卡賓（SELKA-BEAM) EXF-L203(CS-1)」：由多官能性（甲基）丙烯酸酯系單體及（甲 基）丙烯酸酯系預聚物所構成之活性能量射線感應型組成 物（65質量％、比重1.33)、光聚合起始劑（5質量％)、丙二 醇單甲基乙酸酯（30質量％);固體成分濃度（70質量％)]20 © 質量份，調製（A)成分成爲活性能量射線感應型組成物之固 體成分的比重爲1.59。除此以外與調製例2同樣地調製固 體成分濃度約40質量％之硬被覆層用被覆劑4。該被覆劑 之配合示於表1。 調製例5 硬被覆層用被覆劑5 藉由混合含有（A)活性能量射線感應型組成物之硬被 覆劑[JSR股份有限公司製、商品名「歐普斯塔Z7530」： ® 由反應性氧化矽微粒（42質量％)、與多官能性（甲基）丙烯 酸酯系單體及（甲基）丙烯酸酯預聚物（28質量％)所構成之 活性能量射線感應型組成物（合計：7〇質量％、比重1.65)、 光聚合起始劑（3質量％)、及甲基乙基酮（27質量％);固體 成分濃度（73質量％ )] 10質量份、及含有不含反應性氧化矽 微粒之活性能量射線感應型組成物的硬被覆劑[大日精化 工業股份有限公司製、商品名 「謝伊卡賓 EXF-L203 (CS-1)」：多官能性（甲基）丙烯酸酯系單體及（甲 -24- .201026508 基）丙烯酸酯系預聚物（65質量％、比重丨.33)、光聚合起始 劑（5質量％)、及丙二醇單甲基乙酸酯（3〇質量固體成 分濃度（70質量％ )] 90質量份，將活性能量射線感應型組 成物之固體成分的比重調製成1.36。其次，均勻混合球狀 之聚苯乙嫌系微粒[綜硏化學股份有限公司製、平均粒徑 3·5μπι、比重1.〇9]3.75質量份做爲（B)有機微粒、丙二醇單 甲基醚90質量份做爲稀釋溶劑，調製固體成分濃度約40 質量％的硬被覆層用被覆劑5。該被覆劑之配合示於表1。 © 調製例6 硬被覆層用被覆劑6 混合含有（Α)活性能量射線感應型組成物之硬被覆劑 [JSR股份有限公司製、商品名「歐普斯塔Ζ7530」：由反 應性氧化矽微粒（42質量％ )、與多官能性（甲基）丙烯酸酯 系單體及（甲基）丙烯酸酯系預聚物（28質量％)所構成之活 性能量射線感應型組成物（合計：70質量％、比重1.65)、 光聚合起始劑（3質量％)、及甲基乙基酮（27質量％);固體. ® 成分濃度（73質量％ )]30質量份、及含有不含反應性氧化矽 微粒之活性能量射線感應型組成物之硬被覆劑[大日精化 工業股份有限公司製、商品名 「謝伊卡賓 EXF-L203 (CS-1)」：多官能性（甲基）丙烯酸酯系單體及（甲 基）丙烯酸酯系預聚物（65質量％、比重1.33)、光聚合起始 劑（5質量％)、及丙二醇單甲基乙酸酯（30質量％);固體成 分濃度（70質量％ )] 70質量份，調製（A)成分成爲組成物之 固體成分的比重爲1.43。除此以外與調製例2同樣地調製 -25- 201026508 固體成分濃度約40質量％的硬被覆層用被覆劑6。該被覆 劑之配合示於表1 » 調製例7 硬被覆層用被覆劑7 除了使用含有不含（A)反應性氧化矽微粒之活性能量 射線感應型組成物的硬被覆劑[大日精化工業股份有限公 司製、商品名「謝伊卡賓EXF-L2 03(CS-1)」：多官能性（甲 基）丙烯酸酯系單體及（甲基）丙烯酸酯系預聚物（65質量 〇 %、比重1.33)、光聚合起始劑（5質量％)、及丙二醇單甲 基乙酸酯（30質量％);固體成分濃度（70質量％)] 100質量 份以外，與調製例1同樣地調製固體成分濃度約40質量％ 的硬被覆層用被覆劑7。該被覆劑之配合示於表1。 實例1 在厚度80μιη之TAC(三乙醯纖維素）膜[富士軟片股份 有限公司製]的表面上，以梅耶刮條塗布於調製例1所得之 被覆劑1成爲硬化膜厚約ΙΟμιη。於70°C之烤箱乾燥1分 ^ 鐘後，以高壓水銀燈照射3 00mJ/cm2的紫外線以製作防眩 性硬被覆膜。 該硬被覆膜之性能示於表2。 實例2 除了以梅耶刮條塗布於調製例1所得之被覆劑1成爲 硬化膜厚約9μιη以外，進行與實例1同樣的操作以製作防 眩性硬被覆膜。 該硬被覆膜之性能示於表2。 -26- .201026508 實例3 除了以梅耶刮條塗布於調製例2所得之被覆劑2成爲 硬化膜厚約ΙΟμηι以外，進行與實例1同樣之操作以製作 防眩性硬被覆膜。 該硬被覆膜之性能示於表2。 實例4 除了以梅耶刮條塗布於調製例3所得之被覆劑3成爲 硬化膜厚約1 Ομπι以外，進行與實例1同樣之操作以製作 〇 防眩性硬被覆膜。 該硬被覆膜之性能示於表2。 實例5 除了以梅耶刮條塗布於調製例4所得之被覆劑4成爲 硬化膜厚約ΙΟμπι以外，進行與實例1同樣之操作以製作 防眩性硬被覆膜。 該硬被覆膜之性能示於表2。 實例6 ® 除了以梅耶刮條塗布於調製例5所得之被覆劑5成爲 硬化膜厚約1 Ομηι以外，進行與實例1同樣之操作以製作 防眩性硬被覆膜。 該硬被覆膜之性能示於表2。 比較例1 除了以梅耶刮條塗布於調製例6所得之被覆劑6成爲 硬化膜厚約1 〇 μιη以外，進行與實例1同樣之操作以製作 防眩性硬被覆膜。 -27- .201026508 該硬被覆膜之性能示於表2。 比較例2 除了以梅耶刮條塗布於調製例7所得之被覆劑7成爲 硬化膜厚約2.5μιη以外’進行與實例1同樣之操作以製作 防眩性硬被覆膜。 該硬被覆膜之性能示於表2。 比較例3 除了以梅耶刮條塗布於調製例7所得之被覆劑7成爲 ® 硬化膜厚約3 μιη以外’進行與實例1同樣之操作以製作防 眩性硬被覆膜。 該硬被覆膜之性能示於表2。 比較例4 除了以梅耶刮條塗布於調製例7所得之被覆劑7成爲 硬化膜厚約1 〇μιη以外，進行與實例1同樣之操作以製作 防眩性硬被覆膜。 該硬被覆膜之性能示於表2。 -28- .201026508 [表i]201026508 Chemical, plasma treatment, chromic acid treatment (wet), flame treatment, hot air, ozone, ultraviolet irradiation treatment, etc.; also, the method of embossing, examples, solvent treatment, etc. Although the surface treatment method is appropriately selected depending on the type of the plastic film, it is generally used in terms of effect and operability, and the corona discharge treatment method is used. Also, the bottom layer can be set. [Formation of Hard Coating Layer] On at least one side of the transparent plastic film, a conventional method such as a bar coating method, a blade coating method, a roll coating method, a blade coating method, a groove roll coating method, and a gravure coating method are used. A coating film is formed by coating the hard forming material, and after drying, the coating film is cured by irradiation with a dose of radiation to form a hard coating layer. Examples of the active energy ray include ultraviolet rays, electron beams, and the like, which are obtained by using a high-pressure mercury lamp, an electrodeless lamp, a halogenated metal lamp, or the like, and the irradiation amount is usually 100 to 500 mjr/cm 2 , and the electric 3 is by electron beam. Accelerators and the like, the amount of exposure is usually 150 3 kV. Among the active energy rays, ultraviolet rays are particularly suitable. Also in the case of using an electron beam, a cured film can be obtained by adding a photopolymerization initiation mode. The thickness of the hard coating layer thus formed is large in the average particle diameter of the organic fine particles which must be used in the present invention, so that the lower limit is 2 μηη left; 防止 the hard coating film is prevented from being crimped by hardening shrinkage of the hard coating layer. 