TWI361809B

TWI361809B -

Info

Publication number: TWI361809B
Application number: TW096119940A
Authority: TW
Inventors: Ito Shoji; Ueda Ken-Ichi; Noda Nobuhisa; Oka Shigeru; Otome Shigeo; Yamaguchi Hiroko
Original assignee: Nippon Catalytic Chem Ind
Priority date: 2004-08-31
Filing date: 2005-08-10
Publication date: 2012-04-11
Also published as: TWI364429B; TWI386449B; TW200726781A; DE112005002043T5; JP2006096960A; KR20080013029A; KR101004730B1; TW200745189A; WO2006025445A1; JP4825409B2; TW200736318A; KR20070040816A; KR100847061B1; DE112005002043B4; BRPI0514705A

Description

1361809 九、發明說明：【發明所屬之技術領域】本發明關於-種光學用平面狀熱可塑性樹脂組合物，其適合於光學用保護薄膜、光學薄膜、光學薄片等光學用途’含有具内酯環之聚合物做為主成子 „ 瑕刀者或含有具内酯裱聚合物以及其他熱可塑性樹脂組合物。【先前技術】 PMMA所代表之丙烯酸系樹脂，由於光學性能優里、且高的光線穿透率及低的雙折射率，對各種光學材料適岸作為低相位差之光學等向（1SGtrc)pic)材料。然而，近年來，隨者液晶顯示裝置及電漿顯示器、 _ 秀機EL顯不裝置等平面顯不器或紅外線感應器、光波導等進步，對於光學用透明南分：材料’待別是平面狀(薄臈狀或薄片狀等)之光與用透明高分子材料的要求逐漸升高。干平面狀光學用透明高分子材料所要求的特性而士先，可列舉透明性、光學等向性為高，伴隨於該等:用: 之特性’例如亦要求具耐熱性。、用於偏光板等光學保護薄膜中，除了高透明性、學等向性外，亦要求低光學彈性率、耐熱性1光性：古表面硬度、高機械強度、相位差的波長依賴性小、相位：的入射角依賴性小等特性。於相位差薄膜、視角補償薄膜等光學薄膜中透明性、高光璺望a w . , y' ^ 〇九于專向性外，亦要求低光學彈性率、耐熱性、1361809 IX. The present invention relates to a planar thermoplastic resin composition for optical use, which is suitable for optical applications such as optical protective films, optical films, and optical sheets. The polymer is used as a master „ 瑕或 or contains a lactone 裱 polymer and other thermoplastic resin composition. [Prior Art] The acrylic resin represented by PMMA has excellent optical properties and high light penetration. Rate and low birefringence, suitable for various optical materials as low phase difference optical isotropic (1SGtrc) pic) materials. However, in recent years, the liquid crystal display device and plasma display, _ show EL Improvements such as flat display devices such as devices, infrared sensors, optical waveguides, etc., for the transparent south of the optical: the material 'waiting for the flat (thin or thin), light and transparent polymer materials The characteristics required for the transparent planar polymer transparent polymer material are high, and the transparency and optical isotropic properties are high, and the following: For example, it is required to have heat resistance. In optical protective films such as polarizing plates, in addition to high transparency and isotropism, low optical elastic modulus and heat resistance are required. Optical properties: ancient surface hardness and high The mechanical strength, the wavelength dependence of the phase difference is small, and the phase angle dependence of the phase is small. In the optical films such as the retardation film and the viewing angle compensation film, transparency and high light look aw., y' ^ 〇于In addition to the directionality, low optical elastic modulus, heat resistance,

2226-7326B-PF 5 1361809 耐光性、高表面硬度、高機械強度、相位差大、相位差的波長依賴性小、相位差的入射角依賴性小等特性。擴散板、導光板等光學薄片中，除了高透明性、高光學等向性外’亦要求低光學彈性率、耐熱性、耐光性、高表面硬度、高機械強度等特性。特別是，目前使用之光學涛片係由聚甲基丙烯酸甲酯（ΡΜΜΑ)κ製成者，期望能抑制因持有更高耐熱性而導致成形應變（m〇ld strain)之原因所造成光學特性之減低。然而，以往的平面狀光學用透明高分子材料，並無分滿足該等特性者。为卜，就透明性及耐熱性同時兼備之熱可塑性樹脂而 =已知分子鏈中具有絲與醋基之聚合物，由内^化反應而製得具内醋環聚合物(例如參考曰本專利_ 光12等 12:號公報、特開獅先予等向性、耐光性、表面硬度無法充分表現強度亦可滿足者，以往並無進行薄膜化或薄片化之；：械光學用透明高分子材料。再者，僅有具 ❸面狀為使耐熱性提高而增加内醋環：：之聚合物，低的雙折射率【發明内容】明性、耐熱性、％本發明所欲解決之課題係提供，透2226-7326B-PF 5 1361809 Characteristics such as light resistance, high surface hardness, high mechanical strength, large phase difference, small wavelength dependence of phase difference, and small incident angle dependence of phase difference. In the optical sheets such as the diffusion plate and the light guide plate, in addition to high transparency and high optical isotropy, characteristics such as low optical modulus, heat resistance, light resistance, high surface hardness, and high mechanical strength are required. In particular, the optical film currently used is made of polymethyl methacrylate (Kappa), and it is desired to suppress the optical fiber caused by the higher heat resistance and the formation strain (m〇ld strain). Reduced characteristics. However, the conventional transparent optical material for planar optical does not satisfy these characteristics. For example, a thermoplastic resin having both transparency and heat resistance = a polymer having a filament and a vine group in a known molecular chain, and having an internal vinegar ring polymer by internal reaction (for example, reference transcript) Patent _ Light 12, etc. 12: Bulletin, special opening lion first isotropic, light resistance, surface hardness can not fully express the strength can also be satisfied, has not been thinned or thinned in the past;: transparent high mechanical optics Molecular material. Further, only the surface of the vinegar ring is increased in heat resistance, and the polymer is low in birefringence. [Inventive content] Brightness, heat resistance, % The present invention is intended to be solved. Provided by the subject

