[go: up one dir, main page]

TW200946995A - Antiglare hard coat film and polarizer plate using the film - Google Patents

Antiglare hard coat film and polarizer plate using the film Download PDF

Info

Publication number
TW200946995A
TW200946995A TW098110031A TW98110031A TW200946995A TW 200946995 A TW200946995 A TW 200946995A TW 098110031 A TW098110031 A TW 098110031A TW 98110031 A TW98110031 A TW 98110031A TW 200946995 A TW200946995 A TW 200946995A
Authority
TW
Taiwan
Prior art keywords
hard coating
film
fine particles
glare
coating film
Prior art date
Application number
TW098110031A
Other languages
Chinese (zh)
Other versions
TWI453474B (en
Inventor
Tatsuya Izumi
Satoru Shoshi
Tomo Iwata
Jun Furukawa
Tsutomu Furuya
Original Assignee
Lintec Corp
Sumitomo Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp, Sumitomo Chemical Co filed Critical Lintec Corp
Publication of TW200946995A publication Critical patent/TW200946995A/en
Application granted granted Critical
Publication of TWI453474B publication Critical patent/TWI453474B/en

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/38—Anti-reflection arrangements

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

An antiglare hard coat film (14) which comprises a hard coat layer (13) which is formed on a face of transparent plastic film (12') using a material for forming hard coat layer which comprises (A) a composition sensitive to an active energy ray comprising (a) multi-functional (meth)acrylate based monomer and/or (meth)acrylate based prepolymer and (b) silica based fine particles, (B) spherical organic fine particles and (C) a dispersing agent having at least one polar group in a molecule; and a polarizer plate (20) using the film. The thickness of the hard coat layer is larger than the average diameter of (B) spherical organic fine particles. In the antiglare hard coat film provided with the hard coat layer comprising the organic fine powders and the polarizer plate using the film, external haze and 60 DEG specular glossiness of the film can be controlled to prescribed values without reducing contrast.

Description

200946995 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該薄膜之偏光 板。進而詳細言之，本發明係關於一種設置有含有機微粒之 硬被覆層的防眩性硬被覆膜，在對外表面霧値及6CT光澤率 控制在所期望的値時，不會降低對比，爲表面硬度優異之防 眩性硬被覆膜，及一種使用該防眩性硬被覆膜的偏光板。 【先前技術】 在布朗管（CRT)或液晶顯示器（LCD)、電漿顯示器（PDP) . 等的顯示器中，光自外部入射至畫面中，此光反射使得顯示 畫面不容易看清楚，尤其是近年來伴隨著顯示器的大型化， 解決上述問題已成爲日益重要的課題。解決該問題的手段可 例舉一種使用具防眩性硬被覆層的構件。而該防眩性硬被覆 層的形成方法可大致區分爲：（1)爲了形成硬被覆層，於硬化 時使用物理的方法，將表面粗面化的方法，（2)在硬被覆層形 φ 成用的硬被覆劑中混入塡料的方法，（3)於硬被覆層形成用的 硬被覆劑中混入非相溶的二成分，利用該等之相分離（phase separateion)的方法等三種方法。該等藉由在任意表面形成微 細凹凸，而可抑制外光的正反射，防止螢光燈等外光的反 射。該等中以（2)在硬被覆劑塗布劑中混入塡料的方法成爲主 流。塡料方面，一般係使用原來之以二氧化矽爲代表的無機 微粒。使用二氧化矽粒子的理由，可例舉不僅可將所得之硬 200946995 被覆膜的白色度抑制爲低，亦不會因硬化不足導致耐磨耗性 (antiabrasion)降低等。 一方面，有提案一種防眩薄膜，此係於透明基板上形成 由折射率1.40〜1.60的樹脂珠（beads)與電離輻射線硬化型組 成物所構成之防眩層。例如在專利文獻1提案有，以塗膜的 膜厚以上粒徑的有機塡料所致的防眩性薄膜來形成可顯現 防眩性的凹凸，但若爲提高防眩性而將凹凸擴大，將會導致 霧値上昇、透明清晰度（transmission cleanliness value)下降。 ❹ 爲改善該等問題，專利文獻2提案有將顯現防眩性的凹凸形 成用之塗膜膜厚以上粒徑的有機塡料的添加量予以降低，在 添加塗膜膜厚以下粒徑的有機塡料，藉此製作可取得均衡的 防眩性薄膜。 但是，實際上即使以上述的方法可獲得光學物性的平 衡，但因使用微粒粒徑的不均勻，而顯現於凹凸不存在的地 方，並無法獲得全面的防眩性。又，由於膜厚所致外表面霧 〇 値的變動大，使得穩定生產性變差。又，該等系統的膜厚係 取決於微粒的尺寸，要以如表面硬度的膜厚來改變其性能的 物性加以調整則有困難。 另外，其他的方法亦有試著以抑制塡料的沉澱，設計塡 料之平均粒徑以上膜厚的方式，來顯現防眩性的方法亦被使 用。例如在該專利文獻1提案有微量添加用於防止沉澱之二 氧化矽等的無機塡料來控制塡料的沉澱，專利文獻3提案有 少量添加由雲母等膨脹性層狀黏土礦物所成的觸變性劑照 200946995 樣來防止塡料的沉澱。但是，在添加了該等無機物時，會有 硬被覆膜之透明性惡化的問題。 又有提案，在控制塡料沉澱這一點上，亦有使用聚苯乙 烯等比重較輕的有機塡料。該等比重輕的有機塡料，一般而 言，由於與活性能量線硬化型組成物之硬化物的折射率差 大，當使用該等來製作防眩性薄膜時，將成爲來自光擴散性 功能的內部霧値大的防眩性薄膜。內部霧値大的防眩性薄膜 因具有光擴散性，故具有減低近年來使用高精細化之TV或 e 監視器被視爲問題之畫面刺眼感（所謂的閃爍）的效果（參照 專利文獻4、5及6)。 但是，內部霧値大的防眩性薄膜爲低對比，使得減低閃 爍的現象與提高對比成了權衡的關係。因此，在顯示器的設 計中，因而成爲究竟要選擇以對比爲優先之高對比型的防眩 性薄膜，亦或選擇以防止閃爍爲優先之廣用型的防眩性薄 膜。但是，無論高對比型或是廣泛使用型均無法獲得全然無 φ 視另一種性質的防眩性薄膜，故能取得兩者均衡的設計已成 爲必要的課題。 又，防眩性本身的性質受到防眩性薄膜表面凹凸的影 響，作爲該等一般的値可例舉外表面霧値或60°光澤率等。 在進行調節防眩性薄膜的防眩性時，通常進行塡料的含量或 平均粒徑、或膜厚之變更，但藉由該等操作使表面形狀變化 時，不僅外表面霧値或60。光澤率，連內部霧値亦隨之而變 化了，故有無法獲得目標之對比等的問題。 200946995 進而，亦有當外表面霧値變大時，產生外光反射部分的 周邊變白、可見度惡化之所謂褪色（faded color)的現象。 [專利文獻1]特開平6-18706號公報 [專利文獻2]特許第3507344號公報 [專利文獻3]特開2004-294601號公報 [專利文獻4]特許第35077 19號公報 [專利文獻5]特許第3515401號公報 [專利文獻6]特許第4001320號公報 【發明內容】 發明欲解決課題 本發明的目的，係以此情事爲根本，提供一種設置有含 有機微粒之硬被覆層的防眩性硬被覆膜，在將外表面霧値及 60°光澤率控制在所期望的値時，不會降低對比的防眩性硬 被覆膜，及一種使用該防眩性硬被覆膜的偏光板。 解決課題之手段 〇 本發明人等爲了達成該目的，經一再戮力硏究的結果， 首先發現藉由使用含有：含二氧化矽系微粒之活性能量線感 應型組成物；球狀有機微粒；及分子內至少具有一個極性基之 分散劑，的硬被覆層形成材料，以形成硬被覆層，且該厚度 較上述球狀有機微粒的平均粒徑更大，得以達成其目的，基 於該真知灼見，因而完成本發明。 亦即，本發明係提供 200946995 π]—種防眩性硬被覆膜，其特徵係於透明塑膠薄膜表面具有 由使用硬被覆層形成材料所形成的硬被覆層，其中該硬被覆 層形成材料含有：（A)( a)多官能性（甲基）丙烯酸酯系單體及/ 或（甲基）丙烯酸酯系預聚物、（b)含二氧化矽系微粒的活性能 量線感應型組成物；（B)球狀有機微粒；及（C)分子內至少具有 一個極性基的分散劑，且該硬被覆層的厚度比上述（B)球狀 有機微粒的平均粒徑更大； [2] 如第[1]項的防眩性硬被覆膜，其中（〇分子內至少具有一 〇 個極性基的分散劑，其極性基係具有選自呈酸性的官能基及 一至三級胺基中的一種以上； [3] 如第[2]項的防眩性硬被覆膜，其中（C)分子內至少具有一 個極性基的分散劑係具有Ν,Ν-二烷胺基； [4] 如第[1]至[3]項中任一項的防眩性硬被覆膜，其中二氧 化矽系微粒係具有作爲表面官能基的含（甲基）丙烯醯基之基 的二氧化矽微粒； Φ [5]如第[1]至[4]項中任一項的防眩性硬被覆膜，其中（B)球狀 有機微粒的平均粒徑爲6〜l〇Vm; [6] 如第[1]至[5]項中任一項的防眩性硬被覆膜，其中（a)活性 能量線感應型組成物的硬化物，與（B)球狀有機微粒的折射 率差爲0.03以上； [7] 如第[1]至[6]項中任一項的防眩性硬被覆膜，其中硬被覆 層的外表面霧値爲20%以下；及 200946995 [8]—種偏光板，其特徵爲將形成有如第[1]至[7]項中任一項 的防眩性硬被覆膜的面之相反面貼合於偏光鏡而形成。 發明的效果 根據本發明，係提供一種設置有含有機微粒之硬被覆層· 的防眩性硬被覆膜，在將外表面霧値及60°光澤率控制在所 期望的値時，不會降低對比的防眩性硬被覆膜，及使用該防 眩性硬被覆膜的偏光板。 【實施方式】 實施發明之最佳型態 本發明的防眩性硬被覆膜中，在設置於透明塑膠薄膜之 至少單面上之硬被覆層之形成時，使用具有下述組成的硬被 覆層形成材料。 [硬被覆層形成材料] 本發明中硬被覆層形成材料含有（A)活性能量線感應型 組成物、（B)球狀有機微粒及（〇分子內至少具有一個極性基 0 的分散劑。 ((A)活性能量線感應型組成物） 該硬被覆層形成材料中，在作爲（A)成分所使用的活性 能量線感應型組成物中，含有爲必須成分的（a)爲活性能量線 硬化型化合物的多官能性（甲基）丙烯酸酯系單體及/或（甲基） 丙烯酸酯系預聚物’及（b)二氧化矽系微粒。 此外’本發明中，活性能量線係指在電磁波或帶電粒子 線中具有能量量子者’亦即，係指紫外線或電子束等。 200946995 <(a)活性能量線硬化型化合物> 本發明中，（a)活性能量線硬化型化合物方面，係使用多 官能性（甲基）丙烯酸酯系單體及/或（甲基）丙烯酸酯系預聚 物。 該多官能性（甲基）丙烯酸酯系單體方面，可例舉二（甲基） 丙烯酸1，4-丁二醇酯、二（甲基）丙烯酸1,6-己二醇酯、二（甲 基）丙烯酸新戊二醇酯、二（甲基）丙烯酸聚乙二醇酯、二（甲 基）丙烯酸羥基三甲基乙酸新戊二醇酯、二（甲基）丙烯酸二環 ❹ 戊酯、己內酯改性二環戊烯基二（甲基）丙烯酸酯、環氧乙烷 改性磷酸二（甲基）丙烯酸酯、烯丙基化環己基二（甲基）丙烯 酸酯、異三聚氰酸二（甲基）丙烯酸酯、三（甲基）丙烯酸三羥 甲基丙酯、三（甲基）丙烯酸二新戊四醇酯、丙酸改性二新戊 四醇三（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、環氧 丙烷改性三羥甲基丙烷三（甲基）丙烯酸酯、三（丙烯醯氧基乙 基）異三聚氰酸酯、丙酸改性二新戊四醇五（甲基）丙烯酸酯、 〇 二新戊四醇六（甲基）丙烯酸酯、己內酯改性二新戊四醇六（甲 基）丙烯酸酯等的多官能性（甲基）丙烯酸酯。該等單體可使用 單獨一種，亦可組合二種以上使用。 一方面，該（甲基）丙烯酸酯系預聚物方面，可例舉聚酯 丙烯酸酯系、環氧丙烯酸酯系、胺甲酸酯丙烯酸酯系、聚醇 丙烯酸酯系等。在此，聚酯丙烯酸酯系預聚物方面，可例舉 藉由使多價羧酸與多價醇縮合所得兩末端具有羥基的聚酯 寡聚物的羥基，以（甲基）丙烯酸酯化，或藉由將在多價羧酸 -10- 200946995 中加成烯化氧所得之寡聚物末端的羥基’以（甲基）丙烯酸酯 化而獲得。 環氧丙烯酸酯系預聚物，例如藉由在比較低分子量的雙 酚型環氧樹脂或酚醛清漆型環氧樹脂的環氧乙烷（oxirane) 環上，使（甲基）丙烯酸反應進行酯化而獲得。胺甲酸酯丙烯 酸酯系預聚物可例舉藉由將聚醚聚醇或聚酯聚醇與聚異氰 酸酯的反應所得之聚胺甲酸酯寡聚物，以（甲基）丙烯酸酯化 而獲得。進而，聚醇丙烯酸酯系預聚物，可藉由將聚醚聚醇 〇 的羥基，以（甲基）丙烯酸酯化而獲得。該等預聚物可單獨使 用一種，亦可組合二種以上使用，又，亦可與該多官能性（甲 基）丙烯酸酯系單體倂用。 <(b)二氧化矽系微粒> 本發明中，（b)二氧化矽系微粒可使用膠體狀二氧化矽微 粒及/或具有表面官能基的二氧化矽微粒。 膠體狀二氧化矽微粒的平均粒徑爲1〜400nm左右， p 又，具有表面官能基的二氧化矽微粒，表面官能基方面可例 舉具有含（甲基）丙烯醯基的二氧化矽微粒（以下稱爲反應性 二氧化矽微粒）。 上述反應性二氧化矽微粒，可例如使平均粒徑0.005〜 1/zm左右之二氧化矽微粒表面的矽烷醇基，及具有可與該 矽烷醇基反應之官能基的含有聚合性不飽和基的有機化合 物反應，藉此而可獲得。聚合性不飽和基方面，可例舉自由 基聚合性的（甲基）丙烯醯基等。 -11- 200946995 具有可與該矽烷醇基反應之官能基的含有聚合性不飽 和基的有機化合物方面，可例舉使用一般式（I)所示之化合 物等爲佳 R1BACKGROUND OF THE INVENTION 1. 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 does not lower the contrast when the external surface haze and the 6CT gloss ratio are controlled to a desired flaw. It is an antiglare hard coating film excellent in surface hardness, and a polarizing plate using the antiglare hard coating film. [Prior Art] In a display such as a brown tube (CRT) or a liquid crystal display (LCD) or a plasma display (PDP), light is incident on the screen from the outside, and the light reflection makes the display image difficult to see, especially In recent years, with the increase in the size of displays, it has become an increasingly important issue to solve the above problems. A means for solving this problem can be exemplified by using a member having an antiglare hard coating layer. The method for forming the antiglare hard coating layer can be roughly classified into: (1) a method of forming a hard coating layer by using a physical method to harden the surface during hardening, and (2) a hard coating layer shape φ. (3) a method of mixing a hard coating agent into a hard coating agent, (3) mixing a non-coherent two component into a hard coating material for forming a hard coating layer, and using three methods such as phase separation . By forming fine concavities and convexities on any surface, it is possible to suppress the regular reflection of external light and prevent reflection of external light such as a fluorescent lamp. In the above, (2) a method of mixing the crucible in the hard coating agent coating agent becomes a main flow. In the case of dip, the inorganic particles represented by cerium oxide are generally used. The reason why the cerium oxide particles are used is not only that the whiteness of the obtained hard 200994695 coating film can be suppressed to be low, and that the abrasion resistance (antiabrasion) is not lowered due to insufficient curing. On the other hand, there has been proposed an anti-glare film which forms an anti-glare layer composed of a resin bead having a refractive index of 1.40 to 1.60 and an ionizing radiation-curable composition on a transparent substrate. For example, in the anti-glare film which is an organic antimony material having a film thickness equal to or larger than the film thickness of the coating film, irregularities which can exhibit anti-glare properties are formed, but the unevenness is enlarged to improve the anti-glare property. This will cause the haze to rise and the transmission cleanliness value to drop. ❹ In order to improve the above-mentioned problems, Patent Document 2 proposes to reduce the amount of organic coating material having a coating film thickness of not less than the thickness of the coating film for forming an anti-glare property, and to add an organic film having a particle diameter of less than the coating film thickness. By dip, a balanced anti-glare film can be produced. However, in actuality, even if the balance of optical properties is obtained by the above method, the unevenness of the particle diameter is used, and it appears in the place where the irregularities do not exist, and comprehensive anti-glare properties cannot be obtained. Further, the fluctuation of the outer surface haze due to the film thickness is large, so that the stable productivity is deteriorated. Further, the film thickness of these systems depends on the size of the particles, and it is difficult to adjust the physical properties such as the film thickness of the surface hardness to change its properties. In addition, other methods have been tried to suppress the precipitation of the dip, and to design a method in which the average particle diameter of the crucible is larger than the film thickness to exhibit anti-glare properties. For example, in Patent Document 1, it is proposed to control the precipitation of the mash by adding a small amount of an inorganic mash for preventing precipitation of cerium oxide, and Patent Document 3 proposes to add a small amount of contact with an intumescent layered clay mineral such as mica. The denaturant prevents the precipitation of the dip in accordance with 200946995. However, when these inorganic substances are added, there is a problem that the transparency of the hard coating film is deteriorated. There are also proposals for the use of polystyrene and other lighter organic dices in controlling the precipitation of tantalum. The light-weight organic coating material generally has a large refractive index difference from the cured product of the active energy ray-curable composition, and when used to produce an anti-glare film, it will function as a light diffusing property. The interior of the smog is large anti-glare film. Since the anti-glare film having a large internal haze has a light diffusing property, it has an effect of reducing the glare (so-called flicker) of a screen which is considered to be a problem in the recent use of a high-definition TV or e monitor (refer to Patent Document 4). , 5 and 6). However, the internal smog-proof anti-glare film is low-contrast, making the phenomenon of reducing flicker and improving contrast a trade-off. Therefore, in the design of the display, it is necessary to select an anti-glare film which is a high contrast type which is preferred for comparison, or an anti-glare film which is a wide-purpose type which is preferred to prevent flicker. However, irrespective of whether the high-contrast type or the widely-used type cannot obtain an anti-glare film which has no other property depending on the other nature, it has become a necessary subject to achieve a balanced design. Further, the properties of the anti-glare property itself are affected by the unevenness of the surface of the anti-glare film, and examples of such general defects include an outer surface haze or a 60° gloss ratio. When the antiglare property of the antiglare film is adjusted, the content of the dip, the average particle diameter, or the film thickness is usually changed. However, when the surface shape is changed by these operations, not only the outer surface is hazy or 60. The gloss rate, as well as the internal haze, has changed, so there is a problem that the target cannot be compared. Further, in the case where the outer surface smog becomes large, there is a phenomenon in which the periphery of the external light reflecting portion is whitened and the visibility is deteriorated, so-called faded color. [Patent Document 1] Japanese Patent Publication No. 2004-294601 (Patent Document 4) Japanese Patent Publication No. 2004-294601 (Patent Document 4) Patent No. 3507719 [Patent Document 5] [Patent Document 6] [Patent Document 6] Japanese Patent Application No. 4001320 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide an anti-glare property provided with a hard coating layer containing organic fine particles. The hard coating film does not lower the contrast anti-glare hard coating film when the outer surface haze and the 60° gloss ratio are controlled to a desired crucible, and a polarizing film using the anti-glare hard coating film board. Means for Solving the Problem In order to achieve the object, the present inventors have found, through repeated efforts, to find an active energy ray-inductive composition containing: cerium oxide-containing fine particles; spherical organic fine particles; And a hard coating layer forming material having at least one polar group in the molecule to form a hard coating layer, and the thickness is larger than an average particle diameter of the spherical organic fine particles, thereby achieving the object, based on the insight, Thus the present invention has been completed. That is, the present invention provides a 200946995 π]-anti-glare hard coating film characterized in that the surface of the transparent plastic film has a hard coating layer formed by using a hard coating layer forming material, wherein the hard coating layer forming material Containing: (A) (a) a polyfunctional (meth) acrylate monomer and/or a (meth) acrylate prepolymer, and (b) an active energy ray-inducing composition comprising cerium oxide-based particles (B) spherical organic fine particles; and (C) a dispersing agent having at least one polar group in the molecule, and the thickness of the hard coating layer is larger than the average particle diameter of the above (B) spherical organic fine particles; The anti-glare hard coating film according to the item [1], wherein (the dispersing agent having at least one polar group in the fluorene molecule, the polar group having a functional group selected from the group consisting of acidic groups and one to three amino groups) [3] The anti-glare hard coating film of the item [2], wherein the dispersing agent having at least one polar group in the (C) molecule has an anthracene-quinone-dialkylamine group; The anti-glare hard coating film according to any one of [1] to [3], wherein the cerium oxide-based fine particle system has The anti-glare hard coating film of any one of the above [1] to [4], wherein (B) The anti-glare hard coating film of any one of the items [1] to [5], wherein (a) active energy ray sensing The anti-glare hard coating film of any one of the above-mentioned items [1] to [6], wherein the hardened material of the type of the composition is not more than 0.03 or more. The outer surface of the hard coating layer has a haze of 20% or less; and 200946995 [8] is a polarizing plate characterized in that the anti-glare hard coating film according to any one of items [1] to [7] is formed. According to the present invention, an anti-glare hard coating film provided with a hard coating layer containing organic fine particles is provided, and the outer surface is smoggy and 60. ° The gloss ratio is controlled when the desired enthalpy is not reduced, and the anti-glare hard coating film is not reduced, and the polarizing plate using the anti-glare hard coating film is provided. [Embodiment] The best mode of the invention is implemented. invented In the glare hard coating film, a hard coating layer forming material having the following composition is used in forming a hard coating layer provided on at least one surface of the transparent plastic film. [Hard coating layer forming material] Hard in the present invention The coating layer forming material contains (A) an active energy ray-inductive composition, (B) spherical organic fine particles, and a dispersing agent having at least one polar group 0 in the fluorene molecule. ((A) Active energy ray-sensitive composition) In the active energy ray-inducing composition used as the component (A), the hard-coating layer forming material contains (a) an active energy ray-curable compound-based polyfunctional (meth)acrylic acid as an essential component. An ester monomer and/or a (meth)acrylate prepolymer' and (b) cerium oxide-based fine particles. Further, in the present invention, the active energy ray means an energy quantum in an electromagnetic wave or a charged particle ray, that is, an ultraviolet ray or an electron beam. 200946995 <(a) Active energy ray-curable compound> In the present invention, (a) an active energy ray-curable compound is a polyfunctional (meth) acrylate monomer and/or (meth) Acrylate prepolymer. The polyfunctional (meth)acrylate monomer may, for example, be 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate or the like. Neopentyl glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate , caprolactone modified dicyclopentenyl di(meth) acrylate, ethylene oxide modified di(meth) acrylate, allylated cyclohexyl di (meth) acrylate, iso-tri Poly(meth)acrylate polycyanate, trimethylolpropyl tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dineopentaerythritol tris(methyl) Acrylate, neopentyl alcohol tri(meth) acrylate, propylene oxide modified trimethylolpropane tri(meth) acrylate, tris(propylene decyloxyethyl) isocyanurate, Propionic acid modified dine pentaerythritol penta (meth) acrylate, decyl neopentaerythritol hexa(meth) acrylate, caprolactone modified two new Hexa polyfunctional (meth) acrylate, (meth) acrylates. These monomers may be used alone or in combination of two or more. On the other hand, the (meth)acrylate prepolymer may, for example, be a polyester acrylate type, an epoxy acrylate type, a urethane acrylate type or a polyalcohol acrylate type. Here, as the polyester acrylate-based prepolymer, (meth)acrylic acid esterification can be exemplified by a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals obtained by condensing a polyvalent carboxylic acid and a polyvalent alcohol. Or obtained by (meth)acrylation of a hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to the polyvalent carboxylic acid-10-200946995. An epoxy acrylate-based prepolymer, for example, by reacting (meth)acrylic acid on an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or a novolac type epoxy resin Obtained. The urethane acrylate-based prepolymer may be exemplified by a (meth) acrylate by a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate. obtain. Further, the polyhydric acrylate prepolymer can be obtained by esterifying a hydroxyl group of a polyether polyhydrazide with (meth) acrylate. These prepolymers may be used singly or in combination of two or more kinds, or may be used in combination with the polyfunctional (meth) acrylate monomer. <(b) cerium oxide-based fine particles> In the present invention, (b) cerium oxide-based fine particles may be colloidal cerium oxide microparticles and/or cerium oxide microparticles having surface functional groups. The colloidal cerium oxide microparticles have an average particle diameter of about 1 to 400 nm, p, and cerium oxide microparticles having a surface functional group, and the surface functional group may be cerium oxide microparticles having a (meth) acrylonitrile group. (hereinafter referred to as reactive cerium oxide microparticles). The reactive cerium oxide fine particles may, for example, be a stanol group on the surface of the cerium oxide fine particles having an average particle diameter of about 0.005 to 1/zm, and a polymerizable unsaturated group having a functional group reactive with the stanol group. The organic compound is reacted thereby, and is obtained. The polymerizable unsaturated group may, for example, be a free-radical polymerizable (meth) acrylonitrile group. -11-200946995 The organic compound containing a polymerizable unsaturated group having a functional group reactive with the stanol group may, for example, be a compound represented by the general formula (I).