】 Look, the upper limit is around 20 μιη. A preferred thickness of 5 to 15 μηι is 8 to 12 μm. [Anti-glare hard coating film] The method of processing and sanding is the best method and coating performance. The upper air lamp ray 350 has a square, from the point of 5, -15-201026508 (optical characteristics) The optical characteristics of the anti-glare hard coating of the present invention thus formed are better depending on the type thereof. Different situations. In the case of high contrast, the internal haze is usually 〇 to 10%. Even if the internal haze is uneven in this range, it can be sufficiently applied depending on the type of display (design concept) because high contrast can be achieved. When the internal haze 超过 exceeds 10%, high contrast (becoming a general-purpose type) is not obtained. Also, in the case of a general-purpose type, the internal haze is usually 5 to 40%. The internal haze is less than Φ 5%, the performance of suppressing unevenness is insufficient, and when it exceeds 40%, the visibility is lowered. The preferred internal haze of the general-purpose antiglare hard coating film is usually from 10 to 30%, preferably from 15 to 25%. Further, the external haze is preferably 20% or less from the viewpoint of high contrast type, general use type, and visibility, and is preferably 5% or more from the viewpoint of anti-glare property. The external haze is a measure of the total haze 内 and the internal haze of the anti-glare hard coating, and the difference between the internal haze and the internal haze 値 is obtained by the total haze. Further, the 60° gloss lanthanum high contrast type and the general use type are preferably 20 ® to 120, more preferably 20 to 80. The 60° gloss 値 exceeds 120, the surface gloss is large (the light reflection is large), Has an adverse effect on anti-glare. 60° gloss 値 If it is less than 20, it will easily fade to hazel. Further, the total light transmittance of the antiglare hard coating film is preferably 88% or more, more preferably 90% or more. If the overall light transmittance is less than 88%, the transparency may be insufficient. In addition, the measuring method of the optical characteristic 値 described above will be described later. (Effects) The antiglare hard coating film of the present invention achieves the following effects. -16- 201026508 (1) By specifying the difference in weight between the active energy ray-sensitive composition and the organic fine particles, the organic fine particles are scattered in the vicinity of the surface of the hard coating layer, and the desired anti-glare property is exhibited. By controlling the difference in specific gravity, it is possible to control the external haze and the 60° gloss to the desired level. (2) Even in a film thickness larger than the average particle diameter of the organic fine particles, the organic fine particles exist in the vicinity of the surface of the hard coating layer, thereby improving the anti-glare property and reducing uneven coating. Further, in comparison with the conventional anti-glare hard coating film β produced by using organic fine particles having the same average particle diameter, the film thickness is inevitably increased, and the improvement in pencil hardness is expected. (3) By using an active energy ray-sensitive composition containing cerium oxide-based fine particles, an anti-glare hard coating film having a low degree of curing shrinkage and a small curl can be obtained. Further, when an active energy ray-sensitive composition containing cerium oxide-based fine particles is used, it is possible to expand the design of the difference in specific gravity from the organic fine particles. (Other functional layer) In the anti-glare hard coating film of the present invention, an anti-reflection layer such as a lanthanane-based coating film or fluorine may be provided for the purpose of imparting antireflection properties to the uppermost layer as necessary. It is a coating