TW200402364A - Laminated film - Google Patents
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- TW200402364A TW200402364A TW092107767A TW92107767A TW200402364A TW 200402364 A TW200402364 A TW 200402364A TW 092107767 A TW092107767 A TW 092107767A TW 92107767 A TW92107767 A TW 92107767A TW 200402364 A TW200402364 A TW 200402364A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- 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
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- Optics & Photonics (AREA)
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- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
200402364 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關層合薄膜者；更詳細的說，是有關兼具 防止反射機能、與防止帶電機能之層合薄膜者。 【先前技術】 很早以來’在透明樹脂薄膜上設置防止反射層的防止 反射薄膜，就廣泛的被電子機器領域所使用；例如在聚酯 薄膜或聚碳酸酯薄膜上，以噴鍍或蒸著等方法設置多數的 無機氧化物層，將含氟化合物以塗佈法形成防止反射層之 透明樹脂薄膜，被陰極射線管、液晶面板等顯示機器所使 用，使晝像更淸晰。 不過，已往的防止反射層，實質上不具導電性、容易 帶電，會產生塵埃因靜電吸著而污染的問題；因此施行很 多如在基礎薄膜上配合防止帶電劑，在防止反射薄膜上設 置透明導電層等之防止帶電的措施。 不過，施行相關措施之際，如配合防止電帶劑時，會 發生基礎薄膜之透明性降低、著色等光學特性減弱，因防 止帶電劑之析出而產生發黏現象、或發生耐熱性耐久性下 降等問題；又如設置透明導電層時，會由於透明導電層而 使透明性降低、著色等化學特性減弱、加工成本大幅度上 升等問題。 本發明之工作同仁，爲解決上述各問題’深入探討結 果發現，在由透明樹脂所成透明基礎薄膜至少一面的表面 -7 - 3646 (2) (2)200402364 / 上，置（A )由具有較基礎薄膜之折射率爲高之折射率 的化學透明化合物所成之層（以下稱爲a層），其次， 在A層之上設置（B )由具有透明性及導電性的化合物所 成之層（以下稱爲B層）的層合薄膜，可以解決上述各問 題，達成了本發明的目標。 【發明內容】 〔發明之揭示〕 · 本發明相關之層合薄膜，其特徵爲在透明樹脂薄膜至 少一面的表面上，設置有（A )由具有較透明樹脂薄膜之 - 折射率爲高之折射率的光學透明化合物所成之層，更於其 _ 上設置有（B )由具有透明性及導電性的化合物所成之層 ，層合而成的層合薄膜。 構成層合於薄膜表面之（A )層的化合物，其折射率 以較構成層合於其上之（B )層的化合物之折射率高爲佳 而且，構成（B )層的化合物，以導電性高分子化合 物爲佳。 而且，做爲本發明層合薄膜基材的透明樹脂薄膜，以 含有熱可塑性原菠烯系樹脂爲佳。 〔用以實施發明之最佳形態〕 就本發明做具體的說明如下。 本發明之層合薄膜中，構成基材層的透明樹脂薄膜， / -8- (3) (3)200402364 此薄膜爲卷筒狀或單張均可，其厚度，通常以〇 . 1 μ m〜 10,000 /zm爲宜，以1 //m〜5,000 /zm爲佳，最好是 10 // m〜3,〇〇〇 A m之板狀成形品，其表面上有圓點、 稜柱等之形狀均可；對其製造方法沒有特別的限制，射出 成形法、抽出成形法、或溶劑流延法等眾所周知的方法成 形者，均可使用。 又，本發明中之折射率，沒有特別的限制，依據 JIS — K — 7 105之標準’爲23 °c下使用阿具折射計（Abbe M e t e r )測定之値。 本發明薄膜之原料，透明樹脂都可使用，考量其成形 性則以使用熱可塑性樹脂爲佳；具體的說，可以使用丙烯 酸樹脂、酷酸乙醯酯樹脂、聚酯樹脂、聚碳酸酯樹脂、聚 芳酯樹脂、原菠烯〔二環（2，2，1 )庚烯〕系樹脂等等 ;其中’就耐熱性、耐水（濕）性、以及光學特性之平衡 優異等観點而言，以熱可塑性原菠烯系樹脂爲佳。 相關的熱可塑性原菠烯系樹脂，爲含有下列式（1 ) 〜式；（4 )所代表構造單位的樹脂。 9- (4)200402364200402364 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a laminated film; more specifically, it relates to a laminated film that has both anti-reflection function and anti-motor function. [Prior art] Antireflection films provided with an antireflection layer on a transparent resin film have been widely used in the field of electronic equipment for a long time; for example, on a polyester film or a polycarbonate film, they are spray-coated or vapor-deposited. Other methods include setting up many inorganic oxide layers, and forming a transparent resin film of an anti-reflection layer by a coating method using a fluorine-containing compound, which is used by display devices such as a cathode ray tube and a liquid crystal panel to make the daytime image clearer. However, the conventional anti-reflection layer is essentially non-conductive and easy to be charged, which may cause dust to be contaminated by electrostatic adsorption. Therefore, many implementations such as adding anti-static agent to the base film and providing transparent conductive on the anti-reflection film Measures to prevent electrification. However, when the related measures are implemented, if the anti-charge agent is used, the transparency of the base film will be reduced, the optical properties such as coloring will be weakened, the tack phenomenon will occur due to the prevention of the charging agent, or the heat resistance and durability will decrease And other problems; for example, when the transparent conductive layer is provided, the transparency is reduced due to the transparent conductive layer, the chemical characteristics such as coloring are weakened, and the processing cost is greatly increased. In order to solve the above problems, the working colleague of the present invention, as a result of in-depth discussion, it was found that on the surface of at least one side of a transparent base film made of a transparent resin-7-3646 A layer made of a chemically transparent compound with a higher refractive index than the base film (hereinafter referred to as a layer). Second, a layer (B) made of a compound having transparency and conductivity is provided on the A layer. A layered film (hereinafter referred to as layer B) can solve the above problems and achieve the object of the present invention. [Summary of the Invention] [Disclosure of the Invention] · The laminated film related to the present invention is characterized in that (A) is provided on the surface of at least one side of the transparent resin film with (A) a refractive index having a higher refractive index than the transparent resin film. A layer made of an optically transparent compound having a high efficiency is further provided with a laminated film (B) made of a layer made of a compound having transparency and conductivity. The compound constituting the (A) layer laminated on the film surface preferably has a higher refractive index than the compound constituting the (B) layer laminated thereon, and the compound constituting the (B) layer is conductive. Polymeric compounds are preferred. Moreover, as the transparent resin film which is the laminated film substrate of the present invention, it is preferable to contain a thermoplastic orthospinene resin. [Best Mode for Carrying Out the Invention] The present invention will be specifically described as follows. In the laminated film of the present invention, the transparent resin film constituting the base material layer is -8- (3) (3) 200402364 This film can be rolled or single sheet, and its thickness is usually 0.1 μm. It is preferably 10,000 / zm, preferably 1 // m to 5,000 / zm, and most preferably a plate-shaped molded product with a length of 10 // m to 3,000 Am, the surface of which has dots, prisms, etc. The shape can be any shape; there is no particular limitation on the manufacturing method, and it can be used by those molded by well-known methods such as an injection molding method, an extraction molding method, or a solvent casting method. In addition, the refractive index in the present invention is not particularly limited, and 値 measured using an Abbe Meteorometer (Abbe M e t e r) at 23 ° C according to the JIS-K-7105 standard '. The raw material of the film of the present invention can be used as a transparent resin. Considering its moldability, it is better to use a thermoplastic resin. Specifically, acrylic resin, ethyl acetate resin, polyester resin, polycarbonate resin, Polyarylate resin, orthospinene [bicyclo (2,2,1) heptene] -based resin, etc .; among them, in terms of excellent balance of heat resistance, water (wet) resistance, and optical characteristics, A thermoplastic orthospinene resin is preferred. The related thermoplastic orthospinene-based resin is a resin containing a structural unit represented by the following formulae (1) to (4). 9- (4) 200402364
一般式（2) (5)200402364General formula (2) (5) 200402364
R2 R3 一般式（3)R2 R3 General formula (3)
一般式（4) (6) (6)200402364 上述式（1)〜（4)中，R1〜R4爲各自獨立之氫原 子、鹵原子、碳原子數1〜3 0之烴基、或至少一種選自含 有氧原子、氮原子、硫原子、磷原子、及矽原子之一價有 機基；m爲〇〜3之整數；X爲—C— C—、或—C=C—。 本發明使用之含有式（1)〜（4)所表構造單位之熱 可塑性原菠烯系樹脂，可以使用下列①〜⑤所示之聚合體 〇 ① 與上述式（1 )〜（4 )之構造單位相對應原菠烯系 單體（以下稱爲「特定單體」）之加聚體或開環聚合體。 ② 特定單體與共聚合性單體之共加聚體或開環共聚合 ③ 上述開環（共）聚合體之加氫聚合體。 ④ 上述開環（共）聚合體，由於弗里德爾克拉夫茨反 應（Friedel— Crafts Reaction)而環化後之加氫（共）聚 合體。 ⑤ 特定單體、與含不飽和二重結合化合物之飽和共聚 合體。 (特定單體） 適用的特定單體，爲上述式（1)式（4)中，R1及 R3爲氫原子或碳原子1〜1〇之烴基，R2及爲氫原 子或一價之有機基，R2及R4之至少一個爲氫原子及烴 基以外之極性基；m爲〇〜3之整數，以0〜2爲佳，最好 的是m爲0或1。General formula (4) (6) (6) 200402364 In the above formulas (1) to (4), R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least one selected It is a monovalent organic group containing an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom; m is an integer of 0 to 3; X is —C—C—, or —C = C—. The thermoplastic orthospinene resin containing the structural units represented by the formulae (1) to (4) used in the present invention can use the polymers shown in the following ① to ⑤ and the above formulae (1) to (4) The structural unit corresponds to an addition polymer or a ring-opening polymer of an orthospinene monomer (hereinafter referred to as a "specific monomer"). ② Co-addition or ring-opening copolymerization of specific monomers and copolymerizable monomers ③ Hydrogenated polymers of the above-mentioned ring-opening (co) polymers. ④ The above-mentioned ring-opened (co) polymers are cyclized hydrogenated (co) polymers due to the Friedel-Crafts Reaction. ⑤ Saturated copolymers of specific monomers and unsaturated double bond compounds. (Specific monomer) The applicable specific monomer is a hydrocarbon group in which R1 and R3 are a hydrogen atom or a carbon atom of 1 to 10 in the above formula (1) and formula (4), and R2 and a hydrogen atom or a monovalent organic group At least one of R2 and R4 is a polar group other than a hydrogen atom and a hydrocarbon group; m is an integer of 0 to 3, preferably 0 to 2, and most preferably m is 0 or 1.