I CH2 = C — COR2 . · · (I) (式中，R1表示氫原子或甲基，R2表示鹵原子或I CH2 = C — COR2 . · · (I) (wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a halogen atom or

一 OCH2CH2NCO、一 OCHaCH — CH2、一OCH2CH 二 CHa. \/ \/An OCH2CH2NCO, an OCHaCH — CH2, an OCH2CH II CHa. \/ \/

0 N Η -OCHaCHaOHs -OH, -0(CH2)3 - Si(OCH3)3 所示之基）。 此種化合物方面，可使用例如丙烯酸、丙烯酸氯、丙烯 酸2-異氰酸乙酯、丙烯酸環氧丙酯、丙烯酸2,3-亞氨基丙酯、 丙烯酸2-羥基乙酯、丙烯醯氧基丙基三甲氧基矽烷等，及對 應於該等之丙烯酸衍生物的甲基丙烯酸衍生物。該等丙烯酸 衍生物或甲基丙烯酸衍生物可單獨使用，亦可組合二種以上 使用。 如此所得之結合有含聚合性不飽和基的有機化合物之 二氧化矽微粒，其活性能量線硬化成分，係以活性能量線照 射而交聯、硬化。 該反應性二氧化矽微粒具有使所得之硬被覆膜的耐磨 耗性提高的效果。 -12- 200946995 此種活性能量線感應型組成物（A)方面，其含有在二氧 化矽微粒中使具聚合性不飽和基的有機化合物結合所成之 化合物，市面上已有例如JSR公司製，商品名「opstar Z7530」、「opstar Z7524」、「opstar TU4086」等。 本發明中，該（b)成分之二氧化矽系微粒的含量在（A)成 分之活性能量線感應型組成物的固形成分中，通常爲5〜90 質量％左右。較佳爲10〜70質量％。 此外，在該（b)成分之二氧化矽系微粒中，二氧化矽粒子 〇 的平均粒徑，可以雷射繞射•散射法進行測定。該方法係於 對分散了粒子的液體照射雷射光之際，藉由繞射·散射之光 的強度變化，來測定平均粒徑。 ((B)球狀有機微粒） 本發明的硬被覆層形成材料中，（B)成分所使用的球狀 有機微粒方面，可例舉聚矽氧系微粒、三聚氰胺系樹脂微 粒、丙烯酸系樹脂微粒、丙烯酸-苯乙烯系共聚物微粒、聚 φ 碳酸酯系微粒、聚乙烯系微粒、聚苯乙烯系微粒、苯并鳥糞 胺系樹脂微粒等。該等爲球狀且粒度分布狹窄者爲佳。就防 眩性能的觀點而言，該球狀有機微粒的平均粒徑以6〜10//m 爲佳。該平均粒徑爲準照庫爾特粒度分析儀法（coulter counter method)的測定値。又，粒度分布爲以庫爾特顆粒計 數器法測定之平均粒徑在±2以m以內範圍的重量分率 (weight fraction)爲 70%以上較佳。 -13- 200946995 本發明中，該（B)成分的球狀有機微粒可單獨使用一 種，亦可組合二種以上使用，又，就防眩性能的觀點而言， 相對於前述（A)成分之活性能量線感應型組成物的固形成分 100質量份，其配合量較佳爲0.1〜30質量份，更佳爲1〜20 質量份。 本發明中，爲前述（A)成分之活性能量線感應型組成物 的硬化物，與爲該（B)成分之球狀微粒，可因應目的選擇各 種的折射率差。例如，以防眩性薄膜作爲高對比型時，爲了 〇 不顯現內部霧度，折射率差的絕對値以小者爲佳，以0〜0.03 更佳，0〜0.02特佳。又，以防眩性薄膜作爲廣用型時，爲 了顯現可控制內部霧度，以0.03〜0.2爲佳，0.04〜0.1更佳。 此外，活性能量線感應型組成物之硬化物的折射率，係就照 射活性能量線，使其硬化之硬化物之準照ns K 7 1 42的測定 値。又，球狀微粒的折射率，係根據單體組成，由含有單體 的折射率與含有質量比而計算的値。 〇 ((c)分散劑） 本發明的硬被覆層形成材料中，（C)成分所使用的分散 劑爲分子內至少具有一個極性基之物，該極性基方面，可例 舉羧基、羥基、磺基、1級胺基、2級胺基、3級胺基、醯胺 基、4級氣合（ammonio)驗、卩J±陡合（pyridinio)驗、擴基合 (sulphonio)鹼、銹基合（phosphonio)鹼等。該等中以羧基、磺 基、1〜3級胺基爲佳。該等極性基可於分子內導入一個，亦 可導入複數個。 -14· 200946995 分子內具有複數個極性基時，必須成分爲使各自具有極 性基之有機化合物彼此之間相結合的成分，該成分方面，可 例舉聚氧化烯烴二醇等。此種成分的分子量並無特別限定， 可選自數百左右至數十萬左右之廣泛之物。 該分子內至少具有一個極性基的分散劑，在膜厚相較於 球狀有機微粒的平均粒徑更大的硬被覆層中，可抑制該球狀 有機微粒的沉澱，使該微粒多數存在於硬被覆層表面附近， ▲ 具有提高防眩性能的作用。 Ο 關於該機制並非十分明確，但是吾人認爲有下述的考 量。 吾人認爲分散劑中的極性基係配位（coordinate)於球狀 有機微粒表面，導致有機微粒表面的極性產生變化，使得有 機微粒存在於表面附近的機率變高，結果在有機微粒平均粒 徑以上的膜厚中，硬被覆層表面附近亦有有機微粒存在，故 提高了防眩性能。 〇 又，該分散劑中極性基的具體例，可例舉來自烷基之碳 數1〜8的Ν,Ν-二烷基胺基的極性基。相關之導入極性基爲 有效的化合物，就容易取得性的觀點，特別以碳數2〜6的 Ν，Ν-二烷胺基烷醇爲佳。 該Ν，Ν-二烷胺基烷醇的具體例方面，可例舉Ν，Ν-二甲 基胺乙醇、Ν，Ν-二乙基胺乙醇、Ν,Ν-二丙基胺乙醇、Ν，Ν-二 丁基胺乙醇、Ν，Ν-二戊基胺乙醇、Ν,Ν-二己基胺乙醇等、及 -15- 200946995 將該等化合物中的乙醇部分以丙醇或是丁醇取代的化合物 等。此外，二烷基部分的2個烷基可爲相同或相異。 具有來自Ν,Ν-二烷胺基烷醇之極性基的分散劑方面、可 例舉Ν，Ν·二烷胺基烷醇改性聚氧化烯烴乙二醇。 本發明中，（C)成分的分散劑可單獨使用一種，亦可組 合二種以上使用。又，其配合量就硬被覆層的防眩性、耐磨 耗性、其他物性、經濟性等均衡的觀點而言，相對於爲前述 (Α)成分之活性能量線感應型組成物的固形成分1 〇〇質量 ❹ 份’爲0.01〜10質量份，更佳爲0.05〜5質量份。 (光聚合引發劑） 本發明之硬被覆層形成材料中，可依照所期望含有光聚 合引發劑。該光聚合引發劑方面，可例舉苯偶姻、苯偶姻甲 醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻·正丁醚、苯偶姻 異丁醚、乙醯苯、二甲基胺基乙醯苯、2，2-二甲氧基-2-苯基 乙醯苯、2,2-二乙氧基-2-苯基乙醯苯、2_羥基-2-甲基-1-苯基 ❿ 丙烷-1-酮、1-羥基環己基苯酮、2-甲基-1-[4-(甲基硫代）苯 基]-2-嗎啉代-丙烷-^酮、心（2_羥乙氧基）苯基-2(羥基·2_丙） 酮、二苯酮、對苯基二苯酮、4,4，-二乙基胺基二苯酮、二氯 二苯酮、2-甲基蒽醌、2-乙基蒽醌、2-三級丁基蒽醌、2-胺 基蒽醌' 2 -甲基9 -氧硫卩山卩星、2 -乙基9 -氧硫卩山噃、2 -氯9 -氧 硫卩山曜、2,4-二甲基9-氧硫岫α星、2,4-二乙基9-氧硫妯卩星、 苄基二甲基縮酮、乙醯苯二甲基縮酮、對二甲基胺基苯甲酸 酯等。 -16- 200946995 該等可單獨使用一種，亦可組合二種以上使用，又，相 對於全活性能量線硬化型化合物100質量份，其配合量通常 選擇0.2〜10質量份的範圍。此外，在此，全活性能量線硬 化型化合物’係指在（b)二氧化矽系微粒方面於使用反應性二 氧化矽微粒時，含有該化合物之意。 (硬被覆層形成材料的調製） 本發明所使用的硬被覆層形成材料，可因應需要，於適 當的溶劑中以各自設定之比率添加前述（A)成分的活性能量 線感應型組成物、（B)成分的球狀有機微粒、（C)成分的分散 劑’及視需要添加光聚合引發劑或各種添加成分，如抗氧化 劑、紫外線吸收劑、矽烷系偶合劑、光穩定劑、均平劑、消 泡劑等，藉由使其溶解或分散進行調製。 此時所使用的溶劑方面，可例舉己烷、庚烷等的脂肪族 烴、甲苯、二甲苯等的芳香族烴、二氯甲烷、氯化乙烯等的 _化烴、甲醇、乙醇、丙醇、丁醇等的醇、丙酮、甲基乙基 〇 酮、2 -戊酮、異佛爾酮、環己酮等酮、乙酸乙酯、乙酸丁酯 等的酯、乙基溶纖劑等的溶纖劑系溶劑等。 如此所調製之硬被覆層形成材料的濃度，其黏度方面， 若爲能夠塗覆的話’並無特別限制，可因應狀況適當選擇。 [透明塑膠薄膜] 本發明的防眩性硬被覆膜中，在透明塑膠薄膜的至少一 面’使用如前述方式調製的硬被覆層形成材料來形成硬被覆 層。 -17- 200946995 關於該透明塑膠薄膜並無特別限制，可自以往 用硬被覆膜基材之周知的塑膠薄膜中適當選擇而使 塑膠薄膜方面，可例舉聚對酞酸乙二酯（以_ 「PET」）' 聚對苯二甲酸丁二醇酯、聚萘二甲酸乙 聚酯薄膜、聚乙烯薄膜、聚丙烯薄膜、賽璐玢、二 素薄膜、三乙醯纖維素薄膜（以下稱爲「TAC薄膜. 纖維素丁酸酯薄膜、聚氯化乙烯薄膜、聚氯化亞乙 聚乙烯醇薄膜、乙烯-乙酸乙烯酯共聚物薄膜、聚 ^ 膜、聚碳酸酯薄膜、聚甲基戊烯薄膜、聚颯薄膜、 薄膜、聚醚颯薄膜、聚醚醯亞胺基薄膜、聚醯亞胺 氟樹脂薄膜、聚醯胺薄膜、丙烯酸樹脂薄膜、降莰 脂薄膜、環烯烴樹脂薄膜等的塑膠薄膜。此外，以 防眩性硬被覆膜作爲偏光板的保護薄膜使用時，因 向性優異，故以TAC薄膜爲特佳。 該等塑膠薄膜可爲透明或半透明，又，有著色 均可，可因應用途而適當選擇。例如使用於液晶顯 護時，以無色透明的薄膜較爲合適。 該等塑膠薄膜的厚度並無特別限制，可依狀 定，但是通常爲15〜300μιη，較佳爲30〜200/zm 又，此塑膠薄膜在提高與其表面所設置之層的密 下，可依所望於單面或兩面，以氧化法或凹凸化 面處理。上述氧化法方面，可例舉電暈放電處理、 鉻酸處理（濕式）、火焰處理、熱風處理、臭氧· 作爲光學 用。此種 =可稱爲 二酯等的 乙醯纖維 j )、乙醯 烯薄膜、 苯乙烯薄 聚醚醚酮 :基薄膜、 烯基系樹 本發明之 光學的等 、無著色 示體的保 況適當選 的範圍。 性之目的 等施以表 S漿處理、 外線照射 -18- 200946995 處理等，又’凹凸化法方面’可例舉噴砂（sandblast)法、溶 劑處理法等。該等的表面處理法可因應塑膠薄膜的種類而適 當選用’但一般而言，自效果及操作性等之觀點言之，較佳 爲使用電暈放電處理法。又，亦可設置底塗層。 [硬被覆層的形成] 於該透明塑膠薄膜的至少一面上，使用以往周知的方 法’例如棒塗布法、刀塗布法、輥塗布法、刀片塗布（blade coating)法、模塗布法、凹版印刷（gravure)塗布法等，塗覆該 〇 硬被覆層形成材料使其形成塗膜，乾燥後，對此照射活性能 量線使該塗膜硬化，形成硬被覆層。 活性能量線方面，可例舉紫外線或電子束等。上述紫外 線以高壓水銀燈、無電極燈、金屬鹵素燈、氙燈等所獲得的 照射量通常爲100〜500 mJ/cm2，一方面，電子束可以電子束 加速器等來獲得’照射量通常爲150〜350kV。該等活性能量 線中，特別以紫外線較佳。此外，使用電子束時，可不添加 ❹ 光聚合引發劑而獲得硬化膜。 如此所形成之硬被覆層的厚度，必須相較於本發明中所 使用之球狀有機微粒的平均粒徑更大，因此，下限爲7以m 左右，上限方面，就防止因硬被覆層的硬化收縮導致硬被覆 膜捲曲的觀點言之’爲20/zm左右。較佳的厚度爲8〜15"m 之範圍。 [防眩性硬被覆膜] (光學特性） -19- 200946995 如此所形成之本發明防眩性硬被覆膜的光學特性，因其 型態其較佳的値有所不同。 在高對比型時，通常內部霧値爲〇〜10%。即使內部霧 値在此範圍時產生閃爍，亦可達成高對比，故可完全依照顯 示器的種類（設計思想）使用。內部霧値若超過10%時，並無 法獲得高對比（成爲廣用型）。又，在廣用型時，通常內部霧 値爲5〜40%。內部霧値未達5%時，抑制閃爍的性能並不充 分，若超過40%時，可見度降低。廣用型之防眩性硬被覆膜 其較佳的內部霧値通常爲10〜30%，更佳爲15〜25%。 又，外表面霧値就高對比型與廣用型之可見度的観點而 言，以20 %以下爲佳，由防眩性的觀點而言以5 %以上爲佳。 此外，內部霧値係表示僅起因於薄膜內部之光散射的霧 値，外表面霧値係指僅起因於薄膜表面凹凸所致光散射的霧 値，總霧値係表示該內部霧値與外表面霧値的總和。在本發 明的防眩性硬被覆膜中，總霧値相當於JIS K 7 1 3 6所規定的 霧値。硬被覆層的內部霧値及外表面霧値的計算方法記載如 下。 <硬被覆層的內部霧値及外表面霧値的計算方法> 首先，準照JIS K 7136，測定本發明之防眩性硬被覆膜 的霧値（本發明中，爲了與其他霧値區別，故稱爲「總霧値」）。 接著，將厚度20/zm的透明黏著薄片貼著於該防眩性硬 被覆膜的硬被覆層側邊，作爲內部霧値計算用試料。將該黏 著薄片的霧値與內部霧値計算用試料的霧値，以同於上述方 -20- 200946995 法進行測定。其後，藉由自內部霧値計算用試料的霧値減去 該黏著薄片的霧値，來計算防眩性硬被覆膜之硬被覆層的內 部霧値。此外，本發明的防眩性硬被覆膜所使用之透明塑膠 薄膜的霧値，通常未達0.01%，故可無視於其影響。透明塑 膠薄膜的霧値若爲0.01 %以上時，以該計算之自內部霧値進 而減去透明塑膠薄膜之霧値的値，作爲硬被覆層的內部霧 値。 最後，自該總霧値減去內部霧値來計算防眩性硬被覆膜 之硬被覆層的外表面霧値。 進而，無論是高對比型、與廣泛使用型，60°光澤率以 20〜80爲佳》60°光澤率若超過80時，表面光澤率變大（光 的反射大），對防眩性有不良的影響》60°光澤率若不足20, 易產生褪色。又，防眩性硬被覆膜的全透光率以88%以上爲 佳，90%以上更佳。全透光率不足88%，會有透明性不充分 的問題。 ❹ 此外，該60°光澤率係準照JIS K 7105的測定値，該全 透光率係準照ns K 7136的測定値。 (效果） 本發明的防眩性硬被覆膜可產生下述的效果。 (1)關於分散劑的效果並無詳細的解釋機制，但吾人認爲或許 是分散劑的極性基配位於有機微粒表面，導致有機微粒表面 的極性產生變化，具有使有機微粒存在於硬被覆層表面附近 的機率變高的效果。因此，在相較於有機微粒平均粒徑更大 -21- 200946995 的膜厚中，有機微粒亦存在於硬被覆層表面附近，故提高了 防眩性，同時減低塗膜（coating)的不均。 (2) 由於不可避免的膜厚變大，相較於使用同樣大小的有機微 粒所製作之以往的防眩性硬被覆膜，可以預見鉛筆硬度提高 了。 (3) 分散劑的添加量愈多，有機微粒存在於硬被覆層表面附近 的機率變高，故藉由分散劑的添加量，使得調整表面狀態（外 I 表面霧値、60°光澤率）成爲可能》 〇 (其他功能層） 本發明的防眩性硬被覆膜中，可依需要於最上層設置能 賦予防反射性等目的之抗反射層，例如矽氧烷系被膜、氟系 被膜等。此時，該抗反射層的厚度以0.05〜1# m左右爲適 當。藉由設置抗反射層，可解除由太陽光、螢光燈等所致反 射產生畫面反射（reflection)的現象，又，在抑制表面的反射 率，而使全透光率提高、透明性提髙。此外，可因應抗反射 〇 層的種類謀求抗靜電性的提高。 (黏著劑層） 本發明的防眩性硬被覆膜中，於塑膠薄膜之硬被覆層的 相反面上，可形成用於貼著液晶顯示體等之黏附體（adherend) 的黏著劑層。構成黏著劑層的黏著劑方面，較佳爲使用適合 於光學用途的例如丙烯酸系黏著劑、胺甲酸酯系黏著劑、聚 矽氧系黏著劑。該黏著劑層的厚度，通常爲5〜100//m，較 佳爲10〜60 的範圍。 -22- .200946995 進而’於該黏著劑層上，可因應需要設置剝離薄片。該 剝離薄片方面’可例舉於聚對酞酸乙二酯、聚丙烯等各種塑 膠薄膜上，塗覆聚矽氧樹脂等剝離劑而成之物等。關於該剝 離薄片的厚度並無特別限制，通常爲20〜15〇/ζιη左右。 形成此種黏著劑層的防眩性硬被覆膜，適合使用於對 CRT、LCD、PDP等顯示器，可賦予防眩性能或耐磨耗性能 等的構件’特別是極適合使用於LCD等的偏光板黏貼用。 [偏光板] 又’本發明亦提供將前述本發明的防眩性硬硬被覆膜貼 合於偏光鏡所成的偏光板。 LCD中的液晶晶胞一般具有將形成有配向層的2片透明 電極基板，使其配向層作爲內側，以間隔件配置成設定的間 隙，將其周邊密封，於該間隙中夾持液晶材料，同時於上述 2片透明電極基板的外側表面，各自經由黏著劑層配設偏光 板的構造。 0 第1圖表示上述偏光板一例構成的斜視圖。如圖所示， 一般而言，該偏光板10係具有在聚乙稀醇系偏光鏡1的兩 面貼合有三乙醯基纖維素（TAC)薄膜2及2'之三層構造的基 材，之後，於其單面形成用以貼著液晶晶胞等光學零件的黏 著劑層3，進而，於該黏著劑層3貼上剝離薄片4。又，通 常在該偏光板之該黏著劑層3的相反面上，設置有表面保護 薄膜5。 200946995 本發明的偏光板係於偏光鏡1的兩面所設置的τ AC薄膜 2、2'中，在一面TAC薄膜上，設置有關上述本發明的硬被 覆層。在偏光板上設置黏著劑層3、剝離薄片4及表面保護 薄膜5時，特別於表面保護薄膜5側的TAC薄膜2'側上設置 關於本發明的硬被覆層。 在製造本發明之偏光板的方法方面，可藉由例如以下所 示的操作來進行。此外，第2圖表示本發明偏光板一例的構 成的剖面模式圖。 首先，基材的透明塑膠薄膜係使用如TAC薄膜之無光學 異方向性的薄膜12'，於其一面形成本發明的硬被覆層13, 爲防眩性硬被覆膜14。接著，使用接著劑層15、15'，在偏 光鏡11的一面上積層未形成硬被覆層13的TAC薄膜12， 且在偏光鏡的相反面上積層該防眩性硬被覆膜14。於透明塑 膠薄膜上使用TAC薄膜時，爲了提高以接著劑所致積層的密 接性’亦可進行前述表面處理以外的皂化處理等。 φ 藉此，可獲得防眩性能與耐磨耗性能優異的偏光板20。 偏光板20亦可因應需要，於設置硬被覆層13的面上，設置 該第1圖所示可剝離的表面保護薄膜5，或於其相反面上設 置用於黏貼液晶晶胞等光學零件的黏著劑層16,或剝離薄片 17 » 本發明的偏光板可使用於始自LCD的液晶晶胞用、亦可 使用於光量調整用、偏光干涉應用裝置用、光學的缺陷檢驗 器用等。 -24- 200946995 實施例 接著，以實施例進而詳細說明本發明，但本發明並不限 定於該等實施例。 此外，有機微粒的平均粒徑及折射率、活性能量線感應 型組成物的硬化物的折射率以及硬被覆膜的性能，係準照下 述的方法而求得。 <有機微粒> (1) 平均粒徑 © _ 使用庫爾特顆粒計數器[Beckman Coulter(股）製，商品名 「Multi sizer 3」]，作爲0.5 %之離子交換水的分散液，於25°C 以庫爾特顆粒計數器法進行測定。 (2) 折射率 根據有機微粒單體的組成，由含有單體的折射率與含有 質量比來計算平均折射率。 <活性能量線感應型組成物> Q (3)硬化物的折射率 在各調製例中，製作由活性能量線感應型組成物（A)、 光引發劑與稀釋溶劑所成的塗布劑。將該等以同於實施例的 方法於TAC薄膜[富士軟片（股）製，商品名「TAC80TD80ULH」] 上進行塗膜，成爲硬化物之折射率測定用的硬被覆膜。使用 Atago(股）製的阿倍折射計，準照JIS K 7142求得該等硬被覆 層的折射率，以此作爲活性能量線感應型組成物之硬化物的 折射率。 -25- 200946995 <硬被覆膜> (4) 全透光率及總霧値 使用村上色彩技術硏究所（股）製的霧度•透過率計 「HM-150」，準照JIS K 7136，測定全透光率及總霧値。 (5) 內部霧値及外表面霧値 於丙烯酸系黏著劑[日本Carbide公司製，商品名 「PE-1 21」]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， ❺ 製作黏著劑溶液。於厚度50/zm的聚對酞酸乙二酯[東洋防 績公司製，商品名「A4300」]薄膜上，塗布黏著劑溶液，使 乾燥後的厚度成爲20μπι，在l〇〇°C下乾燥3分鐘並製作黏 著薄片。將製作的黏著薄片黏貼於防眩性硬被覆膜的硬被覆 層側作爲內部霧値計算用試料。測定該黏著薄片與內部霧値 計算用試料的霧値，以自內部霧値計算用試料的霧値減去黏 著薄片的霧値之値作爲防眩性硬被覆膜之硬被覆層的內部 φ 霧値。此外，爲了確認，在測定實施例及比較例所使用之防 眩性硬被覆膜之爲透明塑膠薄膜的三乙醯纖維素薄膜之單 體的霧値時，爲不足0.01%，而可被忽略的値。霧値的測定 同上述（4)。 (6) 防眩性的評價 將經由丙烯酸系黏著劑使硬被覆膜貼附於丙烯酸樹脂 黑板[住友化學（股）製]而成的樣本於螢光燈下以目視觀察， 以下述判定基準評價防眩性。 -26- 200946995 〇：螢光燈的抗反射性充分，且褪色少 X:螢光燈的抗反射性不充分，或螢光燈的抗反射性雖然充 分，但是褪色大、可見度差 (7) 60°光澤率 使用日本電色工業（股）製輕便型光澤計「PG-1M」，準 照JIS K 7105進行測定。 (8) 鉛筆硬度 準照JIS K 5400，使用安田精機製作所（股）的鉛筆刮痕 〇 塗膜硬度試驗機「N0553-M1」進行測定。 (9) 塗膜不均 以目視觀察硬被覆層表面根據下述的判定基準評價塗 膜不均。 〇：塗膜面整體看起來很平均 X:塗膜面上防眩性高的部分與低的部分混雜一起，整體看 起來不平均 〇 調製例1 將（A)活性能量線感應型組成物之硬被覆劑[JSR公司 製，商品名「op star Z7 524」，固形成分濃度70質量％、含 有反應性二氧化矽微粒與多官能丙烯酸酯的全活性能量線 硬化型化合物65質量％、光引發劑5質量％、甲基乙基酮30 質量％、硬化物的折射率1.50] 100質量份；（B)球狀有機粒子 的PMM A微粒[綜硏化學公司製，平均粒徑5# m、折射率1.49] 11.25質量份；（C)分散劑之具有三級胺作爲極性基的分散液 -27- .200946995 [日本BYK Chemie公司製，商品名「disperbyk 103」，固形 成分濃度40質量％] 3質量份；稀釋溶劑之丙二醇單甲醚90 質量份予以均勻混合，製作固形成分爲約40質量％的防眩性 硬被覆層用塗布劑1。該塗布劑的配合量如表1所示。 調製例2 除了（B)球狀有機微粒使用丙烯酸微粒[綜硏化學公司 製，平均粒徑8# m、折射率_ 1.55] 11.25質量份；及（C)分散劑 係使用「disperbyk 103」（前述）0.5質量份以外，其他與調 ❹ 製例1 一樣製作固形成分約40質量％的防眩性硬被覆層用塗 布劑2。該塗布劑的配合量如表1所示。 調製例3 除了（C)分散劑使用「disperbyk 103」（前述）〇.75質量份 以外，其他與調製例2相同製作固形成分約40質量％的防眩 性硬被覆層用塗布劑3。該塗布劑的配合量如表1所示。 調製例4 ❹ 除了（C)分散劑使用「disperbyk 103」（前述）ι質量份以 外，其他與調製例2相同製作固形成分約40質量％的防眩性 硬被覆層用塗布劑4。該塗布劑的配合量如表1所示。 調製例5 除了（C)分散劑使用「disperbyk 103」（前述）ι·5質量份 以外，其他與調製例2相同製作固形成分約40質量％的防眩 性硬被覆層用塗布劑5。該塗布劑的配合量如表1所示。 調製例6 -28- .200946995 除了（C)分散劑使用己內酯改性聚乙二醇[日本BYK Chemie公司製，商品名「disperbyklll」，固形成分濃度90 質量％]1質量份以外，其他與調製例2相同製作固形成分約 40質量％的防眩性硬被覆層用塗布劑6。該塗布劑的配合量 如表1所示。 調製例7 除了（C)分散劑使用己內酯改性聚乙二醇[日本BYK Chemie公司製，商品名「disperbykl63」，固形成分濃度45 ❹ 質量％] 1質量份以外，其他與調製例2相同製作固形成分約 40質量％的防眩性硬被覆層用塗布劑7。該塗布劑的配合量 如表1所示。 調製例8 除了（C)分散劑使用兩末端以己內酯及二丁胺乙醇銨鹽 改性的聚乙二醇[日本BYKChemie公司製，商品名「disperbyk 180」，固形成分濃度81質量％]1質量份以外，其他與調製 φ 例2相同製作固形成分約40質量％的防眩性硬被覆層用塗布 劑8。該塗布劑的配合量如表1所示。 調製例9 除了不使用（C)分散劑以外，其他與調製例1相同製作 固形成分約40質量％的防眩性硬被覆層用塗布劑9。該塗布 劑的配合量如表1所示。 調製例10 -29- .200946995 除了（A)成分使用不含二氧化矽微粒的硬被覆劑[大日精 化（股）製，商品名「Seika beam EXF-L203(CS-1)，固形成分 濃度70質量％、含有反應性單體與多官能丙烯酸酯的活性能 量線硬化型化合物65質量％、光引發劑5質量％、丙二醇單 甲基乙酸酯30質量％、硬化物之折射率1.52」100質量份以 外，其他與調製例1相同，製作固形成分約40質量％的防眩 性硬被覆層用塗布劑10。該塗布劑的配合量如表1所示。 調製例11 ❹ 除了不使用（C)分散劑以外，其他與調製例2相同，製 作固形成分約40質量％的防眩性硬被覆層用塗布劑11。該 塗布劑的配合量如表1所示。 調製例12 除了不使用（B)球狀有機微粒以外，其他與調製例1相 同，製作固形成分約40質量％的防眩性硬被覆層用塗布劑 12。該塗布劑的配合量如表1所示。 φ 實施例1 作爲透明塑膠薄膜所使用之厚度80 的TAC薄膜 [富士軟片（股）製，商品名「TAC80TD80ULH」]的表面上，以 麥耶棒塗布機（mayer bar coater)塗覆調製例1所得的塗布劑 1使硬化膜厚成爲約10#m。在70°C的烤爐下使其乾燥1分 鐘後，以高壓水銀燈照射300m〗/cm2的紫外線，形成硬被覆 層，並製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 -30- .200946995 實施例2 除了以麥耶棒塗布機塗覆調製例2所得的塗布劑2，使 硬化膜厚成爲約10/zm以外，其他與實施例1相同，進行操 作，並製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 實施例3 除了以麥耶棒塗布機塗覆調製例3所得的塗布劑3,使 ©硬化膜厚成爲約10/zm以外，其他與實施例1相同進行操 作，並製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 實施例4 除了以麥耶棒塗布機塗覆調製例4所得的塗布劑4，使 硬化膜厚成爲約10//m以外，其他與實施例1相同進行操 作，並製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 〇 實施例5 除了以麥耶棒塗布機塗覆調製例5所得的塗布劑5，使 硬化膜厚成爲約10/zm以外，其他與實施例1相同進行操 作，製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 實施例6 -31- 200946995 除了以麥耶棒塗布機塗覆調製例6所得的塗布劑6，使 硬化膜厚成爲約lOym以外，其他與實施例1相同進行操 作，製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 實施例7 除了以麥耶棒塗布機塗覆調製例7所得的塗布劑7，使 硬化膜厚成爲約10#m以外，其他與實施例1相同進行操 作，製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 實施例8 除了以麥耶棒塗布機塗覆調製例8所得的塗布劑8，使 硬化膜厚成爲約10/zm以外，其他與實施例1相同進行操 作，製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 比較例1 〇 除了以麥耶棒塗布機塗覆調製例9所得的塗布劑9，使 硬化膜厚成爲約lOym以外，其他與實施例1相同進行操 作，製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 比較例2 除了以麥耶棒塗布機塗覆調製例9所得的塗布劑9，使 硬化膜厚成爲約5#m以外，其他與實施例1相同進行操作， 製作防眩性硬被覆膜。 -32- 200946995 該硬被覆膜的性能如表2所示。 比較例3 ，使 行操 除了以麥耶棒塗布機塗覆調製例9所得的塗布劑9 硬化膜厚成爲約4.5/zm以外，其他與實施例1相同進 作，製作防眩性硬被覆膜。 Λ 該硬被覆膜的性能如表2所示。 比較例4 10， 行操 除了以麥耶棒塗布機塗覆調製例1〇所得的塗布劑 使硬化膜厚成爲約10//m以外，其他與實施例1相同進 作，製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 比較例5 1 1 ' 行操 除了以麥耶棒塗布機塗覆調製例所得的塗布劑 使硬化膜厚成爲約l〇#m以外，其他與實施例1相同進 作，製作防眩性硬被覆膜。 〇 該硬被覆膜的性能如表2所示。 比較例6 12， 行操 除了以麥耶棒塗布機塗覆調製例12所得的塗布劑 使硬化膜厚成爲約l〇/zm以外，其他與實施例1相同邊 作，製作防眩性硬被覆膜。 該硬被覆膜的性能如表2所示。 -33- 200946995 表10 N Η -OCHaCHaOHs -OH, -0(CH2)3 - a group represented by Si(OCH3)3). As such a compound, for example, acrylic acid, chloro acrylate, 2-isocyanatoethyl acrylate, glycidyl acrylate, 2,3-iminopropyl acrylate, 2-hydroxyethyl acrylate, propylene methoxy propyl acrylate can be used. A trimethoxy decane or the like, and a methacrylic acid derivative corresponding to the acrylic acid derivatives. These acrylic acid derivatives or methacrylic acid derivatives may be used singly or in combination of two or more. The cerium oxide fine particles obtained by combining the organic compound containing a polymerizable unsaturated group and the active energy ray-hardening component are crosslinked and hardened by irradiation with an active energy ray. The reactive cerium oxide fine particles have an effect of improving the abrasion resistance of the obtained hard coating film. -12- 200946995 The active energy ray-inductive composition (A) contains a compound obtained by combining an organic compound having a polymerizable unsaturated group in cerium oxide microparticles, and is commercially available, for example, from JSR Corporation. The product names are "opstar Z7530", "opstar Z7524", "opstar TU4086", etc. In the present invention, the content of the cerium oxide-based fine particles of the component (b) is usually from about 5 to 90% by mass in the solid content of the active energy ray-sensitive composition of the component (A). It is preferably 10 to 70% by mass. Further, in the cerium oxide-based fine particles of the component (b), the average particle diameter of the cerium oxide particles 〇 can be measured by a laser diffraction/scattering method. This method measures the average particle diameter by varying the intensity of the diffracted and scattered light when the liquid in which the particles are dispersed is irradiated with the laser light. ((B) spherical organic fine particles) The spherical organic fine particles used in the component (B) in the hard coating layer forming material of the present invention may, for example, be a polyfluorinated fine particle, a melamine resin fine particle or an acrylic resin fine particle. Examples of acrylic acid-styrene copolymer fine particles, polyφ carbonate fine particles, polyethylene fine particles, polystyrene fine particles, and benzoguanamine resin fine particles. These are spherical and have a narrow particle size distribution. The spherical organic fine particles preferably have an average particle diameter of 6 to 10/m in terms of antiglare properties. The average particle size is measured by a coulter counter method. Further, the particle size distribution is preferably a weight fraction of an average particle diameter measured within a range of ± 2 m or less as measured by a Coulter Counter Counter Method of 70% or more. In the present invention, the spherical organic fine particles of the component (B) may be used singly or in combination of two or more kinds, and in terms of antiglare properties, with respect to the above (A) component. The solid content of the active energy ray-sensitive composition is 100 parts by mass, and the compounding amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. In the present invention, the cured product of the active energy ray-inductive composition of the component (A) and the spherical fine particles of the component (B) can be selected for various refractive index differences depending on the purpose. For example, when the antiglare film is used as the high contrast type, the absolute value of the refractive index difference is preferably small in order to prevent the internal haze from appearing, and is preferably 0 to 0.03, more preferably 0 to 0.02. Further, when the antiglare film is used as a wide-purpose type, it is preferable to exhibit a controllable internal haze of 0.03 to 0.2, more preferably 0.04 to 0.1. Further, the refractive index of the cured product of the active energy ray-inductive composition is measured by illuminating the active energy ray to make the hardened hardened material ns K 7 1 42 値. Further, the refractive index of the spherical fine particles is calculated from the refractive index of the monomer alone and the mass ratio according to the monomer composition. 〇 ((c) dispersing agent) The dispersing agent used for the (C) component in the hard coating layer forming material of the present invention is a substance having at least one polar group in the molecule, and examples of the polar group include a carboxyl group and a hydroxyl group. Sulfo, class 1 amine, grade 2 amine, grade 3 amine, guanamine, grade 4 ammonia, 卩J±pyridinio, sulphonio base, rust A phosphonio base or the like. Among these, a carboxyl group, a sulfo group, and a 1 to 3-membered amine group are preferred. The polar groups may be introduced into one molecule or a plurality of polar groups. -14· 200946995 When a plurality of polar groups are contained in the molecule, the essential component is a component in which the organic compounds each having a polar group are bonded to each other, and examples of the component include a polyoxyalkylene glycol. The molecular weight of such a component is not particularly limited, and may be selected from a wide range of from about several hundred to several hundreds of thousands. In the hard coating layer having at least one polar group in the molecule, in the hard coating layer having a larger film thickness than the average particle diameter of the spherical organic fine particles, precipitation of the spherical organic fine particles can be suppressed, and the fine particles are mostly present in the hard Near the surface of the coating layer, ▲ has an effect of improving anti-glare properties. Ο The mechanism is not very clear, but I think the following considerations apply. It is believed that the polar group in the dispersant is coordinated to the surface of the spherical organic fine particles, resulting in a change in the polarity of the surface of the organic fine particles, so that the probability of the organic fine particles existing near the surface becomes high, and as a result, the average particle diameter of the organic fine particles is obtained. In the above film thickness, organic fine particles are also present in the vicinity of the surface of the hard coating layer, so that the antiglare property is improved. Further, specific examples of the polar group in the dispersant include a polar group derived from an anthracene-dialkylamino group having 1 to 8 carbon atoms of the alkyl group. In view of the fact that the polar group is an effective compound, it is easy to obtain a viewpoint, and in particular, a ruthenium-dialkylaminoalkanol having 2 to 6 carbon atoms is preferred. Specific examples of the hydrazine and hydrazine-dialkylaminoalkanol include hydrazine, hydrazine-dimethylamine ethanol, hydrazine, hydrazine-diethylamine ethanol, hydrazine, hydrazine-dipropylamine ethanol, and hydrazine. , Ν-dibutylamine ethanol, hydrazine, hydrazine-dipentylamine ethanol, hydrazine, hydrazine-dihexylamine ethanol, etc., and -15-200946995 The ethanol portion of the compounds is replaced by propanol or butanol Compounds, etc. Further, the two alkyl groups of the dialkyl moiety may be the same or different. The dispersant having a polar group derived from an anthracene, fluorene-dialkylaminoalkanol may, for example, be a decyl dialkylaminoalkanol-modified polyoxyalkylene glycol. In the present invention, the dispersing agent of the component (C) may be used singly or in combination of two or more. In addition, the blending amount is a solid content of the active energy ray-inductive composition which is the above-mentioned (Α) component from the viewpoint of the balance of the anti-glare property, the abrasion resistance, the other physical properties, and the economy of the hard coating layer. The 〇〇 mass ' portion is 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass. (Photopolymerization Initiator) The hard coating layer forming material of the present invention may contain a photopolymerization initiator as desired. The photopolymerization initiator may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether or acetophenone. , dimethylaminoethyl benzene, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2-hydroxy-2- Methyl-1-phenylindole propan-1-one, 1-hydroxycyclohexyl benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane- ^ketone, heart (2_hydroxyethoxy)phenyl-2(hydroxy-2-propanone), benzophenone, p-phenylbenzophenone, 4,4,-diethylaminobenzophenone, Dichlorobenzophenone, 2-methylhydrazine, 2-ethylhydrazine, 2-tributylphosphonium, 2-aminopurine' 2 -methyl 9-oxosulfonate, comet, 2 -ethyl 9-oxosulfonium, 2 -chloro 9-oxosulfonium, 2,4-dimethyl 9-oxopurine alpha, 2,4-diethyl 9-oxosulfonium Star, benzyl dimethyl ketal, acetophenone ketal, p-dimethylamino benzoate and the like. -16-200946995 These may be used singly or in combination of two or more kinds, and the compounding amount is usually in the range of 0.2 to 10 parts by mass based on 100 parts by mass of the total active energy ray-curable compound. Here, the fully active energy ray-hardening type compound means that the compound is contained when the reactive cerium oxide fine particles are used in the case of (b) cerium oxide-based fine particles. (Preparation of Hard Coating Layer Forming Material) The hard coating layer forming material used in the present invention may be added to the active energy ray-inductive composition of the component (A) in a suitable ratio in a suitable solvent, if necessary. B) spherical organic fine particles of the component, dispersant of the component (C) and, if necessary, a photopolymerization initiator or various additional components such as an antioxidant, an ultraviolet absorber, a decane coupling agent, a light stabilizer, and a leveling agent An antifoaming agent or the like is prepared by dissolving or dispersing it. The solvent to be used in this case may, for example, be an aliphatic hydrocarbon such as hexane or heptane, an aromatic hydrocarbon such as toluene or xylene, or a hydrocarbon such as dichloromethane or chlorinated ethylene, methanol, ethanol or propylene. Alcohol such as alcohol or butanol, acetone, methyl ethyl fluorenone, ketone such as 2-pentanone, isophorone or cyclohexanone, esters such as ethyl acetate and butyl acetate, ethyl cellosolve, etc. The cellosolve is a solvent or the like. The concentration of the hard coating layer forming material thus prepared is not particularly limited as long as it can be applied in terms of viscosity, and can be appropriately selected depending on the conditions. [Transparent plastic film] In the antiglare hard coating film of the present invention, a hard coating layer is formed on at least one side of the transparent plastic film by using a hard coating layer forming material prepared as described above. -17- 200946995 The transparent plastic film is not particularly limited, and may be appropriately selected from the conventional plastic film of the hard coating substrate, and the polyethylene film may be exemplified by polyethylene terephthalate. _ "PET")' Polybutylene terephthalate, polyethylene naphthalate film, polyethylene film, polypropylene film, cellophane, bismuth film, triacetyl cellulose film (hereinafter referred to as "TAC film. Cellulose butyrate film, polyvinyl chloride film, polyvinyl chloride polyvinyl alcohol film, ethylene-vinyl acetate film, poly film, polycarbonate film, polymethyl pentane Alkene film, polyfluorene film, film, polyether ruthenium film, polyether fluorene-based film, polyamid fluororesin film, polyamide film, acrylic film, sulphur film, cycloolefin resin film, etc. In addition, when the anti-glare hard coating film is used as a protective film for a polarizing plate, it is excellent in the directionality, so TAC film is particularly preferable. The plastic film can be transparent or translucent, and has a coloring. Yes, depending on the purpose Suitable for use in liquid crystal display, for example, a colorless and transparent film is suitable. The thickness of the plastic film is not particularly limited and may be determined according to the shape, but is usually 15 to 300 μm, preferably 30 to 200 / Zm Further, the plastic film can be treated by oxidation or roughening on one side or both sides in accordance with the adhesion of the layer provided on the surface thereof. The above oxidation method can be exemplified by corona discharge treatment, chromium Acid treatment (wet), flame treatment, hot air treatment, ozone. For optical use. Such = acetonitrile fiber, which can be called diester, etc., ethene film, styrene, thin polyetheretherketone: base film The alkenyl-based tree has an appropriate range for the optical condition of the present invention, such as an optical non-coloring body. The purpose of the property is to apply the surface S slurry treatment, the external irradiation -18-200946995 treatment, etc., and the 'concavo-convex method. 