2226-7326B-PF 6 之特性之可充分發揮對應於各種光學用途各種二=熱可塑性樹脂組合物。前述適應於保=，具體而言，使用於偏光板等光學用學彈性率、耐鼓性、：L，可列舉低光性位:的波長依賴性小、相位差的入射角依賴性小等特、目位差薄膜、視角補償薄膜等光學薄膜中，除了古透明性、宾#風埜a 丨示’阿耐〖口’外，可列舉低光學彈性率、对熱性、 “南表面硬度、高機械強度、相位差大、相位差的依賴f生小、相位差的入射角依賴性小等特性；於擴散 ,、導光板等光學薄片巾，除了高透明性'高光學等向性 1’可列舉低光學彈性率、耐熱性、耐光性、高表面硬度、兩機械強度等特性，女、甘3 ^ 尤其疋例如比聚曱基丙烯酸甲酯（pMMA) 更南之耐熱性。本I明者們’為解決上述課題進行致力研究。結果發 ;見將3有具内酯環聚合物作為主成分之熱可塑性樹脂材料或將含有具内酯環聚合物以及其他熱可塑性聚合物之熱可塑性樹脂材料’分別於特定條件下，力口以薄膜化或薄 U __ 寸 "T ^供除了透明性及耐熱性外，分別適合於光學用保善4膜、光學薄膜、光學薄片而具有光學特性及機械特性之光學用平面狀熱可塑性樹脂組合物。亦即’本發明係提供以含有具内酯環聚合物作為主成刀為其特徵之光學用平面狀熱可塑性樹脂組合物（以下有時稱為「光學用平面狀熱可塑性樹脂組合物（Α)」）。前述The characteristics of 2226-7326B-PF 6 can be fully utilized in various optical applications corresponding to various optical applications. In the above, the optical elastic modulus and the drum resistance, such as a polarizing plate, are particularly limited, and the wavelength dependence of the low light position is small, and the incident angle dependency of the phase difference is small. In the optical film such as the head-displacement film and the viewing angle compensation film, in addition to the ancient transparency, the object #风野a ' shows the 'Ai 〗〖mouth', the low optical elastic modulus, the heat, the "Southern surface hardness, high" The mechanical strength, the phase difference is large, the phase difference depends on f-small, and the phase angle dependence of the phase difference is small. In the diffusion, the optical sheet towel such as the light guide plate, in addition to the high transparency 'high optical isotropic 1' Listed as low optical elastic modulus, heat resistance, light resistance, high surface hardness, and two mechanical strengths, the heat resistance of the female, gan 3 ^, especially, for example, more than polymethyl methacrylate (pMMA). We have been working hard to solve the above problems. The results are as follows; see 3 thermoplastic resins with a lactone ring polymer as the main component or thermoplastic resins containing a lactone ring polymer and other thermoplastic polymers. material' In addition to the specific conditions, the force is thinned or thin U __ inch "T ^ in addition to transparency and heat resistance, respectively suitable for optical use of good film 4, optical film, optical sheet and optical and mechanical properties The present invention provides a planar thermoplastic resin composition for optical use characterized by containing a lactone ring polymer as a main forming tool (hereinafter sometimes referred to as " A planar thermoplastic resin composition for optical use (Α). The foregoing