-12- (7) (7)200402364 又，上述極性基，可以使用羥基、羧基、碳原子數1 〜15之烷氧基、醯氧基、烷氧醯基或芳氧醯基、氰基、 氨基、醯胺基、含醯亞胺環之基、甲矽烷基、及鹵原子、 烷氧基或醯氧基部份或全部取代之甲矽烷基等等。 其中’從所得熱可塑性樹脂組成物具有高玻璃轉移點 、低吸濕性之觀點而言，以具有—（CH2 ) nCOOR5式所 代表碳原子1〜1 5之烷氧醯基或芳氧醯基之誘導體基的特 定單體爲佳；上述烷氧醯基或芳氧醯基之誘導體基的式中 ，R5爲碳原子數1〜12之烴基，以烷基爲佳；又，η通 常爲0〜5，η之値小者，所得原菠烯系樹脂的玻璃轉移點 高，較適合使用；η爲〇之特定單體，其合成容易亦適用 〇 上述特定單體的具體例’其可以使用之化合物如下； 雙環〔2.1.1〕庚—2 -烯、三環〔5.2.1. 〇2,6〕— 8 —癸烯 、四環〔4·4·0·12’5.17’1()〕 — 3 —十二烯、五環〔 6.5.1. 13,6·〇2,7.〇9’13 〕 一 4 —十五烯、五環〔 7.4.0. 12.5.19，12.08，13〕一 3 —十五烯、三環〔4.4.0.12,5〕— 3 —十一烯、5 —甲基雙環〔2.2.1〕庚—2 —烯、5 —乙基 雙環〔2.2.1〕—庚—2-烯、5 —己基一雙環〔2.2.1〕一 庚—2-烯、5 —甲氧醯基—雙環〔2.2.1〕—庚一 2 —烯、 5 —甲基一 5 —甲氧醯基一雙環〔2.2.1〕庚一2 -烯、5 — 氰基一雙環〔2.2.1〕庚—2 -烯、8 —甲基一四環〔 4.4.0. 12’5.Γ，1。〕 — 3 - 十二烯、8 —乙基—四環〔 4.4.0. 12^. 1^,10 ] — 3 - 十二烯、8 —甲氧醯基—四環〔 -3 0.JZ -13- (8) (8)200402364 4.4·0.12’5.Γ’1()〕—3 —十二烯、8 -乙氧醯基—四環〔 4·4.0.12’5.Γ’1()〕— 3 —十二烯、8 —正丙氧醯基—四環〔 4.4.0·12’5.Γ’1()〕一3-十二烯 、8 —異丙氧醯基—四環〔 4.4.0·12,5.I7，1。〕一 3 —十二烯、8 —正丁 氧醯基—四環〔 4.4.0.12’5.17’1C)〕一 3 —十 一^燒、8 —甲基—8 —甲氧釀基一 四環〔4.4.0. I2’5.17’1G〕— 3 —十二烯、8 —甲基一8 —乙氧 醯基-四環〔4.4.0.I2,5.Γ，1。〕— 3 —十二烯、8— 甲基一 8 — 正丙氧醯基一四環〔4.4.0.12’5.17’1()〕— 3 -十二烯、8 — 甲基—8 —異丙氧醯基—四環〔4,4.0.I2’5. 17’1G〕— 3 —十 二烯、8 —甲基—8 —正丁氧醯基一四環〔4.4.0.12’5.17’1() 〕—3 —十二烯、五環〔8·4.0.12’5.19’12.08’13〕— 3 —十六 烯、七環〔δΙΟ.Ι3,6」1。’17」12，15·。2’7·。11，16〕— 4 一二十 烯 '七環〔8 . 8.0 . 1 4，7 · 1 1 1，18 · 1 13，16.0 3，8.0 1 2，17〕一 5 —二十 —*嫌、5 —亞乙基—雙環〔2.2.1〕庚一 2-儲、8 —亞乙基 一四環〔4.4.0·12’5·Γ’1()〕— 3 -十二烯、5 —苯基—雙環 〔2.2.1〕庚一2 —烯、8 —苯基—四環〔4.4.0.I2,5.Γ，10〕 一 3 —十一燦、5 —氣—雙環〔2.2.1〕庚—2 —嫌、5 -氯 甲基一雙環〔2.2.1〕庚—2 -烯、5 —三氟甲基—雙環〔 2.2.1〕庚—2 —儲、5 —五氟乙基一雙環〔2.2.1〕庚—2 -烯、5，5 —二氟雙環〔2.2.1〕庚—2-烯、5，6-二氟雙 環〔2.2.1〕庚—2 —烯、5，5 —雙（三氟甲基）雙環〔 2.2.1〕庚—2 —烯、5，6 —雙（三氟甲基）雙環〔2.2.1〕 庚—2 —烯、5 —甲基—5 -三氟甲基雙環〔2.2.1〕庚一 2 —烯、5，5，6 —三氟雙環〔2.2.1〕庚—2 —烯、5，5，6 -14- (9) (9)200402364 —三（氟甲基）雙環〔2.2.1〕庚一 2 —烯、5，5，6，6 — 四氟雙環〔2.2.1〕庚一 2 —烯、5，5，6，6 —四（三氟甲 基）雙環〔2.2.1〕庚—2 —烯、5，5 —二氟—6，6-雙（ 三氟甲基）雙環〔2.2.1〕庚—2 —烯、5，6 —二氟5，6-雙（三氟甲基）雙環〔2.2.1〕庚—2 —烯、5，5，6 —三 氯—5 —二親甲基雙Jg〔2.2.1〕庚—2 —燒、5 —氯—5 — 五氟乙基—6，6 —雙（三氟甲基）雙環〔2.2.1〕庚—2 -烯、5，6 —二氟一 5 -七氟異丙基一 6 —三氟甲基雙環〔 2.2.1〕庚—2-烯、5 —氯—5，6，6 -三氟雙環〔2.2.1〕 庚一 2-烯、5，6 —二氯一 5，6 —雙（三氟甲基）雙環〔 2.2.1〕庚一2 —烯、5，5，6，6 —三氟—6 —三氟曱氧基 雙環〔2.2.1〕庚—2 —烯、5，5，6 —三氟—6-七氟丙氧 基雙環〔2.2.1〕庚—2-烯、8- 氟四環〔4.4.0.1 2，5.17,10 〕一3 —十二烯、8 —氟甲基四環〔4.4.0.I2’5.Γ’10〕— 3 — 十二烯、8 —二氟甲基四環〔4.4.0.I2’5. Γ’1(3〕一 3 —十二 烯、8 —三氟曱基四環〔4.4.0.12,5.17，1G〕— 3 —十二烯、8 —五氟乙基四環〔4.4.0_12,5.17’1G〕— 3 —十二烯、8，8 — 二氟四環〔4·4.0·12’5.Γ’1()〕一3 —十二烯、8，9 —二氟四 環〔4.4.0.12,5.17’10〕— 3 —十二烯、8，8 —雙（三氟甲基 )四環〔4.4.0.12’5.17’1()〕— 3 —十二烯、8，9 —雙（三氟 甲基）四環〔4.4.0.I2’5.17’1G〕一 3 —十二烯、8 —甲基—8 —三氟甲基四環〔4.4.0.12,5」7，10〕— 3 -十二烯、8，8, 9 —三氟四環〔4.4.0.12’5.17，1Q〕— 3 —十二烯、8，8，9 — 三（三氟曱基）四環〔4.4.0.I2,5.17’1Q〕一 3 —十二烯、8-12- (7) (7) 200402364 As the polar group, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 15 carbon atoms, a fluorenyl group, an alkoxyfluorenyl group or an aryloxyfluorenyl group, a cyano group, Amino, fluorenylamino, sulfonylimine ring-containing groups, silyl groups, and halogen atoms, alkoxy or fluorenyloxy partially or completely substituted silyl groups, and the like. Among them, from the viewpoint that the obtained thermoplastic resin composition has a high glass transition point and a low hygroscopicity, it has an alkoxyfluorenyl group or an aryloxyfluorenyl group having 1 to 15 carbon atoms represented by formula (CH2) nCOOR5. A specific monomer of an inducing group is preferred; in the above-mentioned formula of the inducing group of an alkoxyfluorenyl group or an aryloxyfluorenyl group, R5 is a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group; and η is generally If it is 0 to 5, the smaller of η is, the higher the glass transition point of the obtained prospinene-based resin is, and it is more suitable for use. The specific monomer with η being 0 can be easily synthesized and can also be applied. The compounds that can be used are as follows; bicyclic [2.1.1] hept-2-ene, tricyclic [5.2.1. 〇2,6] — 8-decene, tetracyclic [4 · 4 · 0 · 12'5.17'1 ()] — 3-dodecene, pentacyclic [6.5.1. 13,6 · 〇2, 7.〇9'13] 4-pentadecene, pentacyclic [7.4.0. 12.5.19, 12.08 , 13] a 3-pentadecene, tricyclo [4.4.0.12, 5] — 3-undecene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2. 1] -heptan-2-ene, 5-hexyl-bicyclo [2.2.1 ] Hepta-2-ene, 5-methoxyfluorenyl-bicyclo [2.2.1] -Hepta-2-ene, 5-methyl-5-methoxyfluorenyl-bicyclo [2.2.1] Hepta-2- Ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 8-methyl-tetracyclo [4.4.0. 12'5.Γ, 1. ] — 3-Dodecene, 8-ethyl-tetracyclo [4.4.0. 12 ^. 1 ^, 10] — 3-Dodecene, 8-methoxyfluorenyl-tetracyclo [-3 0.JZ -13- (8) (8) 200402364 4.4 · 0.12'5.Γ'1 ()] — 3-dodecene, 8-ethoxyfluorenyl—tetracyclo 〔4 · 4.0.12'5.Γ'1 ()]-3 -dodecene, 8 -n-propoxyfluorenyl-tetracyclo [4.4.0 · 12'5.Γ'1 ()]-3-dodecene, 8-isopropoxyfluorenyl— Fourth Ring [4.4.0 · 12,5.I7,1. ] One 3-dodecene, 8-n-butoxyfluorenyl-tetracyclic ring [4.4.0.12'5.17'1C)] One 3-11-elastomer, 8-methyl-8-methoxymethyl tetracycline [4.4.0. I2'5.17'1G] —3-dodecene, 8-methyl-8-ethoxyfluorenyl-tetracyclo [4.4.0.I2,5.Γ, 1. 〕 — 3-dodecene, 8-methyl-8-n-propoxyfluorenyl-tetracyclo [4.4.0.12'5.17'1 ()] — 3-dodecene, 8-methyl-8-isopropyl Oxyfluorenyl-tetracyclo [4,4.0.I2'5. 17'1G] —3-dodecene, 8-methyl-8-n-butoxyfluorenyl-tetracyclo [4.4.0.12'5.17'1 ( )] 3-dodecene, pentacyclic [8.4.0.12'5.19'12.08'13]-3-hexadecene, heptacyclic [δΙΟ.Ι3,6 ″ 1. "17" 12,15 ·. 2’7 ·. 11,16] — 4 eicosene's seven rings [8. 8.0. 1 4, 7 · 1 1 1, 18 · 1 13, 16.0 3, 8.0 1 2, 17] 1 5 — 20 — * 5-Ethylene-Bicyclo [2.2.1] Hepta-2-Chloride, 8-Ethylene-Tetracyclo [4.4.0 · 12'5 · Γ'1 ()] — 3-Dodecene, 5— Phenyl-bicyclo [2.2.1] hepta-2-ene, 8-phenyl-tetracyclo [4.4.0.I2,5.Γ, 10] a 3-elevencan, 5-gas-bicyclo [2.2. 1] Hept-2-ene, 5-chloromethyl-bicyclo [2.2.1] Hept-2-ene, 5-trifluoromethyl-bicyclo [2.2.1] Heptan-2, Chu, 5-Pentafluoroethyl Base-bicyclo [2.2.1] hept-2-ene, 5,5-difluorobicyclo [2.2.1] hept-2-ene, 5,6-difluorobicyclo [2.2.1] hept-2-ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5-methyl —5-trifluoromethylbicyclo [2.2.1] hepta-2-ene, 5,5,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,5,6 -14- (9) (9) 200402364 —Tris (fluoromethyl) bicyclo [2.2.1] hepta-2-ene, 5, 5,6,6 — Tetrafluorobicyclo [2.2.1] hepta-2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5 —Difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-difluoro5,6-bis (trifluoromethyl) bicyclo [2.2.1] Hept-2-ene, 5,5,6 —trichloro-5 —diphilic methylbis Jg [2.2.1] hept-2-, 5-chloro-5 — pentafluoroethyl-6,6 —bis (Trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5-heptafluoroisopropyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene , 5-chloro-5,6,6-trifluorobicyclo [2.2.1] hepta-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] heptane Mono-2-ene, 5,5,6,6-trifluoro-6-trifluorofluorenylbicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxy Bicyclo [2.2.1] Hepta-2-ene, 8-fluorotetracycline [4.4.0.1 2, 5.17,10] 3-dodecene, 8-fluoromethyltetracycline [4.4.0.I2'5 .Γ'10] — 3-dodecene, 8-difluoromethyl tetracyclo [4.4.0.I2 5. Γ'1 (3) -3-dodecene, 8-trifluorofluorenyltetracycline [4.4.0.12, 5.17, 1G] —3-dodecene, 8-pentafluoroethyltetracycline [4.4. 0_12,5.17'1G] —3-dodecene, 8,8—difluorotetracycline [4 · 4.0 · 12'5.Γ'1 ()] — 3-dodecene, 8,9—difluorotetracycline Ring [4.4.0.12, 5.17'10]-3-dodecene, 8,8-bis (trifluoromethyl) tetracyclo [4.4.0.12'5.17'1 ()]-3-dodecene, 8, 9 —Bis (trifluoromethyl) tetracyclo [4.4.0.I2'5.17'1G] —3-dodecene, 8—methyl-8—trifluoromethyltetracyclo [4.4.0.12,5 ″ 7 , 10] — 3 -dodecene, 8,8,9 —trifluorotetracycline [4.4.0.12'5.17,1Q] — 3 —dodecene, 8,8,9 —tris (trifluorofluorenyl) tetra Ring [4.4.0.I2, 5.17'1Q]-3-dodecene, 8