film or the like. In this case, the thickness of the antireflection layer is suitably from about 0.05 to about ιμηη. By providing the anti-reflection layer, reflection of a picture caused by reflection by sunlight, a fluorescent lamp, or the like is eliminated, and by suppressing the reflectance of the surface, the overall light transmittance is improved, and transparency is improved. Further, with the type of the antireflection layer, the antistatic property can be improved. (Adhesive layer) In the antiglare hard coating film of the present invention, an adhesive layer for adhering to a liquid crystal display can be formed on the reverse surface of the plastic film and the hard coating layer 17-201026508. The adhesive constituting the adhesive layer is, for example, an acrylic adhesive or an amine ester oxygen adhesive for optical use. The thickness of the adhesive layer is usually in the range of 5 to 10 to 60 μm. Further, on the adhesive layer, if necessary, the separator may be provided. For example, on the polyethylene terephthalate plastic film, the thickness of the release agent Φ sheet coated with polyoxymethylene resin or the like is not particularly small. However, it is usually a display such as an anti-glare hard coating film CRT, LCD, or PDP that forms such an adhesive layer, and a member that imparts anti-glare properties, etc., is particularly suitable for use in an LCD or the like [ Polarizing Plate] Further, the present invention provides a polarizing plate comprising the above-described polarizing lens of the present invention. The liquid crystal element in the LCD has a general-purpose electrode substrate, and the alignment layer is inside, and the periphery is sealed by a predetermined gap to sandwich the liquid crystal material on the outer surface of the two transparent electrode substrates. The layer is configured to set a polarizing plate. Fig. 1 is a view showing an example of the above polarizing plate. As shown in the figure, the polarizing plate 10 is generally provided on a polyvinyl alcohol surface with a substrate to which a triethyl cellulose (TAC) film 2 is attached, and then, It is preferable to use a suitable adhesive, and to use a suitable adhesive to form a release sheet on the one surface, preferably by using a suitable adhesive. The peeling, polypropylene, and the like. For the peeling ί 1 5 Ομιη or so. It is suitable for use as a polarizing plate for the ability or scratch resistance. The two sheets of the anti-glare hard coating film of the alignment layer are arranged in a gap and are respectively formed by an adhesive. : Double layer structure of double and 2' of polarizing mirror 1 Light of liquid crystal element -18- 201026508 The adhesive layer 3 of the component is further attached, and the release sheet 4 is attached to the adhesive layer 3. Further, a surface protective film 5 is usually provided on the reverse side of the adhesive layer 3 of the polarizing plate. The polarizing plate of the present invention is provided in the TAC films 2, 2' provided on both sides of the polarizing mirror 1, and the above-mentioned hard coating layer according to the present invention is provided on the other TAC film. In the case where the adhesive layer 3, the release sheet 4, and the surface protective film 5 are provided on the polarizing plate, the hard coating layer according to the present invention is provided particularly on the side of the TAC film 2' on the side of the surface protective film 5. In the method of producing the polarizing plate of the present invention, for example, the operations shown below can be carried out. Further, Fig. 2 is a cross-sectional schematic view showing the configuration of an example of the polarizing plate of the present invention. First, a transparent plastic film having a non-optical anisotropic film 12' such as a TAC film as a base material is used, and a hard coating layer 13 according to the present invention is formed on the other surface to form an anti-glare hard coating film 14. Then, on the one surface of the polarizer 11, the TAC film 1 2 on which the