'Sandblast method, solvent treatment method, etc. can be exemplified. These surface treatment methods can be appropriately selected depending on the type of plastic film, but in general, from the viewpoints of effects and workability, etc., it is preferred that use A corona discharge treatment method. Further, an undercoat layer may be provided. [Formation of a hard coating layer] On at least one surface of the transparent plastic film, a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, or the like is used. A blade coating method, a die coating method, a gravure coating method, or the like, coating the crucible hard coating layer forming material to form a coating film, and after drying, irradiating the active energy ray to harden the coating film The active energy ray may, for example, be an ultraviolet ray, an electron beam, etc. The ultraviolet ray is usually obtained by a high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a xenon lamp, or the like, and the irradiation amount is usually 100 to 500 mJ/cm 2 . On the one hand, the electron beam can be obtained by an electron beam accelerator or the like, and the irradiation amount is usually 150 to 350 kV. Among these active energy rays, ultraviolet rays are particularly preferred. Further, when an electron beam is used, a cured film can be obtained without adding a photopolymerization initiator. The thickness of the hard coating layer thus formed must be larger than the average particle diameter of the spherical organic fine particles used in the present invention. Therefore, the lower limit is about 7 m, and the upper limit is prevented from being hard coated. The viewpoint that the hardening shrinkage causes the hard coating film to curl is '20/zm or so. A preferred thickness is in the range of 8 to 15 "m. [Anti-glare hard coating film] (Optical property) -19- 200946995 The optical characteristics of the antiglare hard coating film of the present invention thus formed are different depending on the type thereof. In the case of high contrast, the internal haze is usually ~10%. Even if the internal mist is flickering in this range, high contrast can be achieved, so it can be used in full accordance with the type of display (design idea). If the internal smog exceeds 10%, there is no way to obtain high contrast (becoming a wide-ranging type). Further, in the case of a wide use type, the internal haze is usually 5 to 40%. When the internal haze is less than 5%, the performance of suppressing flicker is not sufficient, and if it exceeds 40%, the visibility is lowered. A widely used anti-glare hard coating film preferably has an internal haze of usually 10 to 30%, more preferably 15 to 25%. Further, the outer surface smog is preferably 20% or less in terms of the visibility of the high-contrast type and the wide-use type, and more preferably 5% or more from the viewpoint of anti-glare property. Further, the internal haze means a haze caused only by light scattering inside the film, and the outer surface haze means a haze caused only by light scattering due to irregularities on the surface of the film, and the total haze indicates the inside haze and the outside. The sum of the surface smog. In the antiglare hard coating of the present invention, the total haze corresponds to the haze specified in JIS K 7 1 3 6 . The calculation method of the internal haze and the outer surface haze of the hard coating layer is as follows. <Method for Calculating Internal Haze and External Surface Smog of Hard Coating Layer> First, the smog of the anti-glare hard coating film of the present invention is measured in accordance with JIS K 7136 (in the present invention, in order to cope with other mists) The difference is called "total smog". Next, a transparent adhesive sheet having a thickness of 20/zm was placed on the side of the hard coating layer of the antiglare hard coating film to prepare a sample for internal haze calculation. The haze of the adhesive sheet and the haze of the internal haze calculation sample were measured in the same manner as in the above-mentioned method -20-200946995. Then, the internal haze of the hard coating layer of the antiglare hard coating film was calculated by subtracting the haze of the adhesive sheet from the haze of the internal haze calculation sample. Further, the haze of the transparent plastic film used in the antiglare hard coating film of the present invention is usually less than 0.01%, so that the influence thereof can be ignored. When the smog of the transparent plastic film is 0.01% or more, the enthalpy of the transparent plastic film is subtracted from the internal mist by the calculation, and the internal mist of the hard coating layer is used. Finally, the internal haze was subtracted from the total haze to calculate the outer surface haze of the hard coating layer of the antiglare hard coating. Further, regardless of the high contrast type and the widely used type, the 60° gloss ratio is preferably 20 to 80. When the 60° gloss ratio exceeds 80, the surface gloss ratio becomes large (reflection of light is large), and the antiglare property is If the 60° gloss rate is less than 20, it will easily cause fading. Further, the total light transmittance of the antiglare hard coating film is preferably 88% or more, more preferably 90% or more. The total light transmittance is less than 88%, and there is a problem that the transparency is insufficient. Further, the 60° gloss ratio is measured in accordance with JIS K 7105, and the total light transmittance is measured by ns K 7136. (Effects) The antiglare hard coating film of the present invention can produce the following effects. (1) There is no detailed explanation about the effect of the dispersant, but we believe that it may be that the polar group of the dispersant is located on the surface of the organic fine particles, resulting in a change in the polarity of the surface of the organic fine particles, so that the organic fine particles are present in the hard coating layer. The probability of getting near the surface becomes high. Therefore, in the film thickness which is larger than the average particle diameter of the organic fine particles from 21 to 200946995, the organic fine particles are also present in the vicinity of the surface of the hard coating layer, thereby improving the anti-glare property and reducing the unevenness of the coating film. . (2) Since the inevitable film thickness is increased, it is expected that the pencil hardness is improved as compared with the conventional anti-glare hard coating film produced using the same size of organic fine particles. (3) The more the amount of the dispersant added, the higher the probability that the organic fine particles are present in the vicinity of the surface of the hard coating layer, so that the surface state (the outer surface smog, 60° gloss ratio) is adjusted by the amount of the dispersant added.成为 (Other functional layers) In the anti-glare hard coating film of the present invention, an antireflection layer capable of imparting antireflection properties, for example, a siloxane-based coating film or a fluorine-based coating film, may be provided on the uppermost layer as needed. Wait. At this time, the thickness of the antireflection layer is suitably about 0.05 to 1 #m. By providing the anti-reflection layer, it is possible to cancel the reflection of the reflection caused by sunlight, fluorescent lamps, etc., and to suppress the reflectance of the surface, thereby improving the total light transmittance and improving the transparency. . In addition, antistatic properties can be improved in response to the type of antireflection layer. (Adhesive Layer) In the antiglare hard coating film of the present invention, an adhesive layer for adhering to an adherend such as a liquid crystal display can be formed on the opposite surface of the hard coating layer of the plastic film. As the adhesive constituting the adhesive layer, for example, an acrylic adhesive, an urethane-based adhesive, or a polyoxygen-based adhesive suitable for optical use is preferably used. The thickness of the adhesive layer is usually from 5 to 100 / m, preferably from 10 to 60. -22-.200946995 Further, on the adhesive layer, a release sheet can be provided as needed. The release sheet is exemplified by coating a release agent such as polyoxymethylene resin on various plastic films such as polyethylene terephthalate or polypropylene. The thickness of the peeling sheet is not particularly limited and is usually about 20 to 15 Å / ζ ηη. The anti-glare hard coating film which forms such an adhesive layer is suitable for use in a display such as a CRT, an LCD, or a PDP, and can provide an anti-glare property or an abrasion resistance performance, and is particularly suitable for use in an LCD or the like. The polarizing plate is adhered. [Polarizing Plate] The present invention also provides a polarizing plate in which the antiglare hard and hard coating film of the present invention is bonded to a polarizing mirror. The liquid crystal cell in the LCD generally has two transparent electrode substrates on which the alignment layer is formed, and the alignment layer is disposed on the inner side, and the spacer is arranged in a predetermined gap, and the periphery thereof is sealed, and the liquid crystal material is sandwiched in the gap. At the same time, the outer surface of the two transparent electrode substrates is provided with a structure in which a polarizing plate is disposed via an adhesive layer. 0 Fig. 1 is a perspective view showing an example of the configuration of the polarizing plate. As shown in the figure, the polarizing plate 10 is generally provided with a substrate having a three-layer structure of a triacetyl cellulose (TAC) film 2 and a 2' bonded to both surfaces of a polyvinyl alcohol polarizing lens 1. Thereafter, an adhesive layer 3 for adhering to an optical component such as a liquid crystal cell is formed on one surface thereof, and the release sheet 4 is attached to the adhesive layer 3. Further, a surface protective film 5 is usually provided on the opposite surface of the adhesive layer 3 of the polarizing plate. 200946995 The polarizing plate of the present invention is provided in the τ AC film 2, 2' provided on both sides of the polarizing mirror 1, and the hard coating layer of the present invention described above is provided on one side of the TAC film. When the adhesive layer 3, the release sheet 4, and the surface protective film 5 are provided on the polarizing plate, the hard coating layer of the present invention is provided particularly on the side of the TAC film 2' on the side of the surface protective film 5. The method of manufacturing the polarizing plate of the present invention can be carried out by, for example, the operation shown below. Further, Fig. 2 is a schematic cross-sectional view showing a configuration of an example of a polarizing plate of the present invention. First, the transparent plastic film of the substrate is a film 12' having no optical anisotropy such as a TAC film, and the hard coating layer 13 of the present invention is formed on one surface thereof to form an antiglare hard coating film 14. Next, using the adhesive layers 15, 15', a TAC film 12 on which the hard coating layer 13 is not formed is laminated on one surface of the polarizing mirror 11, and the anti-glare hard coating film 14 is laminated on the opposite surface of the polarizing mirror. When a TAC film is used for the transparent plastic film, saponification treatment other than the above surface treatment may be performed in order to improve the adhesion of the laminate due to the adhesive. φ Thereby, the polarizing plate 20 excellent in antiglare performance and abrasion resistance can be obtained. The polarizing plate 20 may be provided with a peelable surface protection film 5 as shown in FIG. 1 on the surface on which the hard coating layer 13 is provided, or may be provided on the opposite surface thereof for attaching optical components such as a liquid crystal cell. Adhesive layer 16 or release sheet 17 » The polarizing plate of the present invention can be used for a liquid crystal cell starting from an LCD, or for use in a light amount adjustment, a polarizing interference application device, or an optical defect tester. -24-200946995 EXAMPLES Next, the present invention will be described in detail by way of examples, but the invention should not be construed as limited to the examples. Further, the average particle diameter and refractive index of the organic fine particles, the refractive index of the cured product of the active energy ray-inductive composition, and the properties of the hard coating film were determined in accordance with the method described below. <Organic microparticles> (1) Average particle diameter © _ A Coulter counter (Beckman Coulter, product name "Multi sizer 3") was used as a dispersion of 0.5% ion-exchanged water at 25 °C was measured by the Coulter Counter method. (2) Refractive index According to the composition of the organic fine particle monomer, the average refractive index is calculated from the refractive index of the contained monomer and the mass ratio. <Active energy ray-sensitive composition> Q (3) Refractive index of cured product In each preparation example, a coating agent composed of an active energy ray-sensitive composition (A), a photoinitiator, and a diluent solvent was prepared. . These methods were applied to a TAC film [manufactured by Fujifilm Co., Ltd., trade name "TAC80TD80ULH"] in the same manner as in the examples to obtain a hard coating film for measuring the refractive index of the cured product. The refractive index of the hard coating layer was determined