-15- (10) (10)200402364 ，8，9，9 —四氟四環〔4.4·0.12’5.Γ’1()〕一 3 —十二烯、8 ，9，9 —四（三氟甲基）四環〔4.4.0·12’5·Γ’1(3〕— 3 —十 二烯、8，8 —二氟—9，9 —雙（三氟甲基）四環〔 4.4.0·12,5.Γ，1()〕— 3 —十二烯、8，9 —二氟一 8，9 —雙（ 三氟甲基）四環〔4.4.0.I2’5.17’1G〕— 3 —十二烯、8，8, 9 —三氟一9 —三氟甲基四環〔4.4.0.I2’5. Γ’10〕— 3 —十二 烯、8， 8， 9 —三氟—9 —三氟甲氧基四環〔 HO.l2’5^7，1。〕— 3 —十二烯、8，8，9 —三氟—9 —五氟 丙氧基四環〔4.4.0.12’5.17，1()〕— 3 -十二烯、8 —氟一 8 — 五氟乙基—9，9 一雙（三氟甲基）四環〔4.4.0.I2,5.17,10 〕一 3 —十二烯、8，9一二氟—8 —七氟異丙基一 9 一三氟 甲基四環〔4.4.0.12’5.17’1()〕— 3 —十二烯、8 —氯一8，9 ，9 —三氟四環〔4.4.0.12,5.17，1()〕— 3 —十二烯、8，9 — 二氯—8，9 —雙（三氟甲基）四環〔4.4.0. Γ2,5.Γ，10〕— 3 —十二烯、8— (2，2，2 -三氟乙氧醯基）四環〔 4.4.0.I2,5.I7’10〕— 3 —十二烯、8 —甲基一8— (2，2，2 —三氟乙氧醯基）四環〔4.4.0.12’5.17’1()〕一3 —十二烯、 二環戊二烯等等。 含甲矽烷基之單體，可以使用之化合物如下：5 -三 甲氧基甲矽烷基一 2-原菠烯、5 -二甲氧基氯甲矽烷基-2-原菠烯、5 -甲氧基氯甲基矽烷基一 2-原菠烯、5 -甲 氧基氫化甲基甲矽烷基一 2-原菠烯、5 -二甲氧基氫化甲 矽烷基一 2-原菠烯、5 —甲氧基二甲基甲矽烷基一 2-原 菠烯、5 —三乙氧基甲矽烷基一 2-原菠烯、5 -二乙氧基 -16- (11) (11)200402364 氯甲矽烷基一 2 -原菠烯、5 -乙氧基氯甲基甲矽烷基- 2 一原菠烯、5 -二乙氧基氫化甲矽烷基一 2-原菠烯、5 -乙氧基二甲基甲矽烷基一 2—原菠烯、5 —乙氧基二乙基甲 矽烷基一 2 -原菠烯、5 -丙氧基二甲基甲矽烷基一 2-原 菠烯、5 —三苯氧基甲矽烷基—2 -原菠烯、5 -二苯氧基 甲基曱矽烷基- 2-原菠烯、5—三甲氧基甲矽烷基甲基-2 —原菠烯、5 -（2-三甲氧基甲矽烷基）乙基一 2-原菠 烯、5— (2 —二甲氧基氯甲矽烷基）乙基—2 —原菠烯、5 一 （1—三甲氧基甲矽烷基）乙基—2 —原菠烯、5— (2 — 三甲氧基甲矽烷基）丙基一 2 —原菠烯、5— ( 1 -三甲氧 基甲矽烷基）丙基一 2 -原菠烯、5 -三乙氧基甲矽烷基乙 基一 2-原菠烯、5 -二甲氧基甲基甲矽烷基甲基一 2-原 菠烯、5 —三甲氧基丙基甲矽烷基一 2 —原菠烯、5 —原菠 烯一 2 —羧酸三甲氧基甲矽烷基丙基、5 —原菠烯一 2 -羧 酸三乙氧基甲矽烷基丙基、5 -原菠烯一 2 -羧酸二甲氧基 甲基曱矽烷基丙基、2-甲基—5 —原菠烯-2—羧酸三甲 氧基甲矽烷基丙基、2-甲基—5 —原菠烯一 2 -羧酸二甲 氧基甲基丙基、2 -甲基一 5 —原菠烯一 2 -羧酸三乙氧基 甲矽烷基丙基等等。 此等特定單體中，以8 -甲基一 8 —甲氧醯基四環〔 4.4.0. 12.5.17，1()〕 — 3 —十二烯、8 —亞乙基四環〔 4.4.0··12,5.Γ’1()〕 一 3 -十二烯、8 —乙基四環〔 4.4.0 · 1 2 ’5. Γ ’1G 〕 — 3 —十二烯、五環〔 7.4.0. 12’5.19’12.08’13〕— 3—十五烯，經聚合而得原菠烯系 (12) (12)200402364 樹脂具有高玻璃轉移點、低吸濕性，較爲適用；特別以8 —甲基一8 —甲氧醯基四環〔4·4,0.12’5·Γ’1()〕一 3 —十二 儀最爲適用。 上述之特定單體，可單獨或兩種以上行共聚合反應使 用0 (共聚合性單體） 本發明用以獲得原菠烯系樹脂之聚合步驟中，以上述 特定單體單獨聚合亦可，該特定單體與共聚合性單體進行 共聚合亦佳。 此時使用之共聚合性單體，具體的說，可以使用如： 乙烯、丙烯、丁烯等碳原子2〜12，較佳是2〜8之烯烴 系化合物；環丁烯、環戊烯、環庚烯、環辛烯、二環戊二 烯等之環烯烴等等’環烯烴之碳原子數，以4〜20爲宜， 以5〜1 2爲佳。 又，聚丁二烯、聚異戊二烯、苯乙烯一 丁二烯共聚合 體、乙烯-非共軛二烯共聚合體、聚原菠烯等之在主鏈上 含有碳原子-碳原子間二重結合的不能和烴系聚合體等之 存在下，特定單體行開環聚合亦可；此時所得開環聚合體 的加氫物，可做爲耐衝擊性大的樹脂原料。 (開環聚合觸媒） 本發明中，開環聚合反應是在複分解觸媒的存在下進 行0 〇〇/ -； -18- (13) (13)200402364 此複分解觸媒，是由（a )至少一種選自鎢、鉬、及 銶之化合物、與（b )至少一種選自週期表第1 A族元素 (如鋰、鈉、鉀等）、第2 A族元素（如鎂、鈣等）、第 2B族元素（如鋅、鎘、汞等）、第3B族元素（如硼、鋁 等）、第4A族元素（如鈦、鍩等）、或第4B族元素（ 如矽、錫、鉛等）等之化合物，其至少一個元素具有該元 素一碳原子結合、或該元素一氫結合者，所組合而成的觸 媒；又爲提高此觸媒之活性，添加後述之添加劑者亦佳。 (加聚作用觸媒） 加聚作用觸媒，通常使用週期表第8族之鎳、鉛、鈷 等之陽離子配位化合物、或形成陽離子配位化合物的觸媒 (獲得飽和共聚合體時，使用之觸媒） 特定單體與含有不飽和二重結合化合物，進行共聚合 反應所使用之觸媒，爲由釩化合物與有機鋁化合物所成者 •，釩化合物，使用以一般式 VO ( OR ) aXb或 V ( OR ) cXd〔但，R 爲烴基，0 Sa$3、〇$bS3、2S(a+b) S3、0Sc$4、0SdS4、3S ( c + d ) $4〕所代表釩化 合物、或此等之電子給予體附加物；電子給予體，可以使 用醇類、酚類、酮類、醛類、羧酸、有機酸或有機酸之酯 、醚、酸醯胺、酸酐、烷氧矽烷等含氮電子給予體，銨、 胺、腈、異氰酸鹽等之含氮電子給予體等等；有機鋁化合 -19- (14) (14)200402364 物觸媒成份，使用至少一種選自至少一個具有鋁〜碳結合 或銘-氫結合者。 觸媒成份之比率爲，對釩原子、鋁原子之比（鋁/釩 )在2以上，以2〜50爲佳，最好是在3〜20之範圍。 (分子量調節劑） 聚合體的分子量之調節，雖可以聚合溫度、觸媒之種 類、溶媒之種類等來進；本發明中，以分子量調節劑在反 應系共存來調節較適宜。 適當的分子量調節劑，可以使用乙烯、丙烯、1 -丁 烯、1 —戊烯、1 —己烯、1 —庚烯、1 —辛烯、1 一壬烯、1 一癸烯等之α —烯烴類及苯乙烯等；其中，以1 一 丁烯、 1 一己烯最爲適宜。 此等分子量調節劑，可單獨或兩種以上混合使用；分 子量調節劑之使用量，對供給開環聚合反應之特定單體1 莫耳，以0.005〜0.6莫耳爲宜，以0.02〜0.5莫耳爲佳。 (聚合反應用觸媒） 聚合反應中使用之溶媒（可溶解特定單體、複分解觸 媒、及分子量調節劑之溶媒），可以使用如：戊烷、己烷 、庚烷、辛烷、壬烷、癸烷之烷類；環己烷、環庚烷、環 辛院、十氫萘、原疲院等之環院類；苯、甲苯、二甲苯、 乙基苯、異丙苯等之芳香族烴；氯丁烷、溴己烷、二氯甲 烷、二氯乙烷、六次甲基二溴、氯苯、氯仿、四氯乙烯等 Ο.浐.Α -20- (15) 200402364 之鹵化烷類；鹵化芳香族化合物；醋酸乙酯、 、醋酸異丁酯、丙酸甲酯等之飽和羧酸酯類； 氫呋喃、二甲氧基乙烷等之醚類等等；此等可 以上混合使用；其中，以芳香族烴最爲適用。 溶媒之使用量，對特定單體之重量比，通 ，以1〜5爲佳。 本發明使用之環狀烴系聚合體之分子量， //在0.2〜5之範圍者爲佳。 (加氫觸媒） 如上所得之（共）聚合體，雖可直接做爲； 菠烯系樹脂使用，但其分子中有烯烴性不飽和3 ，以其加氫後之加氫（共）聚合體，做爲本發E 系樹脂使用，更爲適宜。 加氫反應，通常的方法，是在（共）聚合， 置入加氫觸媒，在常壓〜300大氣壓，最好是3 之氫氣下；0〜200°C，最好是20〜180°C溫度一 〇 加氫觸媒，可以使用通常烯烴性化合物之j 使用者；此加氫觸媒，有不均系觸媒與均勻系） 不均勻系觸媒，可以使用以鈀、鉑、鎳、I 貴金屬觸媒物質，附載於碳、矽土、礬土、二· 擔體的固體觸媒；又，均勻系觸媒，可以使用ί 三乙基鋁、乙醯丙酮鎳/三乙基鋁、辛烯酸鈷/ •Η.〆·〆A -30DC5 酸正丁酯 丁醚、四 獨或兩種 爲 1〜10 固有粘度 發明之原 合存在時 之原菠烯 溶液中， 200氣壓 進行作用 氫反應所 媒。 、釕等之 化鈦等之 烷酸鎳/ 正丁基鋰 -21 - (16) (16)200402364 、二氧化鈦/單氯化一乙基鋁、醋酸鍺、氯三（三苯基膦 )鍺、二氯三（三苯基膦）釕、氯氫醯基三（三苯基膦） 釕、二氯醯基三（三苯基膦）釕等等；觸媒之形態，爲粉 末或粒狀均可。 此等加氫觸媒之使用比率，對（共）聚合體之重量比 ，以1 Χίο—6〜2爲宜。 加氫後所得加氫（共）聚合體，具有優異的熱安定性 ，在成形加工使用或使用時，其特性不會因爲加熱而劣化 ;氫添加率，通常在 50%以上，70%以上較佳，90%以 上更佳，95%以上更好，以在98%爲上上佳。 本發明使用之熱可塑性原菠烯系樹脂，其於30 °C之 氯仿（三氯甲烷）中測得之固有粘度〔//〕，以0.2〜5 dl/公克爲宜，以0.4〜4 dl/公克爲佳；超過5 dl/公克 時，溶液粘度過高，會使加工性降低；低於0.2 dl/公克 時，成形品的強度會發生問題。 又，本發明所使用原菠烯系樹脂之分子量，以凝膠滲 透色層分析法（GPC )測定，其聚苯乙換算之數平均分子 量（Μη)以5，000〜1，〇〇〇,〇〇〇爲宜，重量平均分子量（ Mw)以10,000〜3，000,000爲宜；數平均分子量（Μη)在 8,000 - 700,000，重量平均分子量（Mw)在 2,000〜 1，000,000之範圍，最爲適用。 本發明使用的上述熱可塑性原菠烯系樹脂，是由上述 之開環（共）聚合體、加氫（共）聚合體、飽和共聚合體 、或附加型（共）聚合體、及其加氫（共）聚合體所構成 -22- (17) (17)200402364 ’其中可以添加眾所周知的防止氧化劑、吸收紫外線等以 求安定化；爲提高其加工性，可以添加如滑劑等已往樹脂 加工用之添加劑。 本發明，由上述熱可塑性原菠烯系樹脂所成薄膜（薄 膜）之形成方法是，以溶液流延法或熔融成形法使原菠烯 系樹脂形成薄膜狀，經延伸、表面加壓、塑模擠壓等之處 理’而得均勻厚度之樹脂薄膜的方法；溶液流延法之溶媒 ’可以使用甲苯等上述聚合反應所用之溶媒；熔融成形法 ，可以採用T型塑模擠壓機押出成形的方法、吹塑薄膜法 等之方法；採用熔融成形法時，熔融溫度以200〜3 50 爲且’以250〜330C爲佳’以280 °C〜320 °C爲最適用。 又，本發明中，於形成防止反射膜之前，先對薄板基 材施行增粘塗劑之塗佈、化學蝕刻處理、電暈處理、電漿 處理等之前處理亦佳。 其次，本發明（A)層使用之化合物，爲光學透明且 其折射率高於基礎薄膜之折射率的化合物；對此雖然沒有 特叩的限制，但是必須考量其與基礎薄膜之密著性及耐熱 性而選擇之；又，「光學透明」是指，使用膜厚中全光線 透過率（依Π S - K 7 10 5測定法A之標準測定），通常在 50%以上，在70%以上較適宜，在8〇%以上更適合的意 思；相關的化合物，一般使用丙烯酸系、丙烯酸一氨基甲 酸酯系、環氧系等之透明有機系塗佈材料；此等有機系塗 佈材料爲溶劑乾燥型、熱硬化型、紫外線等之活性能量線 硬化型等各種市售品’只要符合本發明之必要條件都可使 (18) (18)200402364 用；又，鋁、矽、鈦等之透明金屬氧化物、氧化銦錫等之 無機化合物，也可以做爲（A )層使用。 於基礎薄膜上形成（A )層的方法，如爲有機系之塗 佈材料時，可以使用浸漬法、印刷法、旋轉塗佈法，使用 塗佈機法等眾所周知的方法；如爲使用金屬氧化物時，可 以使蒸著法、噴鍍法等眾所周知的方法；又，在基礎薄膜 上形成（A)層之前，爲提高基礎薄膜與（a)層之密著 性，可在基礎薄膜上施行電漿處理、酸處理等眾所周知的 表面處理。 又，塗佈底層塗料亦佳；但，使用底層塗料時，底層 塗料之折射率必須低於（A )層化合物之折射率。 (A)層之厚度，通常爲〇.〇1 //m〜1 /zm，以0.03 M m〜0.3 //m爲佳，更好的是〇·〇5〜0.15 //m;薄於 0.01 // m、或厚於1 # m時，不能充份發揮防止反射機 能；又，爲發揮最大的防止反射機能，必須考量後述（B )層的厚度。 又，本發明中，使用有機系塗佈材料，以形成（A ) 層的方法是’以有機丨谷媒使有機化合物溶解後，其溶液使 用棒桿塗佈機以澆鑄法，塗佈於上述薄板上，再經乾燥及 /或硬化的方法而成。 進行加熱硬化時，加熱溫度以8 0。(：〜1 6 5 °C爲宜，以 1 0 0〜1 5 0 C更佳，加熱時間爲1 0分鐘〜3小時，以3 0分 鐘〜2小時更適合。 以紫外線等之活性能量線照射施行硬化時，以在氮氣 -24- (19) 200402364 等不活性氣體的大氣中進行爲佳；照射能量 線之種類適當選擇之，爲紫外線時，通常在 〜10 J/cm 2之範圍，以100 mJ/cm 2〜： ，以 300 mJ/cm2 〜3 J/cm2 更適合。 其次，本發明之（B)層使用的化合物 且具有導電性之高分子化合物爲佳；又，「 指，使用膜厚中，全光線透過率（依Π S K A之標準測定），通常在50%以上，70%以 以上更好的意思；又，「導電性」是指，於 率，通常在1 χ10_12/Ω 以上，ΐχ 以上較適合的意思；相關的化合物，具體的 聚苯胺、聚吡咯、聚噻吩、聚呋喃、聚硒吩 合物之構造單位上與取代基結合的取代誘導 又，本發明中，構成層合於薄膜表面二 合物，其折射率以高於構成層合於其上之（ 者爲佳，如此可以獲得較高的防止反射效果 在（A)層之上形成（B)層的方法是 述（B )層使用之化合物溶解、分解後，以 法、旋轉塗佈法’使用塗機法等眾所周知的 法，CVD法、氣相聚合法等等而形成；又 性及導電性之化合物所成薄膜，經層合也石 層。 (A)層之厚度，通常爲〇〇1 vm〜i 〜O.j 爲佳，以 〇〇5 //m 〜0.15 36S4 :，依使用能量 .5 0 mJ/cm 2 5 J/ c m 2爲佳 ，以光學透明 光學透明」.是 一 7105測定法 、上較佳，8 0 % •室溫下之導電 1 0 - 1 V Ω · c m 說，可以使用 、以及此等化 :體等等。 L ( A )層的化 〔B )層化合物 〇 ’以溶劑使上 浸漬法、印刷 方法塗佈的方 ，將具有透明 丁以形成（B ) V m ’ 以 〇.〇3 // m更好；薄 -25- (20) 200402364 於ο . 01 // m時，防止反射機能或防止帶電性都不足；另 一方面，此1 // m厚時，難以確保其透明性。 又，爲發揮本發明中最大的防止反射機能，必須控制 (A)層及（B)層之總厚度，通常，（A)層及（B)層 之合計厚度爲0.03 /zm〜1.5 //m、以0.05 //m〜0.5 爲佳、以0.08 /zm〜0.25 //m更好。 又，本發明之層合薄膜，係爲透明者；做爲防止反射 膜時’其透明性爲以多光源分光測色計，測定其全光線透 過率之値。 此全光線透過率，以90%以上爲宜，91%以上爲佳 ’ 92%以上更佳，以94%以上爲最好。 本發明之層合薄膜，透明性及防止帶電性優異，反射 率低’適合使用於各種爲提高顯示裝置之視認性的防止反 射薄膜。 【實施方式】 〔實施例〕 以實施例就本發明做具體的說明如下；本發明對此沒 有特別的限制；又，實施例中之部及％，爲重量份及重量 % ;實施例中之各種測定，依下列方法進行。 〔數平均分子量（Μη)〕-15- (10) (10) 200402364, 8,9,9 —tetrafluorotetracycline [4.4 · 0.12'5.Γ'1 ()]-3-dodecene, 8, 9, 9 — tetra (three Fluoromethyl) tetracyclo [4.4.0 · 12'5 · Γ'1 (3) —3-dodecene, 8,8—difluoro-9,9—bis (trifluoromethyl) tetracyclo [4.4 .0 · 12,5.Γ, 1 ()] — 3-dodecene, 8,9—difluoro-8,9—bis (trifluoromethyl) tetracyclo [4.4.0.I2'5.17'1G ] — 3 —dodecene, 8,8, 9 —trifluoro-9 —trifluoromethyl tetracyclo [4.4.0.I2'5. Γ'10] — 3 —dodecene, 8, 8, 9 —Trifluoro-9 —trifluoromethoxytetracycline [HO.l2'5 ^ 7,1.] — 3-dodecene, 8,8,9 —trifluoro-9 —pentafluoropropoxytetracycline [4.4.0.12'5.17, 1 ()] — 3-dodecene, 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.I2,5.17 , 10] -3-dodecene, 8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracycline [4.4.0.12'5.17'1 ()]-3-dodecene , 8-chloro-8,9,9-trifluorotetracycline [4.4.0.12, 5.17, 1 ()]-3-dodecene, 8, 9- Dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0. Γ2,5.Γ, 10] 3-dodecene, 8- (2,2,2-trifluoroethoxyfluorene Radical) tetracyclo [4.4.0.I2,5.I7'10] —3-dodecene, 8-methyl-8— (2,2,2-trifluoroethoxyfluorenyl) tetracyclo [4.4. 0.12'5.17'1 ()]-3-dodecene, dicyclopentadiene, etc. Monosilyl-containing monomer, the following compounds can be used: 5-trimethoxysilyl-2 Ene, 5-dimethoxychlorosilyl-2-oro-spinene, 5-methoxychloromethylsilyl- 2-orospinene, 5-methoxyhydromethylsilyl- 2- Orthospinene, 5-dimethoxyhydrosilyl-2-orthospinene, 5-methoxydimethylsilyl- 2-orthospinene, 5-triethoxysilyl-2 -Orthospinene, 5-diethoxy-16- (11) (11) 200402364 chlorosilyl-2 -orthospinene, 5 -ethoxychloromethylsilyl-2 -orthospinene, 5 -diethoxyhydrosilyl-2 -orthospinene, 5 -ethoxydimethylsilyl -2 -orthospinene, 5 -ethoxydiethylsilyl-2 -ortho Alkene, 5-propoxydimethylsilyl-2-orthospinene, 5-triphenoxysilyl-2-orthospinene, 5-diphenoxymethylphosphonium silyl- 2- Orthospinene, 5-trimethoxysilylmethyl-2-orthospinene, 5- (2-trimethoxysilyl) ethyl-orthospinene, 5- (2-dimethoxy Chlorochlorosilyl) ethyl-2 orthospinene, 5-mono (1-trimethoxysilyl) ethyl-2, orthospinene, 5- (2-trimethoxysilyl) propyl One 2-orthospinene, 5- (1-trimethoxysilyl) propyl- 2-orthospinene, 5-triethoxysilylethyl- 2-orospinene, 5-dimethyl Oxymethylsilylmethyl-2-orthospine, 5-trimethoxypropylsilyl- 2-orthospinene, 5-ortho-spinyl- 2-carboxylate trimethoxysilylpropane Group, 5-orthospinyl-2-carboxylic acid triethoxysilylpropyl, 5-orthospinyl-2-carboxylic acid dimethoxymethylphosphonium silylpropyl, 2-methyl-5 —Orospinene-2—carboxylic acid trimethoxysilylpropyl, 2-methyl-5 —orthopinene-2—carboxylic acid dimethyl Oxymethylpropyl, 2-methyl-1 5-orthospinyl-2-carboxylic acid triethoxysilylpropyl and the like. Among these specific monomers, 8-methyl- 8-methoxyfluorenyltetracycline [4.4.0. 12.5.17, 1 ()]-3-dodecene, 8-ethylenetetracycline [4.4 .0 ·· 12,5.Γ'1 ()] 3 -dodecene, 8-ethyltetracycline [4.4.0 · 1 2 '5. Γ' 1G]-3 -dodecene, pentacyclic [7.4.0. 12'5.19'12.08'13] — 3-pentadecene, which is polymerized to obtain orthospines (12) (12) 200402364 The resin has a high glass transition point and low hygroscopicity, which is more suitable. ; In particular, 8-methyl- 8-methoxyfluorenyltetracycline [4 · 4, 0.12'5 · Γ'1 ()]-3-12 instrument is most suitable. The above specific monomers can be used alone or in two or more copolymerization reactions. 0 (copolymerizable monomers) In the polymerization step for obtaining an orthospinene resin in the present invention, the above specific monomers can also be polymerized alone. It is also preferable that the specific monomer is copolymerized with a copolymerizable monomer. The copolymerizable monomer used at this time, specifically, an olefin-based compound having 2 to 12, preferably 2 to 8 carbon atoms such as ethylene, propylene, and butene; cyclobutene, cyclopentene, The number of carbon atoms of the cycloolefin, such as cycloheptene, cyclooctene, dicyclopentadiene, and the like, is preferably 4 to 20, and more preferably 5 to 12. In addition, polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polyordinolene, and the like contain carbon atoms-carbon atoms In the presence of a heavy bond that cannot be combined with a hydrocarbon-based polymer, ring-opening polymerization of a specific monomer is also possible; the hydrogenated product of the ring-opening polymer obtained at this time can be used as a resin material with high impact resistance. (Ring-opening polymerization catalyst) In the present invention, the ring-opening polymerization reaction is performed in the presence of a metathesis catalyst in the presence of a metathesis catalyst. -18- (13) (13) 200402364 This metathesis catalyst is composed of (a) At least one compound selected from tungsten, molybdenum, and thallium, and (b) at least one compound selected from Group 1 A elements (such as lithium, sodium, potassium, and the like) and Group 2 A elements (such as magnesium, calcium, and the like) of the periodic table , Group 2B elements (such as zinc, cadmium, mercury, etc.), Group 3B elements (such as boron, aluminum, etc.), Group 4A elements (such as titanium, hafnium, etc.), or Group 4B elements (such as silicon, tin, For compounds such as lead), at least one element has a catalyst composed of the combination of the element-carbon atom or the element-hydrogen combination; in order to improve the activity of this catalyst, those who add the additives described below also good. (Polymerization catalysts) For polyaddition catalysts, cationic coordination compounds such as nickel, lead, and cobalt of Group 8 of the periodic table, or catalysts that form cationic coordination compounds are generally used (to obtain a saturated copolymer) Catalyst) The catalyst used for the copolymerization reaction of specific monomers and unsaturated double-bonded compounds is a compound made of a vanadium compound and an organoaluminum compound. • A vanadium compound, using the general formula VO (OR) aXb or V (OR) cXd [However, R is a hydrocarbon group, 0 Sa $ 3, 0 $ bS3, 2S (a + b) S3, 0Sc $ 4, 0SdS4, 3S (c + d) $ 4] represents a vanadium compound, or this Additions of electron donors, etc .; For electron donors, alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acids or esters of organic