hard coating layer 13 is not formed is laminated on the reverse side by using the adhesive layer 15 and 15' to laminate the anti-glare hard coating film 14. In the case of using a TAC film on a transparent plastic film, other saponification treatments such as the surface treatment described above may be carried out by laminating the adhesive with an adhesive. Thus, the polarizing plate 20 excellent in anti-glare performance and scratch resistance is obtained. The polarizing plate 20 may be provided with the peelable surface protection film 5 shown in FIG. 1 on the surface on which the hard coating layer 13 is provided, or may be attached to the optical element of the liquid crystal element or the like on the reverse surface thereof. Adhesive layer 16 or release sheet 17 of the part. The polarizing plate of the present invention is used for a liquid crystal element in an LCD, and can be used as a light amount adjustment, a polarizing interference application device, an optical defect detector, etc., in -19-201026508. EXAMPLES Next, the present invention will be further illustrated by the examples, but the present invention is not limited by the examples. Further, the average particle diameter and specific gravity of the organic fine particles, the specific gravity of the active energy ray-sensitive composition, and the hard coating film properties were obtained by the following methods. © <Organic Particles> (1) Average particle diameter Measured by Coulter Counter method. (2) Specific gravity at a temperature of 25 ° C The specific gravity of the pycnometer of JIS Z 8807-1976 was measured. <Active energy ray-sensitive composition> (3) Specific gravity at a temperature of 25 ° C The active energy ray-sensitive composition of the active energy ray irradiation was measured by the specific gravity of a pycnometer of JIS Z 8 804. <Hard coating film> (4) The total light transmittance and total haze were measured by using a haze meter "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS K7136, in the examples and comparative examples. The anti-glare hard coating film was prepared, and the total light transmittance and total haze 测定 were measured. Further, the total haze is a total amount of haze due to internal haze (internal haze 与) and external haze 起 due to irregularities on the surface. -20- 201026508 (5) Internal haze 外部 and external haze 添加 Addition of isocyanate crosslinker to 100 parts by mass of acrylic adhesive [manufactured by Carbide Co., Ltd., trade name "PE-121"] 2 parts by mass of Toyo Ink Co., Ltd., trade name "BHS-8515"], and 100 parts by mass of toluene to prepare an adhesive solution. The adhesive solution was applied to a film of polyethylene terephthalate (manufactured by Toyobo Co., Ltd., trade name "Α4 300") having a thickness of 50 μm to a thickness of 20 μm after drying, and dried at 100 ° C for 3 minutes to make an adhesive. sheet. The prepared adhesive sheet was placed on the hard coating layer of the hard coating film to prepare an internal haze determination sample. The haze of the adhesive sheet and the internal haze determination sample was measured, and the haze of the adhesive sheet was subtracted from the haze of the internal haze determination sample, and the internal haze of the hard coating was 値. Further, when the internal haze of the base film (triethylcellulose film) and polyethylene terephthalate used in the examples and the comparative examples was measured in the same manner, less than 0.01% of the enthalpy was regarded as no. The measurement of the haze is the same as (4) above. (6) Evaluation of anti-glare property A sample of the hard-coated® film adhered to an acrylic resin blackboard [manufactured by Sumitomo Chemical Co., Ltd.] via an acrylic adhesive was visually observed under a fluorescent lamp, and the following criteria were used. To assess anti-glare. 