2226-7326B-PF2226-7326B-PF

[式中，R，、R2及R3互相獨立地… 之有機殘基；又，有、不風原子或碳數1至2〇冑機殘基可含有氧原子]。單體==可塑性樹脂組合物包括含有氰化乙烤系熵眸# 平粒早凡之共聚物’較佳#括丙烯腈-苯乙烯系共聚物。权佳包括丙本發明之光輋性、千面狀熱可塑性樹脂組合物之透明改、耐熱性、光學等向性〈边於各種光與用、全之任™者皆高，可充分發揮對應分種九學用途之特性。對應於各種光學用途之特性板等光$ m # 八體而s，使用於偏光 ΰΓ 〇透明性、高光學等向性外，列舉低光學彈性率、耐埶性機;… 耐光性、高表面硬度、高機械強度、相位差的波長性小黧牲地貞性小、相位差的入射角依賴队 _ 优角補禎薄膜等光學薄膜中，除了高透明性、高光學等向性、卜’可列舉低光學彈性率、 t ,、，、性、耐光性、高表面硬度、古又阿機械強度、相位差大、相位差的波長依賴性小、相位祁位差的入射角依賴性小性，於擴散板、導光板等光學薄口予/寻片中，除了高透明性、光學等向性外，可列舉低光學 ° 一【生率、对熱性、耐光性、高表面硬度、高機械強度等特性，尤其疋例如比聚曱基丙烯酸曱酯（PMMA)更高之耐熱性。[In the formula, R, R2 and R3 are each independently an organic residue of the ...; further, a non-wind atom or a carbon number of 1 to 2 胄 the residue of the oxime may contain an oxygen atom]. The monomer == plastic resin composition includes a copolymer containing cyanide bromide entropy 眸 #平粒早凡', preferably a acrylonitrile-styrene copolymer. Quanjia includes the transparency, heat resistance, and optical isotropic properties of the photosensitive, one-dimensional thermoplastic resin composition of the present invention, which is high in all kinds of light and use, and can be fully utilized. The characteristics of the nine-study use. Corresponding to various optical applications, such as the characteristics of the board, light $ m # 八体, used in polarizing ΰΓ 〇 transparency, high optical isotropic, listed low optical elastic modulus, smash resistance machine; ... light resistance, high surface The optical properties of hardness, high mechanical strength, and phase difference are small, and the incident angle of the phase difference depends on the optical film such as the high-transparency and high optical isotropic. Examples thereof include low optical elastic modulus, t, and, and, light resistance, high surface hardness, ancient mechanical strength, large phase difference, small wavelength dependence of phase difference, and incident angle dependency smallness of phase coma. In addition to high transparency and optical isotropic properties in optical thin-film pre-/seepage of diffusing plates and light guide plates, low optical properties can be cited. [Hot rate, heat resistance, light resistance, high surface hardness, high mechanical strength] Other characteristics, especially, for example, higher heat resistance than poly(mercapto methacrylate) (PMMA).

2226-7326B-PF 9 1361809 【實施方式】以下將詳細說明本發明，本發明之範圍不受該等說明 • 之拘束，以下例示以外，只要無損於本發明之要旨的範圍内可貝施適宜地變更。《具内酯環聚合物》 t ^本發明之光學用平面狀熱可塑性樹脂組合物含有具内鲁西“衣聚合物作為主成分，或含有具内酯環聚合物以及其他熱可塑性樹脂。具内酯環聚合物具有下述式（1)所2226-7326B-PF 9 1361809 [Embodiment] The present invention will be described in detail below, and the scope of the present invention is not limited by the description, and is not limited to the scope of the present invention as long as it is not detrimental to the gist of the present invention. change. <<Lactone Ring Polymer>> The optical planar thermoplastic resin composition of the present invention contains a coating material having a Nes? "coating polymer as a main component or a polymer having a lactone ring and other thermoplastic resin. The lactone ring polymer has the following formula (1)

示之内酯環構造： (1) [式中，R1、R2及P3 =上v 之有㈣其地表示氮原子或碳數1至幾殘基’又’有機殘基可含有氧原子]。具内酯環聚合物構造中，造之含有比例，較佳為…。二式()所示之内醋環量％、異祛成m 9〇备里％、更佳為10至70 環構造之含有二佳為1〇至5°質量%。内 "，面硬度二:製例超過90質量%時，所製得 “之3 具内酯環聚合物，亦。之成形加工性降低。以外之構造。上述十’、°八有上述式（1)所示内酯環構式(1)所示内酷環構造以外之構造，炎The lactone ring structure is: (1) wherein R1, R2 and P3 = upper v (d), the ground represents a nitrogen atom or a carbon number of 1 to several residues, and the organic residue may contain an oxygen atom. In the structure of the lactone ring polymer, the content ratio is preferably... The amount of the vinegar ring shown in the formula () is % 、、、 m m m m m m 、、、。。。。。。。。。。。。。。。。。。。。。。。 Internal ", surface hardness 2: When the preparation is more than 90% by mass, the "three lactone ring polymers are produced, and the moldability is lowered. The above tenth, ° eight have the above formula. (1) shows a structure other than the inner ring structure shown by the lactone ring structure (1), inflammation

2226-7326B-PF 10 1361809 特別限定，例如較佳為如後述具内酯環聚合物之製造方法，由（甲基）丙烯酸酯、含羥基單體、不飽和羧酸以及下述式（2) (2)2226-7326B-PF 10 1361809 is particularly limited, for example, a method for producing a lactone ring polymer as described later, and a (meth) acrylate, a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and the following formula (2) (2)

XX

[式中，R表示氫原子或甲基，X表示氫原子、碳數1至20 之烧基、芳基、_〇Ac基、_CN基、_c〇_r5基或-⑶务r6基，Wherein R represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an 〇Ac group, a _CN group, a _c〇_r5 group or a -(3) cyclinyl group,