acids, ethers, amidoamines, anhydrides, alkoxysilanes, etc. can be used. Nitrogen electron donors, nitrogen-containing electron donors such as ammonium, amine, nitrile, isocyanate, etc .; organoaluminum compounds-19- (14) (14) 200402364 catalyst components, using at least one selected from at least one With aluminum ~ carbon bonded or inscribed-hydrogen bonded. The ratio of the catalyst components is such that the ratio of vanadium atoms and aluminum atoms (aluminum / vanadium) is 2 or more, preferably 2 to 50, and most preferably 3 to 20. (Molecular weight regulator) Although the molecular weight of the polymer can be adjusted, the polymerization temperature, the type of the catalyst, and the type of the solvent can be adjusted. In the present invention, it is appropriate to adjust the molecular weight regulator in the reaction system. Suitable molecular weight regulators include α, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Alkenes and styrene; among them, 1-butene and 1-hexene are most suitable. These molecular weight regulators can be used singly or in combination of two or more. The amount of molecular weight regulator used is 1 mole for the specific monomer supplied for the ring-opening polymerization reaction, preferably 0.005 ~ 0.6 mole, and 0.02 ~ 0.5 mole. Ears are better. (Polymerization catalyst) The solvent used in the polymerization reaction (solvent that can dissolve specific monomers, metathesis catalysts, and molecular weight regulators), such as pentane, hexane, heptane, octane, and nonane , Decane, alkane; cyclohexane, cycloheptane, cyclohexyl, decahydronaphthalene, former fatigue, etc .; benzene, toluene, xylene, ethylbenzene, cumene and other aromatic Hydrocarbons; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromo, chlorobenzene, chloroform, tetrachloroethylene, etc. 0.Ο.Α -20- (15) 200402364 Class; halogenated aromatic compounds; ethyl acetate, isobutyl acetate, methyl propionate and other saturated carboxylic acid esters; hydrofuran, dimethoxyethane and other ethers, etc .; these can be mixed on Use; Among them, aromatic hydrocarbons are most suitable. The amount of solvent used, the weight ratio of specific monomers, is preferably 1 to 5. The molecular weight of the cyclic hydrocarbon polymer used in the present invention is preferably in the range of 0.2 to 5. (Hydrogenation catalyst) Although the (co) polymer obtained as above can be used directly; the spinene resin is used, but its molecule has olefinic unsaturated 3, and its hydrogenation (co) polymerization after hydrogenation Body, it is more suitable to use as E-series resin. The hydrogenation reaction is usually carried out by (co) polymerization, placing a hydrogenation catalyst under normal pressure to 300 atmospheres, preferably 3 hydrogen; 0 to 200 ° C, preferably 20 to 180 ° C temperature 10 hydrogenation catalyst, you can use j users of ordinary olefinic compounds; this hydrogenation catalyst, heterogeneous catalyst and homogeneous catalyst) heterogeneous catalyst, you can use palladium, platinum, nickel , I Precious metal catalysts, solid catalysts supported on carbon, silica, alumina, and two carriers; and, even catalysts, you can use triethyl aluminum, acetoacetone nickel / triethyl aluminum Cobalt octanoate / • Η.〆 · 〆A -30DC5 n-butyl butyl ether, four or two of 1 to 10 Intrinsic viscosity of the invention The original spinene solution in the presence of the original combination, 200 pressure Hydrogen reaction medium. Nickel alkanoates / n-butyllithium-21, titanium oxides such as ruthenium, etc.-(16) (16) 200402364, titanium dioxide / monoethylaluminum monochloride, germanium acetate, chlorotris (triphenylphosphine) germanium, Dichlorotris (triphenylphosphine) ruthenium, chlorohydrofluorenyltris (triphenylphosphine) ruthenium, dichlorofluorenyltris (triphenylphosphine) ruthenium, etc .; the form of the catalyst is powder or granular can. The ratio of the use of these hydrogenation catalysts to the weight of the (co) polymer is preferably 1 × 6 ~ 2. The hydrogenated (co) polymer obtained after hydrogenation has excellent thermal stability, and its characteristics will not be deteriorated by heating during use or use during forming processing; the hydrogen addition rate is usually more than 50%, and more than 70%. Good, more than 90% is better, more than 95% is better, and 98% is better. The inherent viscosity [//] of the thermoplastic orthospinene resin used in the present invention measured in chloroform (trichloromethane) at 30 ° C is preferably 0.2 to 5 dl / g, and 0.4 to 4 dl More than 5 dl / g, the solution viscosity is too high, which will reduce the processability; when less than 0.2 dl / g, the strength of the molded product will have problems. In addition, the molecular weight of the orthospinene resin used in the present invention is measured by gel permeation chromatography (GPC), and the polystyrene-equivalent number average molecular weight (Mη) is 5,000 to 1,000,000. The weight average molecular weight (Mw) is preferably 10,000 to 3,000,000; the number average molecular weight (Mη) is 8,000 to 700,000, and the weight average molecular weight (Mw) is in the range of 2,000 to 1,000,000, which is most suitable. . The thermoplastic orthospinene resin used in the present invention is composed of the ring-opening (co) polymer, hydrogenation (co) polymer, saturated copolymer, or additive (co) polymer, and hydrogenation thereof. Composition of (co) polymer-22- (17) (17) 200402364 'Well-known anti-oxidants and UV absorption can be added for stabilization; in order to improve its processability, additives such as lubricants can be added for conventional resin processing Of additives. In the present invention, the method for forming a thin film (film) made of the above-mentioned thermoplastic orthospinene resin is to form the orthospinene resin into a film shape by a solution casting method or a melt molding method. Processes such as die extrusion to obtain resin films of uniform thickness; solvents used in the solution casting method can use toluene and other solvents used in the above-mentioned polymerization reaction; and melt molding methods, which can be extruded using a T-die extruder. Method, blown film method, etc .; when the melt-molding method is used, the melting temperature is 200 ~ 3 50 and 'preferably 250 ~ 330C' is 280 ° C ~ 320 ° C. In the present invention, before forming the antireflection film, it is also preferable to perform a pretreatment such as application of a tackifier, chemical etching treatment, corona treatment, and plasma treatment on the thin plate substrate. Secondly, the compound used in the layer (A) of the present invention is a compound that is optically transparent and has a refractive index higher than that of the base film; although there are no specific restrictions on