by using an Ato refractometer manufactured by Atago Co., Ltd., in accordance with JIS K 7142, as the refractive index of the cured product of the active energy ray-inductive composition. -25- 200946995 <Hard film>> (4) Full light transmittance and total haze using the Murakami Color Technology Research Institute's Haze and Transmittance Meter "HM-150", JIS K 7136, measuring total light transmittance and total haze. (5) Internal smog and external surface smog are added to 100 parts by mass of an acrylic adhesive (product name "PE-1 21" manufactured by Japan Carbide Co., Ltd.), and an isocyanate crosslinking agent is added [manufactured by Toyo Ink Co., Ltd., product name" BHS-8515"] 2 parts by mass and 100 parts by mass of toluene, 制作 An adhesive solution is prepared. Applying an adhesive solution to a film of polyethylene terephthalate (manufactured by Toyo Kogyo Co., Ltd., trade name "A4300") having a thickness of 50/zm to a thickness of 20 μm after drying, and drying at 10 ° C Make a sticky sheet for 3 minutes. The prepared adhesive sheet was adhered to the hard coating layer side of the antiglare hard coating film as a sample for internal haze calculation. The haze of the adhesive sheet and the internal haze calculation sample was measured, and the haze of the adhesive sheet was subtracted from the haze of the internal haze calculation sample as the internal layer of the hard coating layer of the antiglare hard coating film. Smog. In addition, in order to confirm that the haze of the monomer of the triacetyl cellulose film which is a transparent plastic film of the anti-glare hard coating film used in the Example and the comparative example is less than 0.01%, it can be Neglected. The measurement of smog is the same as above (4). (6) Evaluation of anti-glare property A sample obtained by attaching a hard coating film 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. Evaluation of anti-glare properties. -26- 200946995 〇: Fluorescent lamp has sufficient anti-reflection and less fading X: The anti-reflection of fluorescent lamps is not sufficient, or the anti-reflection of fluorescent lamps is sufficient, but the fading is large and the visibility is poor (7) The 60° gloss ratio was measured using a portable gloss meter "PG-1M" manufactured by Nippon Denshoku Industries Co., Ltd., and was measured in accordance with JIS K 7105. (8) Pencil hardness According to JIS K 5400, the pencil scratch of the Yasuda Seiki Seisakusho Co., Ltd. 〇 The film hardness tester "N0553-M1" was used for measurement. (9) Uneven coating film The surface of the hard coating layer was visually observed to evaluate the coating unevenness according to the following criteria. 〇: The overall surface of the coating film looks very average. X: The portion with high anti-glare on the surface of the coating film is mixed with the low portion, and the whole looks uneven. 〇 Modulation Example 1 (A) Active energy ray-sensitive composition Hard coating agent [manufactured by JSR Corporation, "op star Z7 524", solid content concentration: 70% by mass, total active energy ray-curable compound containing reactive cerium oxide fine particles and polyfunctional acrylate, 65 mass%, photoinitiated 5% by mass of the agent, 30% by mass of methyl ethyl ketone, and 1.50 parts by mass of the cured product; (B) PMM A fine particles of spherical organic particles [manufactured by Kyoritsu Chemical Co., Ltd., average particle diameter 5# m, Refractive index 1.49] 11.25 parts by mass; (C) Dispersant having a tertiary amine as a polar group -27-.200946995 [Production name "disperbyk 103", manufactured by BYK Chemie, Japan, solid content concentration: 40% by mass] 3 parts by mass; 90 parts by mass of propylene glycol monomethyl ether of a diluent solvent were uniformly mixed to prepare a coating agent 1 for an antiglare hard coating layer having a solid content of about 40% by mass. The compounding amount of the coating agent is shown in Table 1. Preparation Example 2 In addition to (B) spherical organic fine particles, acrylic fine particles (average particle diameter: 8 # m, refractive index: 1.55), 11.25 parts by mass; and (C) dispersant, "disperbyk 103" were used ( In the same manner as in the preparation of the first example, the coating agent 2 for an antiglare hard coating layer having a solid content of about 40% by mass was produced in the same manner as in the above-mentioned. The compounding amount of the coating agent is shown in Table 1. Preparation Example 3 A coating agent 3 for an antiglare hard coating layer having a solid content of about 40% by mass was produced in the same manner as in Preparation Example 2 except that the dispersing agent ("disperbyk 103" (described above) was used in an amount of 75 parts by mass. The compounding amount of the coating agent is shown in Table 1. Preparation Example 4 A coating agent 4 for an antiglare hard coating layer having a solid content of about 40% by mass was produced in the same manner as in Preparation Example 2 except that the dispersing agent ("disperbyk 103" (the above) was used in the amount of the dispersing agent. The compounding amount of the coating agent is shown in Table 1. Preparation Example 5 A coating agent 5 for an antiglare hard coating layer having a solid content of about 40% by mass was produced in the same manner as in Preparation Example 2 except that the dispersing agent ("disperbyk 103" (described above) was used in an amount of 5 parts by mass. The compounding amount of the coating agent is shown in Table 1. Preparation Example 6 -28-.200946995 In addition to (C) dispersant, caprolactone-modified polyethylene glycol (manufactured by BYK Chemie Co., Ltd., trade name "disperbyklll", solid component concentration: 90% by mass], 1 part by mass, In the same manner as in Preparation Example 2, a coating agent 6 for an antiglare hard coating layer having a solid content of about 40% by mass was produced. The blending amount of the coating agent is shown in Table 1. Preparation Example 7 In addition to the (C) dispersant, a caprolactone-modified polyethylene glycol (manufactured by BYK Chemie Co., Ltd., trade name "disperbykl 63", solid content concentration: 45 ❹ mass%] 1 part by mass, and other preparation examples 2 The coating agent 7 for an antiglare hard coating layer having a solid content of about 40% by mass was produced in the same manner. The blending amount of the coating agent is shown in Table 1. Preparation Example 8 In addition to the (C) dispersant, polyethylene glycol modified with caprolactone and dibutylamine ethanolammonium salt at both ends (manufactured by BYK Chemie Co., Ltd., trade name "disperbyk 180", solid content concentration: 81% by mass] was used. In the same manner as in the preparation of φ Example 2, the coating agent 8 for an antiglare hard coating layer having a solid content of about 40% by mass was produced. The compounding amount of the coating agent is shown in Table 1. Preparation Example 9 A coating agent 9 for an antiglare hard coating layer having a solid content of about 40% by mass was produced in the same manner as in Preparation Example 1 except that the (C) dispersant was not used. The blending amount of the coating agent is shown in Table 1. Preparation Example 10 -29-.200946995 A hard coating agent containing no cerium oxide particles is used as the component (A). [Daily Seiki Co., Ltd., trade name "Seika beam EXF-L203 (CS-1), solid component concentration 70% by mass, 655% by mass of the active energy ray-curable compound containing a reactive monomer and a polyfunctional acrylate, 5% by mass of a photoinitiator, 30% by mass of propylene glycol monomethyl acetate, and 1.52% of a cured product. In the same manner as in Preparation Example 1, except for 100 parts by mass, a coating agent 10 for an antiglare hard coating layer having a solid content of about 40% by mass was produced. The compounding amount of the coating agent is shown in Table 1. Preparation Example 11 A coating agent 11 for an antiglare hard coating layer having a solid content of about 40% by mass was produced in the same manner as in Preparation Example 2 except that the (C) dispersant was not used. The compounding amount of the coating agent is shown in Table 1. In the same manner as in Preparation Example 1, except that the (B) spherical organic fine particles were not used, the coating agent 12 for an antiglare hard coating layer having a solid content of about 40% by mass was produced. The compounding amount of the coating agent is shown in Table 1. φ Example 1 A TAC film having a thickness of 80 used for a transparent plastic film [manufactured by Fujifilm Co., Ltd., trade name "TAC80TD80ULH"] was coated with a mayer bar coater. The obtained coating agent 1 had a cured film thickness of about 10 #m. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 m / cm 2 were irradiated with a high pressure mercury lamp to form a hard coating layer, and an antiglare hard coating film was produced. The properties of the hard coating are shown in Table 2. -30-.200946995 Example 2 The same procedure as in Example 1 was carried out except that the coating agent 2 obtained in Preparation Example 2 was applied by a Meyer bar coater to have a cured film thickness of about 10/zm. Diffuse hard coating. The properties of the hard coating are shown in Table 2. Example 3 An anti-glare hard coating was produced in the same manner as in Example 1 except that the coating agent 3 obtained in Preparation Example 3 was applied by a Meyer bar coater to have a thickness of the cured film of about 10/zm. membrane. The properties of the hard coating are shown in Table 2. Example 4 An anti-glare hard coating was produced in the same manner as in Example 1 except that the coating agent 4 obtained in Preparation Example 4 was applied by a Meyer bar coater to have a cured film thickness of about 10/m. membrane. The properties of the hard coating 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 agent 5 obtained in Preparation Example 5 was applied by a Meyer bar coater to have a cured film thickness of about 10/zm. . The properties of the hard coating are shown in Table 2. Example 6 -31-200946995 An anti-glare hard coating was produced in the same manner as in Example 1 except that the coating agent 6 prepared in Preparation Example 6 was applied by a Meyer bar coater to have a cured film thickness of about 10 μm. membrane. The properties of the hard coating are shown in Table 2. (Example 7) An antiglare hard coating film was produced in the same manner as in Example 1 except that the coating agent 7 obtained in Preparation Example 7 was applied by a Meyer bar coater to have a cured film thickness of about 10 #m. The properties of the hard coating are shown in Table 2. (Example 8) An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating agent 8 obtained in Preparation Example 8 was applied by a Meyer bar coater to have a cured film thickness of about 10/zm. The properties of the hard coating are shown in Table 2. Comparative Example 1 防 An anti-glare hard coating film was produced in the same manner as in Example 1 except that the coating agent 9 obtained in Preparation Example 9 was applied by a Meyer bar coater to have a cured film thickness of about 10 μm. The properties of the hard coating are shown in Table 2. Comparative Example 2 An antiglare hard coating film was produced in the same manner as in Example 1 except that the coating agent 9 obtained in Preparation Example 9 was applied by a Meyer bar coater to have a cured film thickness of about 5 #m. -32- 200946995 The properties of the hard coating are shown in Table 2. In Comparative Example 3, an anti-glare hard coating was produced in the same manner as in Example 1 except that the coating agent 9 obtained by coating the preparation example 9 was coated with a Meyer bar coater to have a cured film thickness of about 4.5/zm. membrane.性能 The properties of the hard coating are shown in Table 2. Comparative Example 4 10 The same procedure as in Example 1 was carried out except that the coating agent obtained in Preparation Example 1 was applied by a Meyer bar coater to have a cured film thickness of about 10/m, and an anti-glare hardness was produced. Covered film. The properties of the hard coating are shown in Table 2. Comparative Example 5 1 1 ' The operation was carried out in the same manner as in Example 1 except that the coating agent obtained by the preparation example was applied by a Meyer bar coater to have a cured film thickness of about 1 〇 #m, and an anti-glare hardness was produced. Laminating.性能 The properties of the hard coating are shown in Table 2. Comparative Example 6 12 The same procedure as in Example 1 was carried out except that the coating agent obtained in Preparation Example 12 was applied by a Meyer bar coater to have a cured film thickness of about 1 Å/zm, and an anti-glare property was hardly produced. Laminating. The properties of the hard coating are shown in Table 2. -33- 200946995 Table 1