Ac表示乙醯基，R5 s P6主_ — ·. K及K表不虱原子或碳數1至20之有機殘基]所不之單體所成組群中至少選出一種單體，聚合所形成之聚合物構造單元（反覆構造單元）。、具内知％聚合物之構造中，上述式⑴所示之内醋環構把以外構造之含有比例，於（甲基）丙稀酸醋聚合形成之聚合物構造單元f θ ® μ a «« (反覆構造早元）時，較佳為丨〇至95質更佳為10至90皙旦0/ i^ 〇、至90質量再佳為4〇至9〇質量％、特佳為50 °’ ； δ有羥基單體聚合形成之聚合物Ac represents an ethyl fluorenyl group, R5 s P6 main _ — · K and K are not argon atoms or organic residues having a carbon number of 1 to 20, and at least one monomer is selected from the group of monomers. A polymer building unit (repeated building unit) formed. In the structure of the known polymer, the internal vinegar ring structure represented by the above formula (1) is a polymer structural unit formed by polymerizing (meth)acrylic acid vinegar in a ratio of the external structure, f θ ® μ a « « (Reconstructed early structure), preferably from 丨〇 to 95, preferably from 10 to 90 0 0/ i^ 〇, to 90 mass, preferably from 4 〇 to 9 〇 mass%, especially preferably 50 ° ' ; δ polymer formed by polymerization of hydroxy monomer

(反覆構造單元）拄 ^ ^ ^ 傅&早7C )時’較佳為。至30質量％、更佳為。再佳為〇至15質量%、特佳為。至1〇質”2。不飽和缓酸聚合形成之聚合物構造單元構。單又’ 時’較佳為〇至3〇質量％、更佳為〇至2()質量^;元） °至15質量%、特佳為◦至10質量%。再者佳為示單體聚合形成述式（2)所車交至15 1 &物構造單元（反覆構造單元佳為〇至30質量γ早兀）時’ 質量％、特佳為〇至u質量為具内酯環¥ & ^ 可 Λ D物之製造方法，並無特別限定，例虫(Repeat construction unit) 拄 ^ ^ ^ Fu & early 7C) is preferable. Up to 30% by mass, more preferably. It is better to be 15% by mass, especially good. To 1 enamel" 2. Polymer structural unit structure formed by unsaturated acid retardation polymerization. The single 'time' is preferably 〇 to 3 〇 mass%, more preferably 〇 to 2 () mass ^; yuan) ° to 15% by mass, especially preferably ◦ to 10% by mass. Further, it is shown that the monomer is polymerized to form the formula (2) and the car is delivered to the 15 1 & structural unit (repeated structural unit is preferably 〇 to 30 mass γ early)兀) When the mass %, especially the 〇 to u mass is a lactone ring ¥ & ^ Λ D material manufacturing method, there is no particular limitation, the worm

2226-7326B-PF 1361809 於聚合步驟終製得分子鏈中且古，,_# t 衣付刀卞鍵γ具有搜基與酯基之聚合物（a) 後’將所製什聚合物（a)加孰虛理v 〈〜加，，.、爆理而將内酯環構造導入聚合物，進行内酯環縮合步驟而製得。聚合步驟中，例如將下述式（3): R8 CH2=C—CH—OH ⑶ COOR7 [式中’ R7及R»互相獨立地表示氣原子或碳數i至2〇之有機殘基]所示之單體，進行配合單體成份之聚合反應，製得分子鏈中具有羥基與酯基之聚合物。上述式(3)所示單體，例如可列舉2_(羥甲基)丙烯酸甲醋、2-⑽甲基）丙料乙自旨、2_㈣基）丙烯酸異丙雖、 2-(經甲基)丙稀酸正丁醋、2_(窥甲基)丙烤酸第三丁酉旨等。該等單體可單獨使用或2種以上併用。該等單體中，較佳為2-(經甲基）丙稀酸甲輯、2_(經甲基）丙稀酸乙醋，2226-7326B-PF 1361809 In the final step of the polymerization step, the molecular chain is obtained, and the _# t 付卞卞 γ has a polymer based on the ester group (a) and then the polymer (a) Adding a lactone ring structure to a polymer and adding a lactone ring condensation step to obtain a ruthenium v. In the polymerization step, for example, the following formula (3): R8 CH2=C—CH—OH (3) COOR7 [wherein R 7 and R» independently represent a gas atom or an organic residue having a carbon number of i to 2 Å] The monomer shown is subjected to polymerization reaction with a monomer component to obtain a polymer having a hydroxyl group and an ester group in the molecular chain. Examples of the monomer represented by the above formula (3) include 2-(hydroxymethyl)acrylic acid methyl vinegar, 2-(10)methyl)propyl propylene, 2-(4-)yl isopropyl acrylate, and 2-(methyl). Propionic acid n-butyl vinegar, 2_ (peep methyl) propane acid, third butyl sulphate and so on. These monomers may be used singly or in combination of two or more. Among these monomers, 2-(meth)propionic acid A, 2_(methyl)acrylic acid vinegar, is preferred.