this, it is necessary to consider its adhesion to the base film and Heat resistance is selected; "optical transparency" refers to the use of the total light transmittance in the film thickness (measured according to the standard of Π S-K 7 10 5 measurement method A), usually 50% or more, 70% or more More suitable, more than 80% more suitable meaning; related compounds, generally use acrylic, acrylic mono-urethane-based, epoxy-based transparent organic coating materials; these organic coating materials are Various commercially available products such as solvent-drying type, heat-curing type, and active energy ray-curing type such as ultraviolet rays can be used as long as they meet the requirements of the present invention (18) (18) 200402364; Inorganic compounds such as transparent metal oxides and indium tin oxide can also be used as the (A) layer. For the method of forming the (A) layer on the base film, if it is an organic coating material, a well-known method such as a dipping method, a printing method, a spin coating method, or a coater method can be used; if a metal oxide is used, For example, a well-known method such as vapor deposition method or thermal spraying method can be used. Before forming the (A) layer on the base film, in order to improve the adhesion between the base film and the (a) layer, it can be performed on the base film. Well-known surface treatments such as plasma treatment and acid treatment. It is also good to apply a primer; however, when using a primer, the refractive index of the primer must be lower than the refractive index of the (A) layer compound. (A) The thickness of the layer is usually 0.001 // m ~ 1 // zm, preferably 0.03 M m ~ 0.3 // m, more preferably 0.005 ~ 0.15 // m; thinner than 0.01 // m, or thicker than 1 # m, the anti-reflection function cannot be fully exerted; in order to exert the maximum anti-reflection function, the thickness of the layer (B) described later must be considered. In the present invention, an organic coating material is used to form the (A) layer by dissolving an organic compound with an organic medium and then applying the solution to the above using a rod coater by a casting method. Sheets are then dried and / or hardened. When performing heat hardening, the heating temperature is 80 °. (: ~ 1 6 5 ° C is more suitable, 100 ~ 150 ° C is more preferable, heating time is 10 minutes to 3 hours, 30 minutes to 2 hours is more suitable. Active energy rays such as ultraviolet rays When curing is performed by irradiation, it is better to perform in the atmosphere of inert gas such as nitrogen-24- (19) 200402364; the type of energy rays to be irradiated is appropriately selected. In the case of ultraviolet rays, it is usually in the range of ~ 10 J / cm 2. 100 mJ / cm 2 to: 300 mJ / cm 2 to 3 J / cm 2 is more suitable. Second, the compound used in the layer (B) of the present invention and a conductive polymer compound is preferred; In the use of the film thickness, the total light transmittance (measured according to the standard of Π SKA) is usually more than 50%, and more preferably 70% or more. In addition, "conductivity" refers to the rate, usually 1 x 10_12 / Above Ω and above χχ are more suitable meanings; the related compounds, specific polyaniline, polypyrrole, polythiophene, polyfuran, polyselenophenate and the structural unit of the substituent are combined to induce substitution. In the present invention, The constituent laminate is laminated on the surface of the film, and its refractive index is higher than that of the constituent laminate. The better one is to obtain a higher anti-reflection effect. The method for forming the (B) layer on the (A) layer is to dissolve and decompose the compound used in the (B) layer, and then apply the method by spin coating. The cloth method is formed by a well-known method such as a coater method, a CVD method, a gas phase polymerization method, and the like; and a thin film made of a compound that is conductive and conductive is also laminated by a layer. (A) The thickness of the layer is usually 〇〇1 vm ～ i ～ Oj is better, 〇 05 / m ～ 0.15 36S4 :, depending on the use of energy. 50 mJ / cm 2 5 J / cm 2 is better, it is optically transparent and optically transparent. The 7105 method is better, 80%. • Conductive at room temperature 10-1 V Ω · cm. It can be used, and so on: bulk, etc. Layer (B) layer of L (A) layer. The compound 〇 ′ is coated with a solvent by an upper dipping method or a printing method, and it has transparent butyl to form (B) V m ′, preferably 0.003 // m; thin -25- (20) 200402364 in ο When 01 // m, the anti-reflection function or the electrification prevention property are insufficient; on the other hand, when the thickness is 1 // m, it is difficult to ensure its transparency. The largest anti-reflection function in Ming Dynasty must control the total thickness of (A) layer and (B) layer. Generally, the total thickness of (A) layer and (B) layer is 0.03 /zm~1.5 // m, 0.05 / /m~0.5 is preferable, and 0.08 / zm ~ 0.25 // m is more preferable. Moreover, the laminated film of the present invention is transparent; when used as an anti-reflection film, its transparency is measured by multi-light spectrometry. Meter to determine the total light transmittance. The total light transmittance is preferably 90% or more, more preferably 91% or more, more preferably 92% or more, and most preferably 94% or more. The laminated film of the present invention is excellent in transparency and antistatic property and has a low reflectance, and is suitable for various antireflection films for improving the visibility of a display device. [Embodiments] [Examples] The following specifically describes the present invention with examples; the present invention is not particularly limited thereto; and the parts and% in the examples are parts by weight and% by weight; Various measurements were performed according to the following methods. [Number average molecular weight (Μη)]