硬被覆娜成材料(塗覆劑） (A)活性能量線感應型組成物 (B)球狀有讎粒子 折射率差 (C)分散劑 塗覆劑 反應性二氧化 硬化物的 固形成分含量 平均粒徑 含量 〔(B)-(A) 含量 種類 矽粒子含量 折射率 (質量份） (㈣ 折射率 (質量份） 硬化物〕 種 類 償量份） (質量％) 實施例1 調製例1 39 1.50 100 5 1.49 16.1 -0.01 disperbykl03 1.7 實施例2 調製例2 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.3 實施例3 調製例3 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.4 實施例4 調製例4 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.6 實施例5 調製例5 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.9 實施例6 調製例6 39 1.50 100 8 1.55 16.1 0.05 disperbyklll 1.3 實施例7 調製例7 39 1.50 100 8 1.55 16.1 0.05 disperbykl63 0.6 實施例8 調製例8 39 1.50 100 8 1.55 16.1 0.05 disperbyk!80 1.2 比較例1 調製例9 39 1.50 100 5 1.49 16.1 -0.01 — 0 比較例2 調製例9 39 1.50 100 5 1.49 16.1 -0.01 — 0 比較例3 調製例9 39 1.50 100 5 1.49 16.1 -0.01 — 0 比較例4 調製例10 _ 1.52 100 5 1.49 16.1 -0.03 disperbykl03 1.7 比較例5 調製例11 39 1.50 100 8 1.55 16.1 0.05 - 0 比較例6 調製例Π 39 1.50 100 — — 0 — disperbykl03 2.9 註：（A)成分中反應性二氧化矽粒子的含量爲（A)成分之固 形成分中的値。 -34- 200946995 表2 瞻覆層 硬塗翻的件能 的厚度 全透光率 霧値(％) (jwm) (%) 全霧値 內部籌値 外表面霧值 6(Γ光澤率 防眩性 塗膜不均 鈴筆硬度 寅施例1 10 88.35 11.9 2.7 9.2 26.9 〇 〇 3Η 實施例2 10 89.63 25.9 20.7 5.2 74.1 〇 〇 3Η 實施例3 10 90.02 26.5 20.1 6.4 64.1 〇 〇 3Η 實施例4 10 90.21 29.4 20.3 9.1 35.6 〇 〇 3Η 實施例5 10 89.92 34,8 21.9 12.9 28.2 〇 〇 3Η 實施例6 10 92.45 29.5 20.2 9.3 46.9 〇 〇 3Η 實施例7 10 92.06 25.2 19.6 5.6 73.3 〇 〇 3Η 實施例8 10 92.85 32.8 20.8 12.0 31.0 〇 〇 3Η 比較例1 10 92.27 3.5 3.5 <0.1 84.1 X 〇 3Η 比_2 5.0 91.27 2.0 1.4 0.6 57.5 〇 X 2Η 比跡J3 4.5 90.07 44.5 3.7 40.8 7.5 X X 2Η 比較例4 10 93.45 24.0 22.8 1.2 87.1 X 〇 3Η 比咖5 10 89.18 26.0 22.8 3.2 87.8 X 〇 3Η 比較例ό 10 92.28 0.27 <0.1 0.27 92.0 X 〇 3Η 由上述表1、2可知如下。 實施例1 (高對比型）顯示，在PMMA微粒中添加分散劑， 即使相對於平均粒徑5^m之有機微粒爲膜厚大的硬被覆 層，亦可顯現外表面霧値，並獲得防眩性。一方面，在比較 例1中，由於不添加分散劑’則幾乎沒有形成表面凹凸，外 -35- 200946995 表面霧値變小，無法獲得防眩性。而爲了形成表面凹凸，在 使硬被覆層的膜厚大約等同有機微粒之平均粒徑的比較例2 中，出現凹凸變得不存在的部分，而成了對防眩性有不均的 面e進一步使膜厚變薄時（比較例3)，外表面霧値變得非常 大，成了稱爲褪色的狀態。 在比較例5中，即使不添加分散劑，根據有機微粒的種類 亦多少可獲得一些外表面霧度，但是無法獲得充分的外表面 霧値。相對於此，可知在實施例2〜5(廣用型）中，根據分散 劑的添加量，外表面霧値有所變化，但內部霧値則幾無變 化。又，在實施例6〜8(廣用型）中，即使變更分散劑的種類， 相較於比較例5更能提高外表面霧値爲自明。 比較例4由於不含二氧化矽系微粒，故無法獲得充分的外 表面霧値。而比較例6爲無有機微粒的系統且添加了分散劑 的例子，幾乎無顯現外表面霧度，並無法獲得防眩性。 如此一來，本發明的防眩性硬被覆膜在不影響對比的情況 φ 下，使得控制防眩性的程度成爲可能。 產業上可利用性 本發明的防眩性硬被覆膜，爲設置有含有機微粒之硬被覆 層的防眩性硬被覆膜，在將外表面霧値及60°光澤率控制在 所期望的値時，不會降低對比，適合使用於對CRT、LCD、 PDP等的顯示器可賦予防眩性能或是耐磨耗性能等的構 件，特別適合於LCD等的偏光板。 【圖式簡單說明】 -36- 200946995 第1圖係表示偏光板一例的構成之斜視圖。 第2圖係表示本發明偏光板之一例的構成之剖面模式 圖。 【主要元件符號說明】 1 聚乙烯醇系偏光鏡 2,2',12,12' TAC薄膜 3,16 黏著劑層 4,17 ❿ 5 剝離薄片 表面保護薄膜 10 偏光板 11 偏光鏡 13 硬被覆層 14 防眩性硬被覆膜 15,15' 接著劑層 20 偏光板 -37-Hard-coated nano-material (coating agent) (A) Active energy ray-inductive composition (B) Spherical yttrium particle refractive index difference (C) Dispersant coating agent Reactive di- oxidized solid content Particle size [(B)-(A) Content type 矽 Particle content Refractive index (parts by mass) ((4) Refractive index (parts by mass) Hardened material) Type of compensation (% by mass) Example 1 Preparation Example 1 39 1.50 100 5 1.49 16.1 -0.01 disperbykl03 1.7 Example 2 Preparation Example 2 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.3 Example 3 Preparation Example 3 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.4 Example 4 Preparation Example 4 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.6 Example 5 Preparation Example 5 39 1.50 100 8 1.55 16.1 0.05 disperbykl03 0.9 Example 6 Preparation Example 6 39 1.50 100 8 1.55 16.1 0.05 disperbyklll 1.3 Example 7 Preparation Example 7 39 1.50 100 8 1.55 16.1 0.05 disperbykl63 0.6 Example 8 Modification Example 8 39 1.50 100 8 1.55 16.1 0.05 disperbyk! 80 1.2 Comparative Example 1 Preparation Example 9 39 1.50 100 5 1.49 16.1 -0.01 - 0 Comparative Example 2 Modulation Example 9 39 1 .50 100 5 1.49 16.1 -0.01 — 0 Comparative Example 3 Preparation Example 9 39 1.50 100 5 1.49 16.1 -0.01 — 0 Comparative Example 4 Modulation Example 10 _ 1.52 100 5 1.49 16.1 -0.03 disperbykl03 1.7 Comparative Example 5 Modulation Example 11 39 1.50 100 8 1.55 16.1 0.05 - 0 Comparative Example 6 Preparation Example 39 1.50 100 — — 0 — disperbykl03 2.9 Note: The content of the reactive cerium oxide particles in the component (A) is 値 in the solid component of the component (A). -34- 200946995 Table 2 Thickness of the hard-coated material of the coating layer Full-light transmittance smog (%) (jwm) (%) Full smog internal solution external surface fog value 6 (Γ gloss rate anti-glare Uneven coating hardness of the coating film Example 1 10 88.35 11.9 2.7 9.2 26.9 〇〇3Η Example 2 10 89.63 25.9 20.7 5.2 74.1 〇〇3Η Example 3 10 90.02 26.5 20.1 6.4 64.1 〇〇3Η Example 4 10 90.21 29.4 20.3 9.1 35.6 〇〇3Η Example 5 10 89.92 34,8 21.9 12.9 28.2 〇〇3Η Example 6 10 92.45 29.5 20.2 9.3 46.9 〇〇3Η Example 7 10 92.06 25.2 19.6 5.6 73.3 〇〇3Η Example 8 10 92.85 32.8 20.8 12.0 31.0 〇〇3Η Comparative Example 1 10 92.27 3.5 3.5 <0.1 84.1 X 〇3Η Ratio _2 5.0 91.27 2.0 1.4 0.6 57.5 〇X 2Η Ratio Trace J3 4.5 90.07 44.5 3.7 40.8 7.5 XX 2Η Comparative Example 4 10 93.45 24.0 22.8 1.2 87.1 X 〇 3 Η 咖 5 5 89.18 26.0 22.8 3.2 87.8 X 〇 3 Η Comparative Example 92 92 92.28 0.27 < 0.1 0.27 92.0 X 〇 3 Η From the above Tables 1 and 2, the following is shown. Example 1 (high contrast type) display, Add dispersion to PMMA particles Even if the organic fine particles having an average particle diameter of 5 μm are hard coating layers having a large film thickness, the outer surface haze can be exhibited and anti-glare properties can be obtained. On the other hand, in Comparative Example 1, since no dispersion is added The agent' has almost no surface irregularities, and the surface smog becomes small, and the anti-glare property cannot be obtained. In order to form the surface unevenness, the film thickness of the hard coating layer is approximately equal to the average particle diameter of the organic particles. In the case of the example 2, when the surface e of the unevenness of the anti-glare property is further reduced, the film thickness becomes thinner (Comparative Example 3), and the outer surface smog becomes very large. In Comparative Example 5, even if no dispersant is added, some outer surface haze can be obtained depending on the type of the organic fine particles, but sufficient outer surface haze cannot be obtained. In Examples 2 to 5 (wide-use type), the outer surface haze changed depending on the amount of the dispersant added, but the internal haze did not change. Further, in Examples 6 to 8 (wide-use type), even if the type of the dispersant was changed, the outer surface haze was improved as compared with the comparative example 5. In Comparative Example 4, since the cerium oxide-based fine particles were not contained, sufficient outer surface haze could not be obtained. On the other hand, Comparative Example 6 is an example in which no organic fine particles were added and a dispersing agent was added, and almost no outer surface haze was observed, and antiglare property could not be obtained. As a result, the anti-glare hard coating film of the present invention makes it possible to control the degree of anti-glare property without affecting the contrast φ. INDUSTRIAL APPLICABILITY The anti-glare hard coating film of the present invention is an anti-glare hard coating film provided with a hard coating layer containing organic fine particles, and the outer surface haze and the 60° gloss ratio are controlled to be desired. It is suitable for components that can provide anti-glare performance or wear resistance to displays such as CRT, LCD, PDP, etc., and is particularly suitable for polarizing plates such as LCDs. BRIEF DESCRIPTION OF THE DRAWINGS -36- 200946995 Fig. 1 is a perspective view showing a configuration of an example of a polarizing plate. Fig. 2 is a schematic cross-sectional view showing the configuration of an example of a polarizing plate of the present invention. [Main component symbol description] 1 Polyvinyl alcohol polarizer 2, 2', 12, 12' TAC film 3, 16 Adhesive layer 4, 17 ❿ 5 Release sheet surface protection film 10 Polarizing plate 11 Polarizing mirror 13 Hard coating layer 14 anti-glare hard coating 15,15' adhesive layer 20 polarizing plate-37-