由於耐熱性提升之效果高，特佳為2_(經甲基)丙烯酸"旨。於聚合步驟供作單體成分中，上述式⑺所示單體之人 ^比例較佳為5线質量％、更佳為心則量％ ::1。至60質量%、特佳為！。至5〇質量上述式單體$冬古)斤不體之3有比例不足5質量％時，所製得聚合物之耐熱性、 :::性及表面硬度為降低。相反地’上述式。)所示單體 “比例超過90質量%時，聚合步驟及環化縮發生膠化，所製得聚合物之成形加工性降低。a中於聚合步驟供作單體成分中，亦可配合上述式（3)所示Due to the high heat resistance improvement effect, it is particularly preferred as 2_(meth)acrylic acid " In the monomer component to be used in the polymerization step, the proportion of the monomer represented by the above formula (7) is preferably 5 % by mass, more preferably 9% by weight. Up to 60% by mass, especially good! . The heat resistance, ::: and surface hardness of the obtained polymer are lowered when the ratio of the above-mentioned monomer of the above-mentioned type of monomer is less than 5% by mass. Conversely, the above formula. When the ratio of the monomer shown is more than 90% by mass, the polymerization step and the cyclization are gelatinized, and the formability of the obtained polymer is lowered. In a polymerization step, a monomer component may be blended as described above. Equation (3)

2226-7326B-PF 12 1361809 單體以外之單體。該等單體並無特別限定者，可列舉如（曱基）丙烯酸酯、含羥基單體、不飽和羧酸、及下述式（2) CH9-Ο R4 (2)2226-7326B-PF 12 1361809 Monomers other than monomers. The monomers are not particularly limited, and examples thereof include (meth) acrylate, a hydroxyl group-containing monomer, an unsaturated carboxylic acid, and the following formula (2) CH9-Ο R4 (2)

XX

[式中’R表示虱原子或甲基，X表示氫原子、碳數1至之烷基、芳基、-〇Ac基、-CN基、-C0-R5基或-C0-0-R6基，Wherein 'R represents a halogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to an alkyl group, an aryl group, an -〇Ac group, a -CN group, a -C0-R5 group or a -C0-0-R6 group. ,

Ac表示乙醯基，R6表示氫原子或碳數i至2〇之有機殘基]所示之單體。該等單體可單獨使用或2種以上併用。 (甲基）丙烯酸酯，以上述式（3)所示單體以外之（甲基）丙烯酸S曰為限，並無特別限定者，例如可列舉丙烯酸甲酯、丙烯1乙|曰、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酉旨、丙料環己冑、丙烯酸Μ等丙烯㈣；甲基丙稀曱自曰、甲基丙烯酸酯乙酉旨、甲基丙烯酸酯丙酯、曱基烯“曰正丁自曰、曱基丙烯酸酯異丁酯、甲基丙烯酸酯第三丁醋、甲基丙烯酸酿環己gl、甲基丙烯酸醋戊酷等甲基丙蝉酸酯等；等等。連寻（曱基）丙烯酸酯可單獨使用或2 種以上併用。兮*莖以甲基）丙烯酸酯中，由於所製得之聚合物之耐熱性及透明性優異’較佳為甲基丙烯酸甲酯。使用上述式（3)所 w , ^ ^ , y、之早體以外之（曱基）丙烯酸酯 %，於聚合步驟供作搞士& 成刀中其所含有比例，以充分發揮本毛明之效果為上，至90質量％、再佳為4n 至95質量％、更佳為10 0/。 ‘、、至90質量％、特佳為50至90質量含有羥基之單體以上述式（3)所示之單體以外之含有Ac represents an ethyl hydrazide group, and R6 represents a monomer represented by a hydrogen atom or an organic residue having a carbon number of i to 2 Å. These monomers may be used singly or in combination of two or more. The (meth) acrylate is not particularly limited, and is not particularly limited as long as the (meth)acrylic acid S oxime other than the monomer represented by the above formula (3), and examples thereof include methyl acrylate, propylene 1 曰曰, and acrylic acid. Butyl acrylate, isobutyl acrylate, acrylic acid, propylene, propylene, propylene, etc.; tetramethyl methacrylate, methacrylate, propyl methacrylate, fluorenyl methacrylate Alkenes such as 曰丁丁曰, 曱 acrylate isobutyl acrylate, methacrylate third butyl vinegar, methacrylic acid cycline gl, methacrylic acid vinegar and other methyl propyl phthalate; The thiol-based acrylate may be used singly or in combination of two or more. In the case of methyl acrylate in 兮* stem, the heat resistance and transparency of the obtained polymer are excellent, and methacrylic acid is preferred. Methyl ester. Using the above formula (3), w, ^ ^, y, the % (mercapto) acrylate other than the early body, in the polymerization step, the ratio of the content contained in the knife and the knife is fully utilized. The effect of the present hair is up to 90% by mass, preferably 4% to 95% by mass, more Preferably, it is 10 0 /. 、, to 90% by mass, particularly preferably 50 to 90% by mass. The monomer having a hydroxyl group is contained other than the monomer represented by the above formula (3).

2226-7326B-PF 13 1361809 羥基之單體為限’並無特別限定者’例甲基苯乙烯、α-羥基乙基笨乙稀'2 + 〇沛z (羥基乙基）丙烯酸甲 _等2,基院基)丙稀酸；等等。該等含有經基之單體，可單獨使用或2種以上併用。使用上述式（3)所示之單濟以冰夕人‘ 早體以外之含有羥基時，於聚合步驟供作單體成分中JL所会古点丨 ”所3有比例’以充分發揮本發明之效果為上’較佳〇至3〇質量％、更侄為〇至2〇質量％、再佳為0至15質量％、特佳為〇至1〇質量％。2226-7326B-PF 13 1361809 The monomer of the hydroxyl group is limited to 'not particularly limited', such as methyl styrene, α-hydroxyethyl stupid Ethyl 2, 〇 z z (hydroxyethyl) acrylate, etc. 2 , base-based) acrylic acid; and so on. These monomers containing a radical may be used singly or in combination of two or more. When the hydroxyl group other than the early body of the ice cube is used in the above-mentioned formula (3), the ratio of the JL in the monomer component is 3 in the polymerization step to fully exert the present invention. The effect is from 'preferably 〇 to 3 〇 mass%, more 〇 to 〇 2% by mass, more preferably from 0 to 15% by mass, particularly preferably from 〇 to 1% by mass.