使用東曹製HLC - 8〇2〇型凝膠滲透色層分析（gpc )裝置’以Η型柱筒，於四氫呋喃（thf )溶媒中40°C •26- (21) (21)200402364 下測定，所得分子量爲標準聚苯乙烯換算値。 〔氫添加率〕 單獨聚合體加氫時，以60MHz，NMR測定，酯 基之甲基氫與烯烴系氫之個別吸收強度之比，或石臘系氫 與烯烴系氫之個別吸收強度之比，來測定氫添加率；又， 爲共聚合體加氫時，聚合後之共聚合體之iH — NMR吸收 、與氫化後之加氫共聚合體者，相比較而算出氫添加率。 〔玻璃轉移溫度（Tg)〕 以精工公司製掃描熱量計（DSC)之DSC— 6200，在 氮氣之大氣中，升溫速度爲1 0 °C /分鐘下測定之。 〔薄膜之厚度〕 以度盤式厚度指示器測定之。 〔全光線透過率〕 以π S - K — 7 1 0 5測定法A之標準測定之。 〔反射率之測定〕 以附帶積分球分光光度計（日立製、U3410型）、 5 5 0 n m之光線波長測定之。 〔防止帶電性〕 ρρ -27、 (22) / 200402364 使用乾燥的毛巾，在1 0公分正方形的薄膜表面（層 合面）於加重1公斤下擦拭1 5次；其次以乾燥的滑石粉 (通過2 0 0篩目之細粉），散佈於經毛布擦拭的薄膜表面 ;其後，在離開散佈滑石粉的薄膜表面3 0公分處，以吹 髮機吹送冷風（關掉加熱器）5分鐘，以目視評估滑石粉 之殘留情況。 又’本評估在2 3 °C，相對濕度1 5 %之環境下進行， 其評估標準如下。 φ 〇：薄膜之透明性沒有變化。 △:薄膜稍有混濁，還可透過薄膜看到另一面。 · X :滑石粉附著於薄膜上，薄膜的透明性顯著的下降 _ ，透過薄膜很難看到另一面。 〔合成例〕 將8—甲基一 8—甲氧醯基四環〔4.4.0.12,5. I7，10〕—3 —十二烯100公克、1，2—二甲氧基乙烷60公克、環己 · 烷240公克、1 一己烯9公克、及氯化二乙基鋁0.96莫耳 /公升之甲苯溶液3.4毫升，置入內容積！公升之氮氣取 化熱壓器中；另一方面，在別的燒瓶中，加入六氫化鎢之 〇·〇5莫耳/公升之1，2—二甲氧乙烷溶液20毫升、與三 聚乙醛之0.1莫耳/公升之1，2-二甲氧基乙烷溶液10 毫升’於氮氣的大氣中混合之；將此混合液4.9毫升，加 入上述熱壓器中之混合物；其次，使熱壓器加熱至8 〇。〇 並保持’攪拌4小時以進行複分解開環聚合反應。 -3 00 / -28- (23) (23)200402364 在所得聚合體溶液中，加入1，2 -二甲氧基乙烷與 環己烷之2/ 8重量比的混合溶媒，使聚合體/溶媒之重 量比成爲1 / 1 0後，加入三乙醇胺20公克，在室溫下攪 拌1 〇分鐘；於此溶液中，更加入甲醇5 0 0公克，加熱3 〇 分鐘後靜置之；分離成兩層，除去其上層，再加入甲醇 5 〇 〇公克，攪拌靜置後除去上層；同樣操作進行2次，將 所得之下層，以環己烷、1，2-二甲氧基乙烷適當稀釋之 ，可得聚合體濃度10%之環己烷/1，2 —二甲氧基乙烷 溶液。 將20公克做爲加氫觸媒之鈀/矽土氧化鎂（日揮化 學製、鈀之量爲5 % )加入此溶液中，置入熱壓器內，在 氫氣壓力40公斤/平方公分、165°C溫度下反應4小時後 ’過濾除去加氫觸媒，即得加氫聚合體溶液；在所得加氫 聚合體溶液中，加入防止氧化劑季戊四醇一四（3 -（ 3， 5 一一一第二級丁基一 4一羥基苯基）丙酸酯〕，其添加量 對加氫聚合體爲0 . 1 %，在3 6 0 °C減壓下進行脫溶媒；其 次’在氮氣的大氣中，使用溶融押出機，使加氫聚合體粒 狀化；此所得加氫聚合體，稱之爲「樹脂A」。 樹脂A之聚苯乙烯換算重量平均分子量爲7.0 χίο4 、400 ΜΗΖ之NMR測定，其實質的加氫率爲100% •’又，以D S C測定，其玻璃轉移點爲1 6 8。(3。 〔合成例2〕 將5 —亞乙基一 2 一四環十二烯，以與合成例1相同 -29- (24) (24)200402364 操作，進行複分解開環聚合後，經加氫、造粒而得「樹脂 B」。 樹脂B之聚苯乙烯換算重量平均分子量爲55 χίο4 、400 MHz之1H— NMR測定，其實質的加氫率爲ι〇〇% ;又，以D S C測定，其玻璃轉移點爲1 4 〇 °C。 〔合成例3〕 將雙環〔2.2.1〕庚—2-烯75公克、5-己基一雙環 〔2.2.1〕庚一2 —烯36公克、甲苯555公克、1—己烯 2.〇毫莫耳，置入2公升，在氮氣大氣中之熱壓器中。 將三乙基鋁0.2毫莫耳、三氟化硼乙基醯鹵化合物 1.8毫莫耳、及預先準備好，以己烷溶液之辛酸鎳與六氟 化銻酸，依莫耳比1 : 1，在一 10 °C下反應，將副產之沈 澱Measured using Toshiba HLC-8020 gel permeation chromatography (gpc) device in a Η-type cartridge in tetrahydrofuran (thf) solvent at 40 ° C • 26- (21) (21) 200402364 The obtained molecular weight is standard polystyrene equivalent 値. [Hydrogen addition rate] When the individual polymer is hydrogenated, the ratio of the individual absorption intensities of the methyl hydrogen of the ester group and the olefin-based hydrogen, or the ratio of the individual absorption intensities of paraffin-based hydrogen and the olefin-based hydrogen is measured at 60 MHz and NMR. To measure the hydrogen addition rate; when hydrogenating the copolymer, the iH-NMR absorption of the copolymer after polymerization is compared with the hydrogenated copolymer after hydrogenation to calculate the hydrogen addition rate. [Glass Transition Temperature (Tg)] Measured with DSC-6200, a scanning calorimeter (DSC) manufactured by Seiko Co., Ltd., in a nitrogen atmosphere at a temperature rise rate of 10 ° C / min. [Thickness of film] Measured with a dial-type thickness indicator. [Total Light Transmittance] Measured in accordance with π S-K-7 105 measurement method A. [Measurement of reflectance] Measured with a wavelength of light of 5 50 nm using an integrating sphere spectrophotometer (Hitachi, U3410 type). 〔Charging prevention〕 ρρ -27, (22) / 200402364 Using a dry towel, wipe the film surface (laminated surface) of 10 cm square with a weight of 1 kg for 15 times; followed by dry talc powder (pass 2 0 0 fine mesh powder), spread on the surface of the film wiped with a woolen cloth; then, 30 cm away from the surface of the film spreading talc powder, blow cold air (turn off the heater) with a blower for 5 minutes, Visually evaluate the residual condition of talc. The evaluation was performed in an environment of 2 3 ° C and a relative humidity of 15%. The evaluation criteria are as follows. φ 〇: There is no change in the transparency of the film. △: The film is slightly cloudy, and the other side can be seen through the film. · X: Talc powder adheres to the film, and the transparency of the film decreases significantly. It is difficult to see the other side through the film. [Synthesis example] 8-methyl-8-methoxyfluorenyltetracycline [4.4.0.12,5. I7,10]-3-dodecene 100 g, 1,2-dimethoxyethane 60 g , 240 g of cyclohexane, 9 g of 1-hexene, and 3.4 ml of a toluene solution of 0.96 mol / liter of diethylaluminum chloride, put in the inner volume! Liter of nitrogen was taken from the autoclave; on the other hand, in another flask, 0.05 ml of tungsten hexahydride / liter of 1,2-dimethoxyethane solution 20 ml was added, and 10 ml of a 0.1 mol / liter solution of 1,2-dimethoxyethane in acetaldehyde was mixed in an atmosphere of nitrogen; 4.9 ml of this mixed solution was added to the mixture in the autoclave; second, The autoclave is heated to 80 °. 〇 and kept 'stirred for 4 hours to perform metathesis ring-opening polymerization. -3 00 / -28- (23) (23) 200402364 In the obtained polymer solution, a mixed solvent of 2/8 weight ratio of 1,2-dimethoxyethane to cyclohexane was added to make the polymer / After the weight ratio of the solvent became 1/10, 20 grams of triethanolamine was added, and the mixture was stirred at room temperature for 10 minutes. In this solution, 500 grams of methanol was further added, and the mixture was left to stand after heating for 30 minutes. Two layers, the upper layer was removed, and 500 g of methanol was added, and the upper layer was removed after being left to stir; the same operation was performed twice, and the obtained lower layer was appropriately diluted with cyclohexane and 1,2-dimethoxyethane. In other words, a cyclohexane / 1,2-dimethoxyethane solution having a polymer concentration of 10% can be obtained. Add 20 grams of palladium / silica magnesia (made by Nippon Chemical Co., Ltd., 5% palladium in 5%) as a hydrogenation catalyst to this solution, put it in a autoclave, and press the hydrogen pressure at 40 kg / cm2, 165 After reacting at a temperature of 4 ° C for 4 hours, the hydrogenation catalyst is filtered off to obtain a hydrogenated polymer solution. To the obtained hydrogenated polymer solution, an oxidant pentaerythritol tetrakis (3-(3, 5-1-1) is added. Secondary butyl-4-hydroxyphenyl) propionate], the addition amount of which is 0.1% to the hydrogenated polymer, desolvent under reduced pressure at 360 ° C; secondly 'in the atmosphere of nitrogen The melted extruder was used to granulate the hydrogenated polymer; the obtained hydrogenated polymer was referred to as "resin A." The polystyrene-equivalent weight average molecular weight of resin A was 7.0 χίο4, 400 ΜΗZ NMR measurement, Its substantial hydrogenation rate is 100%. Also, as measured by DSC, its glass transition point is 168. (3. [Synthesis Example 2] 5-Ethylene-2 tetracyclododecene was The operation is the same as in Synthesis Example 1. -29- (24) (24) 200402364, after performing metathesis ring-opening polymerization, hydrogenation and granulation “Resin B” was obtained. The polystyrene-equivalent weight average molecular weight of Resin B was measured by 1H-NMR at 55 × 4, 400 MHz, and its substantial hydrogenation rate was ιο ％; and its glass transition point was measured by DSC It is 14 ° C. [Synthesis Example 3] 75 g of bicyclic [2.2.1] hept-2-ene, 5-hexyl-bicyclo [2.2.1] 36 g of hept-2-ene, 555 g of toluene, 1 —Hexene 2.0 millimoles, placed in a 2 liter autoclave in a nitrogen atmosphere. Triethylaluminum 0.2 millimoles, boron trifluoride ethyl halide compound 1.8 millimoles, and Prepared in advance, nickel octoate in hexane solution and antimony hexafluoride were reacted at a molar ratio of 1: 1 at 10 ° C to precipitate the by-products.