Claims (1)

200946995 七、申請專利範圍： ι_一種防眩性硬被覆膜，其特徵係於透明塑膠薄膜表面具有 由使用硬被覆層形成材料所形成的硬被覆層，其中該硬被 覆層形成材料含有：（A)(a)多官能性（甲基）丙烯酸酯系單體 及/或（甲基）丙烯酸酯系預聚物、（b)含二氧化矽系微粒的活 性能量線感應型組成物；（B)球狀有機微粒；及（C)分子內至 少具有一個極性基的分散劑，且該硬被覆層的厚度比上述 (B)球狀有機微粒的平均粒徑更大。 2. 如申請專利範圍第1項的防眩性硬被覆膜，其中（c)分子內 至少具有一個極性基的分散劑，其極性基係具有選自呈酸 性的官能基及一至三級胺基中的一種以上。 3. 如申請專利範圍第2項的防眩性硬被覆膜，其中（C)分子內 至少具有一個極性基的分散劑係具有N，N-二烷胺基。 4. 如申請專利範圍第1至3項中任一項的防眩性硬被覆膜， 其中（b)二氧化矽系微粒係具有作爲表面官能基的含（甲基） 〇 丙烯醯基之基的二氧化矽微粒。 5. 如申請專利範圍第1至3項中任一項的防眩性硬被覆膜， 其中（B)球狀有機微粒的平均粒徑爲6〜10# m。 6. 如申請專利範圍第1至3項中任一項的防眩性硬被覆膜， 其中（A)活性能量線感應型組成物的硬化物，與（B)球狀有 機微粒的折射率差爲0.03以上。 7. 如申請專利範圍第1至3項中任一項的防眩性硬被覆膜， 其中硬被覆層的外表面霧値爲20%以下。 -38 - 200946995 8.—種偏光板，其特徵爲將形成有如申請專利範圍第1至7 項中任一項的防眩性硬被覆膜的面之相反面貼合於偏光 鏡而形成。200946995 VII. Patent application scope: ι_ An anti-glare hard coating film characterized in that the surface of the transparent plastic film has a hard coating layer formed by using a hard coating layer forming material, wherein the hard coating layer forming material contains: (A) (a) a polyfunctional (meth) acrylate monomer and/or a (meth) acrylate prepolymer, and (b) an active energy ray-sensitive composition containing cerium oxide-based fine particles; (B) spherical organic fine particles; and (C) a dispersing agent having at least one polar group in the molecule, and the thickness of the hard coating layer is larger than the average particle diameter of the (B) spherical organic fine particles. 2. The anti-glare hard coating film according to claim 1, wherein (c) a dispersing agent having at least one polar group in the molecule, the polar group having a functional group selected from an acidic group and a mono- to tertiary amine More than one in the base. 3. The antiglare hard coating film of claim 2, wherein the dispersing agent having at least one polar group in the (C) molecule has an N,N-dialkylamine group. 4. The anti-glare hard coating film according to any one of claims 1 to 3, wherein (b) the cerium oxide-based fine particles have a (meth) fluorene-containing fluorenyl group as a surface functional group. Base of cerium oxide particles. 5. The anti-glare hard coating film according to any one of claims 1 to 3, wherein (B) the spherical organic fine particles have an average particle diameter of 6 to 10 #m. 6. The anti-glare hard coating film according to any one of claims 1 to 3, wherein (A) the cured product of the active energy ray-sensitive composition, and (B) the refractive index of the spherical organic fine particles The difference is 0.03 or more. 7. The antiglare hard coating film according to any one of claims 1 to 3, wherein the outer surface of the hard coating layer has a haze of 20% or less. -38 - 200946995 8. A polarizing plate which is formed by bonding a surface opposite to a surface on which an anti-glare hard coating film according to any one of claims 1 to 7 is bonded to a polarizing mirror. -39--39-
TW098110031A 2008-03-28 2009-03-27 Antiglare hard coat film and polarizer plate using the film TWI453474B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008087295A JP5149052B2 (en) 2008-03-28 2008-03-28 Anti-glare hard coat film and polarizing plate using the same