〇: Fluorescent lamps have sufficient anti-reflective properties and fade to light brown. X: The anti-reflective properties of fluorescent lamps are insufficient, or the anti-reflective properties of fluorescent lamps are sufficient, but they are faded into pale brown and poorly discernible. (7) 60° gloss was measured in accordance with JIS K 7105 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. -21- 201026508 (8) Pencil hardness was measured in accordance with JIS K 5 400 using the pencil scratching film hardness tester "No 553-M1" of Yasuda Seiki Co., Ltd. (9) Coating failure The surface of the hard coating layer was visually observed, and coating unevenness was evaluated in accordance with the following criteria. 〇: The entire coated surface was uniformly seen. X: The coated surface was mixed with a portion having a high anti-glare property and a low portion, and 全体 all the unevenness was observed. (10) The film thickness is the TAC (three-six) of the anti-glare hard coating film produced in the examples and the comparative examples, and the transparent plastic film used in the production of the anti-glare hard coating film. The base cellulose film was measured for thickness by a constant pressure thickness ["MH-15M" manufactured by Nikon Co., Ltd.], and the film thickness of the hard coating layer was calculated by taking the difference. Preparation Example 1 Hard coating agent for hard coating layer 1 A hard coating agent containing (A) active energy ray-sensitive composition [JSR Co., Ltd., trade name "Opsta Z7 530": From reactive cerium oxide Active energy ray-sensitive composition composed of fine particles (42% by mass), polyfunctional (meth) acrylate monomer, and (meth) acrylate prepolymer (28% by mass) (total: 70 mass) %, specific gravity 1.65), photopolymerization initiator (3 mass%), and methyl ethyl ketone (27 mass%); solid content concentration (73 mass%)] 1 part by mass, spherical poly Acrylic acid A-22-201026508 ester (PMMA)-based fine particles [manufactured by Kyosei Chemical Co., Ltd., average particle size 3μηι, specific gravity 1.19] 3.75 parts by mass as (B) organic fine particles and propylene glycol monomethyl ether 90 parts by mass In order to dilute the solvent, the coating material 1 for a hard coating layer having a solid content concentration of about 40% by mass was prepared. The composition of the coating agent is shown in Table 1. 〇 Preparation Example 2 Coating agent for hard coating layer 2 In addition to changing the spherical cerium particles [manufactured by Kyoritsu Chemical Co., Ltd., average particle size 3 μιη, specific gravity 1·19] 7 In the same manner as in the preparation example 1, the coating material 2 for a hard coating layer having a solid concentration of about 40% by mass was prepared in the same manner as in the preparation example. The composition of the coating agent is shown in Table 1. Preparation Example 3 The coating agent for the hard coating layer 3, except for the spherical fine particles (manufactured by Nippon Kasei Co., Ltd., average particle size 3 μm, specific gravity 1.19), 11.25 parts by mass as (Β) organic fine particles, and preparation examples (1) A coating composition 3 for a hard coating layer having a solid content concentration of about 40% by mass is prepared in the same manner. The composition of the coating agent is shown in Table 1. Preparation Example 4 A hard coating agent containing a (Α) active energy ray-sensitive composition is mixed with a coating material for a hard coating layer [JSR Corporation, trade name "Opsta Ζ 7 530": by reactive cerium oxide particles ( 42% by mass), an active energy ray-sensitive composition composed of a polyfunctional (meth)acrylate monomer and a (meth)acrylate prepolymer (28% by mass) (total: 70% by mass) , specific gravity 1.65), -23- 201026508 photopolymerization initiator (3 mass%), and methyl ethyl ketone (27 mass%); solid content concentration (73 mass%)] 80 parts by mass, and containing no Hard coating agent for active energy ray-sensitive composition of reactive cerium oxide particles [made by Daisei Seiki Co., Ltd., trade name "SELKA-BEAM EXF-L203 (CS-1)": Active energy ray-sensitive composition (65 mass%, specific gravity: 1.33) composed of a functional (meth) acrylate monomer and a (meth) acrylate prepolymer, and a photopolymerization initiator (5 