Ni ( SbF6 ) 2除去，用甲苯溶液稀釋後之辛酸鎳的六氟化 銻酸變性，其鎳原子濃度爲〇 . 2 〇毫莫耳之順序，使此觸 媒成份加入；於3 0°C下攪拌3小時，進行附加聚合反應 ;其後以甲醇使聚合反應停止。 在所得聚合體溶液中，加入甲苯5 00毫升、水660毫 升 '乳酸47.5毫莫耳，經攪拌、混合、與觸媒成份反應 m @合體與水靜置分離；將含有觸媒成份之反應物的 水相除去後的聚合體溶液，置入4公升的異丙醇中，使聚 € Μ II @ ’除去未反應單體與殘留之觸媒渣；將凝固的聚 合體乾燥後，即得「樹脂C」。 -30- (25) (25)200402364 樹脂C的聚苯乙烯換算之數平均分子量爲12.5x1 Ο4 、又，以D S C測定之玻璃轉移點爲3 1 6 °C。 〔實施例1〕 樹脂A溶解於二氯甲烷中，可得濃度3 0 %之溶液； 以此溶液塗佈於鏡面之玻璃板上，在常壓、4 0 °C下經8小 時，再於常壓1 2 0 °C經8小時，最後自玻璃板剝下，置於 1 2 0 °C之真空乾燥機中乾燥8小時，即得溶媒殘留量在0.5 %以下，厚度100 // m之薄膜A ;薄膜A的全光線透過 率爲94%，折射率爲1.51。 在所得薄膜A的一面上，用旋轉塗法將JSR社製之 「奧氟多—JN7 102」，以獲得硬化膜厚爲0.12 // m之程 度塗佈、硬化；硬化是以在1 2(TC加熱10分鐘進行；又 ，「奧氟多一 JN7 102」之硬化物的折射率爲1.68。 其次，在「奧氟多-JN7102」之硬化皮膜之上，用旋 轉塗佈法，將聚（3 -辛基噻吩）之三氯甲烷溶液（0.05 <莫耳/公升）塗佈之，形成乾燥膜厚0.09 /zm之皮膜 〇 所得層合薄膜爲薄膜A。 〔實施例2〕 將樹脂B溶解於環己烷，調成濃度爲3 0 %之溶液， &此溶液塗佈於鏡面之玻璃板上，在常壓50°C下經8小 時’再於常壓下1 20 °C經8小時，最後自玻璃板剝下，置 -31 - (26) (26)200402364 於1 2 〇 °c真空乾燥機中乾燥8小時，即得溶媒殘留量在 0.5 %以下，厚度10 0 // m之薄膜B ;薄膜B的全光線透 過率爲94%，折射率爲1>52。 使用所得樹脂B，進行與實施例1相同的操作，可得 層合薄膜；此層合薄膜爲樹脂B - 1。 〔實施例3〕 將樹脂C溶解於甲苯中，調成濃度爲3 〇 %之溶液； 以此溶液塗佈於鏡面之玻璃化上，在常壓6 0 °C下經8小 時，再於常壓1 50°C下經8小時，最後自玻璃板剝下，置 於1 5 0 °C之真空乾燥機中，乾燥8小時，即得溶媒殘留量 在〇 · 5 %以下，厚度1 〇〇 // m之薄膜C ;薄膜C之全光線 透過率爲94%，折射率爲1.52。 使用所得薄膜C，進行與實施例1相同的操作，即得 層合薄膜；此層合薄膜爲薄膜C - 1。 〔比較例1〕 在薄膜A之一面的表面上，施行與實施例1相同的 操作，形成「奧氟多—JN7 102」之硬化皮膜；其次，在「 奧氟多一 JN7102」之硬化皮膜上，用旋轉塗法將JSR社 製之「奧氟多—JN - 7215」，以獲得硬化膜厚爲0.09// m 之程度塗佈、硬化；硬化是以在1 2 0 °C加熱6 0分鐘進行 ;又，「奧氟多—JN 7 2 1 5」之硬化物的折射率爲1.4 1 ; (27) (27)200402364 〔比較例2〕 在薄膜A之一面的表面上，用旋轉塗布法，將聚（3 一辛基噻吩）之三氯甲烷溶液（〇 . 〇 5毫莫耳/公升）塗佈 之，形成乾燥膜厚0 . 〇 9 // m之皮膜。 所得層合薄膜爲薄膜A - 3。 測定薄膜A — 1〜A - 3、B — 1、及C〜1之反射率， 與評估其防止帶電性，結果如表1所示。 表1 薄膜 全光線透過率(％) 反射率(％) 防止帶電性 實施例1 Α-1 97 0.8 〇 實施例2 Β-1 97 0.8 〇〜△ 實施例3 C-1 97 0.8 〇〜△ 比較例1 Α-2 97 0.8 X 比較例2 Α-3 92 5.2 〇 〔產業上利用性〕 本發明之層合薄膜、透明性及導電優異、反射率低， 適合使用於各種爲提高顯示裝置之視認性的防止反射薄膜 -33-Ni (SbF6) 2 was removed, and the hexafluoric antimony acid of nickel octoate was denatured after diluting with toluene solution, and the nickel atom concentration was in the order of 0.20 millimoles. After stirring for 3 hours, an additional polymerization reaction was performed; thereafter, the polymerization reaction was stopped with methanol. To the obtained polymer solution, 500 ml of toluene and 660 ml of water, 47.5 millimoles of lactic acid were added, and after stirring, mixing, reacting with the catalyst component m @ 合体 and water were left to separate; reactants containing the catalyst component The polymer solution after the removal of the aqueous phase was put into 4 liters of isopropanol to make the polymer II @ 'remove unreacted monomers and residual catalyst residue; after drying the solidified polymer, " Resin C ". -30- (25) (25) 200402364 Resin C has a polystyrene-equivalent number average molecular weight of 12.5 × 10 4 and a glass transition point measured by DSC of 3 1 6 ° C. [Example 1] Resin A was dissolved in dichloromethane to obtain a solution with a concentration of 30%; and this solution was coated on a mirrored glass plate, and it was subjected to normal pressure and 40 ° C for 8 hours, and then After 8 hours at atmospheric pressure 1 2 0 ° C, it is finally peeled from the glass plate and dried in a vacuum drier at 1 20 ° C for 8 hours. The solvent residue is below 0.5% and the thickness is 100 // m. Film A; The total light transmittance of Film A is 94%, and the refractive index is 1.51. On one side of the obtained film A, "Olfodor-JN7 102" manufactured by JSR Corporation was applied by a spin coating method to obtain a cured film having a thickness of 0.12 // m, and hardened; the hardening was performed at 1 2 ( TC heating was carried out for 10 minutes; the refractive index of the hardened product of "Ofludo-JN7 102" was 1.68. Next, on the hardened film of "Ofludo-JN7102", the poly ( 3-Octylthiophene) was coated with a chloroform solution (0.05 < mole / liter) to form a film with a dry film thickness of 0.09 / zm. The resulting laminated film was film A. [Example 2] Resin B Dissolved in cyclohexane, adjusted to a solution with a concentration of 30%, & This solution was coated on a mirrored glass plate, at 8 ° C for 50 hours at normal pressure, and then at 1 20 ° C for 10 minutes at normal pressure. 8 hours, finally peeled from the glass plate, and placed in -31-(26) (26) 200402364 and dried in a vacuum dryer at 120 ° C for 8 hours, the solvent residue is below 0.5%, and the thickness is 10 0 // m film B; film B has a total light transmittance of 94% and a refractive index of 1> 52. Using the obtained resin B, the same operation as in Example 1 was performed to obtain a layer This laminated film is resin B-1. [Example 3] Resin C was dissolved in toluene and adjusted to a solution with a concentration of 30%; this solution was coated on the glass surface of the mirror surface, and was under normal pressure. After 8 hours at 60 ° C, 8 hours at 150 ° C under normal pressure, and finally peeled from the glass plate, put it in a vacuum dryer at 150 ° C, and dry for 8 hours to obtain the solvent residue. Film C with an amount of 0.5% or less and a thickness of 1000 // m; the total light transmittance of film C was 94% and the refractive index was 1.52. Using the obtained film C, the same operation as in Example 1 was performed, that is, A laminated film was obtained; this laminated film was film C-1. [Comparative Example 1] The same operation as in Example 1 was performed on the surface of one surface of film A to form a hardened film of "Orfido-JN7 102" ; Secondly, on the hardened film of "Orfondo-JN7102", spin coating was used to apply "Ofludo-JN-7215" manufactured by JSR to obtain a hardened film thickness of 0.09 // m, Hardening; hardening is performed by heating at 120 ° C for 60 minutes; the refractive index of the hardened product of "Ofondo-JN 7 2 1 5" is 1.4 1 (27) (27) 200402364 [Comparative Example 2] On the surface of one surface of film A, a poly (3-octylthiophene) trichloromethane solution (0.05 mol / It is coated to form a dry film having a thickness of 0.09 // m. The obtained laminated film is a film A-3. Table 1 shows the reflectances of the films A—1 to A—3, B—1, and C to 1 and the evaluation of their antistatic properties. Table 1 Total light transmittance (%) and reflectance (%) of the film. Example 1 A-1 97 0.8 〇 Example 2 Β-1 97 0.8 〇 ~ △ Example 3 C-1 97 0.8 〇 ~ △ Comparison Example 1 Α-2 97 0.8 X Comparative Example 2 Α-3 92 5.2 〇 [Industrial Applicability] The laminated film of the present invention is excellent in transparency and electrical conductivity and low in reflectance, and is suitable for various visual recognitions for improving display devices. Anti-reflective film-33-
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002106555A JP2003300268A (en) | 2002-04-09 | 2002-04-09 | Laminated film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW200402364A true TW200402364A (en) | 2004-02-16 |
Family
ID=28786430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW092107767A TW200402364A (en) | 2002-04-09 | 2003-04-04 | Laminated film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2003300268A (en) |
| AU (1) | AU2003220821A1 (en) |
| TW (1) | TW200402364A (en) |
| WO (1) | WO2003084741A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006035475A1 (en) * | 2004-09-27 | 2006-04-06 | Jsr Corporation | Laminated body and manufacturing method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0618086B2 (en) * | 1985-06-07 | 1994-03-09 | 三井石油化学工業株式会社 | Transparent conductive film |
| JPH077616B2 (en) * | 1986-03-05 | 1995-01-30 | 三井石油化学工業株式会社 | Conductive composite material |
| JP3223527B2 (en) * | 1991-06-17 | 2001-10-29 | ジェイエスアール株式会社 | Transparent conductive composite material |
| JPH07230715A (en) * | 1994-02-16 | 1995-08-29 | Sekisui Chem Co Ltd | Transparent conductor |
| JP2790993B2 (en) * | 1995-12-28 | 1998-08-27 | 三井化学株式会社 | Conductive composite materials and high-frequency circuit boards |
| JP4139480B2 (en) * | 1998-08-04 | 2008-08-27 | 藤森工業株式会社 | Substrate with transparent electrode |
| JP4238501B2 (en) * | 2001-04-27 | 2009-03-18 | Ｊｓｒ株式会社 | Thermoplastic norbornene resin-based optical film |
-
2002
- 2002-04-09 JP JP2002106555A patent/JP2003300268A/en not_active Withdrawn
-
2003
- 2003-04-02 AU AU2003220821A patent/AU2003220821A1/en not_active Abandoned
- 2003-04-02 WO PCT/JP2003/004220 patent/WO2003084741A1/en active Application Filing
- 2003-04-04 TW TW092107767A patent/TW200402364A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003300268A (en) | 2003-10-21 |
| AU2003220821A1 (en) | 2003-10-20 |
| AU2003220821A8 (en) | 2003-10-20 |
| WO2003084741A1 (en) | 2003-10-16 |
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