不飽和缓酸，例如可列舉丙稀酸、甲基㈣酸H 酸㈣1d)、t取代丙烯酸、^取代甲基丙烯酸等。S玄等不飽和羧酸可單獨佶 j平躅使用或2種以上併用。該等不飽和羧酸中，由於充分發禮土, 刀發揮本發明之效果，特佳為丙烯酸、甲基丙烯酸。使用不飽和羧酸時，於聚人击 '永σ步驟供作單體成分中直所含有比例’以充分發揮本發明政果為上，較佳0至30質量％、更佳為0至20質詈％、至杜丸η 、買里％再佳為〇至15質量％、特佳為 0至1 0質量％。兩上述式（2)所示單體，例 J夕J举本乙烯、甲基乙烯、乙烯基甲笨、丙烯腈、美土乙烯基酮、乙烯、丙烯、醋酸6烯醋等。該等單體’可單獨使用或2種以上併用該等單體中，由於充分發揮本發明之效果，。曱基苯乙烯。柯、使用上述式（2)所千夕 J所不之早體時，於聚合步驟供分中其所含有比例，以充八路搞士 ' 成以充刀發揮本發明之效果為上，較佳Examples of the unsaturated acid retardant include acrylic acid, methyl (tetra) acid H acid (tetra) 1d), t-substituted acrylic acid, and substituted methacrylic acid. The S-supplemental unsaturated carboxylic acid may be used alone or in combination of two or more. Among these unsaturated carboxylic acids, the knives exert the effects of the present invention because they are sufficient for the present invention, and acrylic acid and methacrylic acid are particularly preferred. When an unsaturated carboxylic acid is used, it is preferable to use a ratio of "in the sigma sigma step as a ratio of the monomer component" to give full play to the present invention, preferably from 0 to 30% by mass, more preferably from 0 to 20詈%%, to Duwan η, and Buy%% are preferably 15% by mass, and particularly preferably 0% to 10% by mass. Two of the monomers represented by the above formula (2), and examples thereof, include ethylene, methylethylene, vinylmethyl styrene, acrylonitrile, melamine, ethylene, propylene, and acetate. These monomers ' may be used singly or in combination of two or more kinds thereof, and the effects of the present invention are sufficiently exerted. Mercaptostyrene. Ke, when using the early formula of the above formula (2), the ratio contained in the polymerization step is to be used to fill the effect of the invention.

2226-7326B-PF 14 丄 % 質量％'更佳為Gi2Gft%、再佳為〇至15質量、特佳為〇至10質量％。 :=成份而製得分子鍵中具有經基與醋基之聚合反應之形態’較佳為使用溶劑之聚為溶液聚合。 m2226-7326B-PF 14 丄 %% by mass% is more preferably Gi2Gft%, more preferably 〇 to 15%, particularly preferably 〇 to 10% by mass. The composition of the molecular bond having a polymerization reaction of a base group and a vine group is preferably a solution polymerization using a solvent. m