mass%) ), propylene glycol monomethyl acetate (30% by mass); solid formation Partial concentration (70% by mass)] 20 parts by mass, the specific component of the component (A) to be prepared as an active energy ray-sensitive composition has a specific gravity of 1.59. In the same manner as in the preparation example 2, the coating material 4 for a hard coating layer having a solid content concentration of about 40% by mass was prepared. The composition of the coating agent is shown in Table 1. Preparation Example 5 Hard coating agent for hard coating layer 5 A hard coating agent containing (A) active energy ray-sensitive composition [JSR Co., Ltd., trade name "Opsta Z7530": ® by reactive cerium oxide Active energy ray-sensitive composition composed of fine particles (42% by mass), polyfunctional (meth) acrylate monomer, and (meth) acrylate prepolymer (28% by mass) (total: 7〇) Mass%, specific gravity: 1.65), photopolymerization initiator (3 mass%), and methyl ethyl ketone (27 mass%); solid content concentration (73 mass%)] 10 parts by mass, and containing no reactive oxidation Hard coating agent for active energy ray-sensitive composition of cerium particles [manufactured by Daisei Seiki Co., Ltd., trade name "Sheikh Kabin EXF-L203 (CS-1)": polyfunctional (meth) acrylate system Monomer and (A-24-.201026508) acrylate prepolymer (65 mass%, specific gravity 33.33), photopolymerization initiator (5 mass%), and propylene glycol monomethyl acetate (3) 〇Quality solid content concentration (70% by mass)] 90 parts by mass, active energy The specific gravity of the solid content of the radiation-inducing composition was adjusted to 1.36. Secondly, the spherical polystyrene-based microparticles were uniformly mixed [manufactured by Nippon Chemical Co., Ltd., average particle size 3·5 μπι, specific gravity 1.〇9] 3.75 In the mass fraction, 90 parts by mass of (B) organic fine particles and propylene glycol monomethyl ether were used as a diluent solvent to prepare a coating layer 5 for a hard coating layer having a solid concentration of about 40% by mass. The composition of the coating material is shown in Table 1. © Preparation Example 6 Hard coating agent for hard coating layer 6 A hard coating agent containing a (Α) active energy ray-sensitive composition [JSR Corporation, trade name "Opsta Ζ 7530": from reactive cerium oxide particles ( 42% by mass), an active energy ray-sensitive composition composed of a polyfunctional (meth)acrylate monomer and a (meth)acrylate prepolymer (28% by mass) (total: 70% by mass) , specific gravity 1.65), photopolymerization initiator (3 mass%), and methyl ethyl ketone (27 mass%); solid. ® component concentration (73 mass%)] 30 parts by mass, and containing no reactive oxidation Active energy ray-sensing type Hard coating agent for products [Dai Ri Jing Chemical Co., Ltd., trade name "Sheikh Kabin EXF-L203 (CS-1)": polyfunctional (meth) acrylate monomer and (meth) acrylic acid Ester prepolymer (65 mass%, specific gravity 1.33), photopolymerization initiator (5 mass%), and propylene glycol monomethyl acetate (30 mass%); solid content concentration (70 mass%)] 70 mass In the same manner as in Preparation Example 2, the coating material 6 for hard coating layer having a solid content concentration of about 40% by mass was prepared in the same manner as in Preparation Example 2 except that the specific component (A) was prepared in the same manner as in Preparation Example 2. The composition of the coating agent is shown in Table 1 » Preparation Example 7 Coating agent for hard coating layer 7 In addition to using a hard coating agent containing an active energy ray-sensitive composition containing no (A) reactive cerium oxide particles [Dai Ri Jing Chemical Industry Co., Ltd., the product name "Sheikh Kabin EXF-L2 03 (CS-1)": a polyfunctional (meth) acrylate monomer and a (meth) acrylate prepolymer (65 mass %) In the same manner as in Preparation Example 1, except that the specific gravity was 1.33), the photopolymerization initiator (5 mass%), and the propylene glycol monomethyl acetate (30% by mass); the solid content concentration (70% by mass); 100 parts by mass. The coating material 7 for a hard coating layer having a solid content concentration of about 40% by mass was prepared. The composition of the coating agent is shown in Table 1. (Example 1) The coating material 1 obtained by the preparation of the Meyer scraper on the surface of a TAC (triethyl fluorene cellulose) film (manufactured by Fujifilm Co., Ltd.) having a thickness of 80 μm was prepared to have a cured film thickness of about ιμηη. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high pressure mercury lamp to prepare an antiglare hard coating film. The properties of the hard coating film are shown in Table 2. (Example 2) An antiglare hard coating film was produced in the same manner as in Example 1 except that the coating material 1 obtained by the preparation of the Meyer strip was prepared to have a cured film thickness of about 9 μm. The properties of the hard coating film are shown in Table 2. -26-.201026508 Example 3 An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating material 2 obtained by the preparation of the Meyer strip was prepared to have a cured film thickness of about ΙΟμηι. The properties of the hard coating film are shown in Table 2. (Example 4) An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating material 3 obtained by the preparation of the Meyer strip was prepared to have a cured film thickness of about 1 μm. The properties of the hard coating film are shown in Table 2. Example 5 An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating material 4 obtained by the preparation of the Meyer strip was prepared to have a cured film thickness of about ΙΟμπι. The properties of the hard coating film are shown in Table 2. Example 6 ® An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating material 5 obtained by the preparation of the Meyer strip was prepared to have a cured film thickness of about 1 μm. The properties of the hard coating film are shown in Table 2. Comparative Example 1 An antiglare hard coating film was produced in the same manner as in Example 1 except that the coating material 6 obtained by the preparation of the Meyer strip was prepared to have a cured film thickness of about 1 μm. -27- .201026508 The properties of the hard coating are shown in Table 2. Comparative Example 2 An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating material 7 obtained by the preparation of the Meyer strip was prepared to have a cured film thickness of about 2.5 μm. The properties of the hard coating film are shown in Table 2. Comparative Example 3 An antiglare hard coating film was produced in the same manner as in Example 1 except that the coating material 7 obtained by the preparation of the Meyer scraper was prepared to have a cured film thickness of about 3 μm. The properties of the hard coating film are shown in Table 2. Comparative Example 4 An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating material 7 obtained by the preparation of the Meyer scraper was prepared to have a cured film thickness of about 1 μm. The properties of the hard coating film are shown in Table 2. -28- .201026508 [Table i]
被 覆 劑 種 類 (Α)活性倉睛射線感應型組成物 (Β)有機微粒 活性缝射線感應麵 成物中反應性氧化矽微 粒的含有比例0 (質量％) 於 25°C 之比重 麵 平均 粒徑 (βΤΛ) 粒子添加 量2) 償量％) 於 25°C 之it* 調製例1 1 60 1.65 ΡΜΜΑ系微粒 3 5.4 1.19 調製例2 2 60 1.65 ΡΜΜΑ系微粒 3 10.7 1.19 調製例3 3 60 1.65 ΡΜΜΑ系微粒 3 16.1 1.19 調製例4 4 48 1.59 PMMA mm 3 10.7 1.19 調製例、 5 6 1.36 聚苯乙烯系微粒 3.5 5.4 1.09 調製例ό 6 18 1.43 ΡΜΜΑ系微粒 3 10.7 1.19 調製例7 7 0 1.33 ΡΜΜΑ系微粒 3 5.4 1.19 1) 顯示其爲（A)成分之活性能量射線感應型組成物（固體成 分）中之反應性氧化矽微粒的含有比例。 2) 顯示相對於其爲（A)成分之活性能量射線感應型組成物 (固體成分）之其爲（B)成分的有機微粒添加量的比例。 表2Coating type (Α) active warehouse eye ray-sensitive composition (Β) organic particle active ray-sensing surface-like content of reactive cerium oxide particles 0 (% by mass) Specific surface area average particle diameter at 25 ° C (βΤΛ) Particle addition amount 2) Replenishment %) It* at 25 ° C Modification Example 1 1 60 1.65 Lanthanide particles 3 5.4 1.19 Preparation example 2 2 60 1.65 Lanthanide particles 3 10.7 1.19 Preparation example 3 3 60 1.65 ΡΜΜΑ Fine Particles 3 16.1 1.19 Preparation Example 4 4 48 1.59 PMMA mm 3 10.7 1.19 Preparation Example, 5 6 1.36 Polystyrene Particles 3.5 5.4 1.09 Preparation Example 18 6 18 1.43 Lanthanide Particles 3 10.7 1.19 Preparation Example 7 7 0 1.33 Fine Particles 3 5.4 1.19 1) The content ratio of the reactive cerium oxide fine particles in the active energy ray-sensitive composition (solid content) of the component (A) is shown. 2) The ratio of the amount of the organic fine particles added as the component (B) relative to the active energy ray-sensitive composition (solid component) which is the component (A) is shown. Table 2