Publications (2)

Publication Number Publication Date
TW200946995A true TW200946995A (en) 2009-11-16
TWI453474B TWI453474B (en) 2014-09-21

Family

ID=41114083

Family Applications (1)

Application Number Title Priority Date Filing Date
TW098110031A TWI453474B (en) 2008-03-28 2009-03-27 Antiglare hard coat film and polarizer plate using the film

Country Status (4)

Country Link
JP (1) JP5149052B2 (en)
KR (1) KR101151503B1 (en)
TW (1) TWI453474B (en)
WO (1) WO2009119905A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102162863A (en) * 2010-02-24 2011-08-24 琳得科株式会社 Anti-dazzle hard film and polarizer equipped with hard film
CN110573914A (en) * 2017-05-29 2019-12-13 株式会社大赛璐 Manufacturing method of anti-glare film

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009288655A (en) * 2008-05-30 2009-12-10 Nitto Denko Corp Antiglare hard coat film, polarizing plate and image display apparatus using the same, method for evaluating the same and method for producing the same
JP2009288650A (en) * 2008-05-30 2009-12-10 Nitto Denko Corp Antiglare hard coat film, polarizing plate and image display apparatus using the same
JP5116166B2 (en) * 2008-11-28 2013-01-09 日東電工株式会社 Hard coat film, optical element and image display device
JP5290046B2 (en) * 2009-05-14 2013-09-18 リンテック株式会社 Anti-glare hard coat film and polarizing plate using the same
JP2011081219A (en) 2009-10-07 2011-04-21 Nitto Denko Corp Hard-coated antiglare film, and polarizing plate and image display including the same
JP5522720B2 (en) 2009-10-07 2014-06-18 日東電工株式会社 Antiglare hard coat film, polarizing plate and image display device using the same, and method for producing antiglare hard coat film
JP2011081217A (en) 2009-10-07 2011-04-21 Nitto Denko Corp Hard-coated antiglare film, polarizing plate and image display including the same, and method for producing the hard-coated film
JP5592671B2 (en) * 2010-03-02 2014-09-17 リンテック株式会社 Anti-glare hard coat film and polarizing plate using the same
JP5552516B2 (en) * 2012-10-04 2014-07-16 日東電工株式会社 Anti-glare hard coat film, polarizing plate and image display device using the same
JP5470433B2 (en) * 2012-10-04 2014-04-16 日東電工株式会社 Anti-glare hard coat film, polarizing plate and image display device using the same
JP2013167890A (en) * 2013-04-05 2013-08-29 Nitto Denko Corp Hard-coated antiglare film, polarizing plate and image display device including the same, and method for producing hard-coated antiglare film
JP2013178534A (en) * 2013-04-05 2013-09-09 Nitto Denko Corp Hard-coated antidazzle film, and polarizing plate using the same, and image display device
JP2013178533A (en) * 2013-04-05 2013-09-09 Nitto Denko Corp Hard-coated antiglare film, polarizing plate and image display device using the same, and method for manufacturing hard-coated antiglare film
JP6475920B2 (en) * 2014-03-26 2019-02-27 リンテック株式会社 Touch panel
WO2015145618A1 (en) * 2014-03-26 2015-10-01 リンテック株式会社 Anti-glare hard coat film
JP2015057655A (en) * 2014-10-14 2015-03-26 日東電工株式会社 Antiglare hard coat film, polarizing plate and image display device using the same, and method for producing antiglare hard coat film
JP2016200806A (en) * 2015-04-10 2016-12-01 日東電工株式会社 Polarizing film set with pressure-sensitive adhesive layer, liquid crystal panel and liquid crystal display device
JP6871756B2 (en) * 2017-02-20 2021-05-12 リンテック株式会社 Image display device with position detection function
JP2019105694A (en) * 2017-12-11 2019-06-27 株式会社ダイセル Antiglare film, and method for producing the same and application
JP2019179268A (en) * 2019-07-01 2019-10-17 リンテック株式会社 Antiglare hard-coat film
CN111100314B (en) * 2019-12-19 2022-05-03 合肥乐凯科技产业有限公司 Preparation method of anti-glare hardened film for polarizer
US11740388B2 (en) * 2020-02-13 2023-08-29 Benq Materials Corporation Anti-glare film and polarizer with the same
KR20220122325A (en) * 2021-02-26 2022-09-02 동우 화인켐 주식회사 Polarizing plate and image display device including same
JP2023146802A (en) * 2022-03-29 2023-10-12 リンテック株式会社 anti-glare film

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0618706A (en) * 1992-01-24 1994-01-28 Dainippon Printing Co Ltd Scratch-resistant antiglare film, polarizing plate and method for producing the same
JP3507719B2 (en) * 1998-02-17 2004-03-15 大日本印刷株式会社 Anti-glare film, polarizing element and display device
TWI334492B (en) * 2003-03-05 2010-12-11 Fujifilm Corp High refractive index layer, production process of curable coating composition, antireflection film, polarizing plate and image display device using thereof
JP2005156642A (en) * 2003-11-20 2005-06-16 Fuji Photo Film Co Ltd Antireflection film, polarizing plate, and image display device using the same
JP4746863B2 (en) * 2004-11-11 2011-08-10 リンテック株式会社 Anti-glare hard coat layer forming material and anti-glare hard coat film
JP2007011323A (en) * 2005-06-03 2007-01-18 Bridgestone Corp Antireflection film, antireflective light-transmitting window material having the antireflection film, and display filter having the antireflective light-transmitting window material
CN101208620B (en) * 2005-06-28 2011-04-27 日东电工株式会社 Antiglare hardcoat film

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102162863A (en) * 2010-02-24 2011-08-24 琳得科株式会社 Anti-dazzle hard film and polarizer equipped with hard film
CN110573914A (en) * 2017-05-29 2019-12-13 株式会社大赛璐 Manufacturing method of anti-glare film
CN110573914B (en) * 2017-05-29 2022-06-07 株式会社大赛璐 Method for producing anti-glare film

Also Published As

Publication number Publication date
KR101151503B1 (en) 2012-05-30
JP2009244305A (en) 2009-10-22
JP5149052B2 (en) 2013-02-20
TWI453474B (en) 2014-09-21
KR20100120307A (en) 2010-11-15
WO2009119905A1 (en) 2009-10-01

Similar Documents

Publication Publication Date Title
TW200946995A (en) Antiglare hard coat film and polarizer plate using the film
CN102576094B (en) Optical laminate and method for producing optical laminate
TWI491907B (en) Optical film
TWI489130B (en) Anti-glare hard coating film and polarizing plate using the same
TWI607231B (en) Hard coat film
TWI497106B (en) An anti-reflection film and a polarizing plate using the same
TWI433778B (en) Antiglare hard coat film and polarizing plate using the film
JP6237796B2 (en) Optical laminate, polarizing plate, and image display device
JP3694153B2 (en) Anti-glare hard coat film
TWI534001B (en) Hard coat film
JP4135232B2 (en) Hard coat film or sheet
JP2020076993A (en) Light diffusing layer forming paint, projection screen film, and projection screen
JP2012053178A (en) Antiglare and antistatic hard-coat film and polarizing plate
TW201524785A (en) High hardness film
TWI519826B (en) Antiglare hard coat film and polarizing plate using the film
JP2012048099A (en) Antiglare-antistatic hard coat film and polarizer
JP2004050535A (en) Anti-glare laminate, method for producing the same, and display medium