聚合溫度及聚人拉P # σ時間，可隨所使用單體之種類或比例寻而變化，例如較祛1取為♦ δ溫度為〇至150〇c、聚合時間 '"、·至20小時，更較佳為聚合溫度為8〇至】合時間為1至10小時。象用岭幻聚合形態時，聚合溶劑並無特別限定者如可列舉甲笑、-田— 一本、乙基苯等芳香族烴系溶劑；甲基 2酮：：基異丁基酮等酮系溶劑;四氫呋喃等醚系溶劑; 。該等溶劑可單獨使用或2種以上併用。又，溶劑之 >:點過高日夺’由於最終所製得之具内醋環聚合物之殘餘揮 Φ 發成分變多m為5G至2G(rc之溶劑為較佳。於聚合反應時，必要時’可添加聚合起始劑。聚合起始劑並無特別限定者’例如可列舉異丙苯過氧化氯、二異丙基苯過氧化氫d三丁基過氧化物、月桂醯基料化物、苯甲醯基過氧秦第三丁基過氧化物異丙基羧酸醋：第三物雞過氧化物_2_乙基己醋等有機過氧化物； 15 1361809 無特別設定者。進行聚合時’為了抑制反應液之膠化，以控制聚合反 …c* δ物中所生成之聚合物之濃度為5 〇質量％以下為佳。具體而§，聚合反應混合物中所生成之聚合物之濃度超過 5〇質量％時，以於聚合反應混合物中合宜地添加聚合溶劑而控制聚合物之濃度為5〇質量%以下為佳。聚合反應混合物中所生成之聚合物濃度更佳為45質量％以下，再佳為質里％以下。又，聚合反應混合物中所生成之聚合物濃度過低時，生產性降低，較佳為10質量％以上，更佳為2〇質 %以上。於聚合反應混合物中適宜添佳聚合溶劑之形態，並無別限疋者，例如可連續地添加聚合溶劑，亦可間歇地添 -聚S溶丨。根據如此之聚合反應混合物中控制所生成聚合物濃度’從而可充分控制反應液之膠化，特別是由於内酿環含有比例容易增加而提高耐熱性，分子鏈中羥基與酷基之比例亦增高時’可充分控制膠化。添加之聚合溶劑， =如可為與聚合反應初期混合時所使用之溶劑為同種類之溶劑’可為不同種類之溶劑’較佳為與聚合反應初期混合時所使用之溶劑為同種類之溶劑。又，添加之聚合溶劑，可僅為1種之單-溶劑或2種以上之混合溶劑。以上之聚合步驟終了時所製得之聚合反應混合物中，通常除了所製得之聚合物外，含有入w i ，奋琍，不需要將溶劑完王除去，將聚合物以固體狀態取出，較权住馮於含有溶劑之 “、，導入至後續内醋環化縮合步驟。又，必要時，可以The polymerization temperature and the concentration of P # σ can vary depending on the type or proportion of the monomers used, for example, 祛1 is ♦ δ temperature is 〇 to 150〇c, polymerization time '",· to 20 In the hour, it is more preferred that the polymerization temperature is from 8 Torr to a combined time of from 1 to 10 hours. When the polymerization solvent is used, the polymerization solvent is not particularly limited, and examples thereof include an aromatic hydrocarbon solvent such as a smirk, a field, a benzene, and an ethylbenzene; and a ketone such as methyl ketone or ketobutyl ketone; a solvent; an ether solvent such as tetrahydrofuran; These solvents may be used singly or in combination of two or more. Further, the solvent >: the point is too high, because the residual styrene component of the internal vinegar ring polymer obtained by the final change is mG 5G to 2G (the solvent of rc is preferred. When necessary, a polymerization initiator may be added. The polymerization initiator is not particularly limited, and examples thereof include cumene peroxide chlorine, diisopropylbenzene hydrogen peroxide d-butyl peroxide, and lauryl sulfonate. Compound, benzamidine peroxymethyl tert-butyl peroxide isopropyl carboxylic acid vinegar: third organic peroxide such as chicken peroxide _2_ethyl hexanoic acid; 15 1361809 No special setting When the polymerization is carried out, in order to suppress the gelation of the reaction liquid, it is preferred to control the concentration of the polymer formed in the polymerization anti-c* δ to be 5 〇 mass% or less. Specifically, § is formed in the polymerization mixture. When the concentration of the polymer exceeds 5% by mass, it is preferred to add a polymerization solvent to the polymerization reaction mixture to control the concentration of the polymer to be 5% by mass or less. The concentration of the polymer formed in the polymerization mixture is more preferably 45% by mass or less, and preferably less than 5% by mass. When the concentration of the polymer formed in the polymerization mixture is too low, the productivity is lowered, preferably 10% by mass or more, more preferably 2% by mass or more. The form of the polymerization solvent is suitably added to the polymerization mixture, and there is no For example, the polymerization solvent may be continuously added, or the poly-S solution may be added intermittently. According to the concentration of the polymer produced in the polymerization mixture, the gelation of the reaction liquid can be sufficiently controlled, in particular Since the proportion of the inner ring is easily increased to improve the heat resistance, and the ratio of the hydroxyl group to the base in the molecular chain is also increased, the gelation can be sufficiently controlled. The added polymerization solvent, if used, can be used in combination with the initial stage of polymerization. The solvent is the same type of solvent 'may be a different type of solvent'. It is preferably a solvent of the same type used when mixing with the initial stage of the polymerization reaction. Further, the added polymerization solvent may be only one type of single solvent or a mixed solvent of two or more kinds. In the polymerization reaction mixture obtained at the end of the above polymerization step, usually in addition to the obtained polymer, it is contained in the wi, It is not necessary to remove the solvent, and the polymer is taken out in a solid state, and the solvent is contained in the solvent, and is introduced into the subsequent condensing step of the vinegar. Further, if necessary,

2226-7326B-PF 162226-7326B-PF 16

1361809 固體狀態取出後，於後續内酯環化縮合步驟中再添加合適之溶劑。於聚合步驟所製得之聚合物，為分子鏈中具有經基I 酯基之聚合物（a)，聚合物（a)之質量平均分子量較佳為1361809 After removal in the solid state, a suitable solvent is added to the subsequent lactone cyclization condensation step. The polymer obtained in the polymerization step is a polymer (a) having a base I ester group in the molecular chain, and the mass average molecular weight of the polymer (a) is preferably