被覆劑 (A)成分 硬被 硬被挪之性能 讎 (B)成分 找度 霧度値(％) 60。光 防眩 娜 塗布 比重差 (im) 麵率 總霧 內部霧 外部霧 mm 性 硬度 不勻 (%) 度値 度値 度値 寅例1 1 0.46 10 91.82 26.00 0.93 25.07 52.1 〇 3H 〇 *例2 1 0.46 9 92.03 27.24 0.72 26.52 50.8 〇 3H 〇 實例3 2 0.46 10 92.35 40.23 2.76 37.47 28.1 〇 3H 〇 實例4 3 0.46 10 93.01 48.33 3.22 45.11 19.9 〇 3H 〇 實例5 4 0.40 10 91.34 9.37 0.15 9.22 95.2 〇 3H 〇 實例6 5 0*27 10 92.27 51.65 19.89 31.76 21.3 〇 3H 〇 比較例1 6 0.24 10 92.59 6.36 4.87 1.49 142.6 X 3H 〇 比較例2 7 0.14 2.5 91.83 47.15 1.66 45.49 23.3 〇 2H 〇 比較例3 7 0.14 3 90.49 34.40 2.85 31.55 26.3 〇 2H X 比較例4 7 0.14 10 92.65 12.66 11.08 1.58 139.6 X 3H 〇 -29- 201026508 實例1至6中任一者，（A)成分-(B)成分比重差均超過 0.25，防眩性、鉛筆硬度、塗布不均之任一者均良好。 比較例1至4中任一者，（A)成分-(B)成分比重差均未 滿0.25，防眩性、鉛筆硬度及塗布不均中任一者以上不足。 本發明之防眩性硬被覆膜係設置包含有機微粒之硬被 覆層的防眩性硬被覆膜，適用做爲可控制外部霧度値及60° 光澤値於所希望之値，同時因膜厚所致之外部霧度値變動 少且可穩定生產，對於CRT、LCD、PDP等之顯視器，賦 ® 予防眩性能或耐擦傷性能等的構件，特別適合做爲LCD等 之中的偏光板用。 【圖式簡單說明】 第1圖係顯示偏光板之一範例之構成的斜視圖。 第2圖系顯示本發明偏光板之一範例之構成的截面模 式圖。 【主要元件符號說明】 1 聚乙烯醇系偏光鏡 2 TAC膜 2， TAC膜 3 黏著劑層 4 剝離片 5 表面保護膜 10 偏光板 11 偏光鏡 12 TAC膜 -30- 201026508 125 TAC膜 13 硬被覆層 14 防眩性硬被覆膜 15 接著劑層 1 5 5 接著劑層 16 黏著劑層 17 剝離片 20 偏光板The coating agent (A) is hard and hard to be transferred. 雠 (B) Component Finding degree Haze 値 (%) 60. Light anti-dark coating specific gravity difference (im) Surface ratio Total fog Internal fog External fog mm Hardness unevenness (%) Degree of temperature and humidity Example 1 1 0.46 10 91.82 26.00 0.93 25.07 52.1 〇3H 〇*Example 2 1 0.46 9 92.03 27.24 0.72 26.52 50.8 〇3H 〇Example 3 2 0.46 10 92.35 40.23 2.76 37.47 28.1 〇3H 〇Example 4 3 0.46 10 93.01 48.33 3.22 45.11 19.9 〇3H 〇Example 5 4 0.40 10 91.34 9.37 0.15 9.22 95.2 〇3H 〇Example 6 5 0*27 10 92.27 51.65 19.89 31.76 21.3 〇3H 〇Comparative Example 1 6 0.24 10 92.59 6.36 4.87 1.49 142.6 X 3H 〇Comparative Example 2 7 0.14 2.5 91.83 47.15 1.66 45.49 23.3 〇2H 〇Comparative Example 3 7 0.14 3 90.49 34.40 2.85 31.55 26.3 〇2H X Comparative Example 4 7 0.14 10 92.65 12.66 11.08 1.58 139.6 X 3H 〇-29- 201026508 In any of Examples 1 to 6, the difference in specific gravity of component (A)-(B) exceeds 0.25, anti-glare Any of the properties, pencil hardness, and uneven coating were good. In any of Comparative Examples 1 to 4, the difference in specific gravity between the component (A) and the component (B) was less than 0.25, and any one of the antiglare property, the pencil hardness, and the coating unevenness was insufficient. The anti-glare hard coating film of the present invention is provided with an anti-glare hard coating film containing a hard coating layer of organic fine particles, and is suitable for controlling external haze and 60° gloss, and at the same time, The external haze caused by the film thickness is less fluctuating and can be stably produced. For CRT, LCD, PDP, etc., components such as anti-glare or scratch resistance are particularly suitable for use as LCDs. For polarizing plates. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing a configuration of an example of a polarizing plate. Fig. 2 is a cross-sectional view showing the constitution of an example of a polarizing plate of the present invention. [Main component symbol description] 1 Polyvinyl alcohol polarizer 2 TAC film 2, TAC film 3 Adhesive layer 4 Release sheet 5 Surface protection film 10 Polarizing plate 11 Polarizing mirror 12 TAC film -30- 201026508 125 TAC film 13 Hard coating Layer 14 anti-glare hard coating 15 subsequent layer 1 5 5 adhesive layer 16 adhesive layer 17 release sheet 20 polarizing plate
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