1，0 00 至 2, 000, 000、更佳為 5, 000 至 1，000, 000、再佳為 10，.000 至 500, 000、特佳為 50, 000 至 500, 〇〇〇。於聚合步驟所製得之聚合物（a)’於後續内酯環化縮合步驟中，以加熱處理而將内酯環倒入聚合物，形成具内酯環之聚合物。為於聚合物（a)導入内酯環之反應係以加熱而將聚合物（a)之分子鏈中存在之羥基與酯基縮合環化而產生内酯環構造之反應，由該環化縮合反應產生副產物為醇類。内酯環構造係形成於聚合物之分子鏈中（聚合物之主骨架中）’而賦予高耐熱性。導入内酯環構造之環化縮合反應之反應率不充分時’無法充分提升耐熱性，或者於成形時之加熱處理之成形中發4給人）5_ ,, 又/ T發生鈿合反應，所生成之醇類於成形品中以泡狀或銀線狀（silver streak)存在。内醋環化縮合步驟中所製得之聚内酉旨環之聚合物，較佳為具有下述式（丨）所示之内醋環構造：1,0 00 to 2, 000, 000, more preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 50,000 to 500, 〇〇〇. The polymer (a)' obtained in the polymerization step is subjected to heat treatment to pour the lactone ring into the polymer in the subsequent lactone cyclization condensation step to form a polymer having a lactone ring. The reaction in which the lactone ring is introduced into the polymer (a) is heated to condense the hydroxyl group present in the molecular chain of the polymer (a) with the ester group to form a lactone ring structure, and the cyclization condensation is carried out. The reaction produces by-products as alcohols. The lactone ring structure is formed in the molecular chain of the polymer (in the main skeleton of the polymer) to impart high heat resistance. When the reaction rate of the cyclization condensation reaction in which the lactone ring structure is introduced is insufficient, 'the heat resistance cannot be sufficiently improved, or the heat treatment is performed in the formation of the heat treatment at the time of molding. 5_, and /T undergoes a kneading reaction. The produced alcohol is present in the molded article in the form of a bubble or a silver streak. The polymer of the inner ring of the inner ring obtained by the internal vinegar cyclization condensation step preferably has an inner vine ring structure represented by the following formula (丨):

[式中，R1、R2及V 之有機殘基；又，有互相獨立地表示氣原子或碳數機殘基可含有氧原子]。至20[In the formula, the organic residues of R1, R2 and V; in addition, independently of each other, the gas atom or the carbon number residue may contain an oxygen atom]. To 20

2226-7326B-PF 17 !3618〇9 加熱處理聚合物⑷之方法，並以：習知之方法。例如，根據聚合步驟二之者二:用之I反應混合物，將其直接：’合劑溶劑存在下’必要時使用閉環觸媒進二：者:可於亦可使用具備將揮發成份去除之直空裝置：；、處或者，熱爐或反應裝置，具備脫揮裝置之擠塵機等脱揮裝置之加環化縮合反應進行時，除了聚合物⑷之^加熱處理。 =7性:脂。又，進行環化縮合反應時，存 %化細合反應觸媒之一般所使用之把 "化觸媒或醋交換觸媒，亦可使用錯酸、丙酸、安V;:4 使用…利：開:類作為觸媒。再者，亦可 6"61303號公報所 ^ 254608 &公報或特開昭醆鹽等。驗性化合物、有機繞酸鹽、碳媒。使W機!ult用有機碟化合物作為環化縮合反應觸二二大!:物作為觸媒，可提升環化縮合反應率， :時可大幅減低所製得具内g旨環之聚合物之著色。再者， :有機麟化合物作為觸媒’併用後述之脫揮步驟時，可抑制初期所製得分子量減低，可賦予優異之機械強度。可使用作為環化输人。士可列舉甲基亞石黃酸、乙/亞媒之有機填化合物，例如亞顿惟，該等亦可：成：酸、苯基亞續酸等烧基(芳基）酸)以及其等之單s旨或二δ:互變異構物之院基(芳基)次膦 . -曰’一曱基次膦酸（phosphinic 扣⑷、二乙基次膦酸'二苯基次膦酸、苯基甲基次膦酸、2226-7326B-PF 17 !3618〇9 A method of heat-treating the polymer (4) by a conventional method. For example, according to the second step of the polymerization step 2: using the I reaction mixture, directly: 'in the presence of a mixture solvent', if necessary, using a closed-loop catalyst to enter the second: the: can also use the direct space to remove volatile components When the cyclization condensation reaction of the devolatilizer such as a slewing device such as a devolatilizer is carried out, the apparatus is heated except for the polymer (4). =7 sex: fat. Further, when the cyclization condensation reaction is carried out, it is generally used to reduce the amount of the reaction catalyst, and the catalyst or vinegar exchange catalyst can also be used, and the acid, propionic acid, and An V can be used. Lee: Open: Class as a catalyst. Furthermore, it is also possible to use the 254608 & Test compounds, organic acid salts, carbon media. Let the W machine!ult use the organic dish compound as the cyclization condensation reaction to touch the second big thing!: As the catalyst, the cyclization condensation reaction rate can be increased, and the polymer obtained by the inner ring can be greatly reduced. Coloring. Further, when the organic lining compound is used as a catalyst, and the devolatilization step described later is used, the molecular weight obtained at the initial stage can be suppressed from being lowered, and excellent mechanical strength can be imparted. Can be used as a circular input. The organic filling compounds of methyl linoleic acid and B/sub-media can be cited, such as Aton, which can also be: acid, phenyl phthalic acid, etc., and the like. Single s or two δ: a terephthalic (aryl) phosphine of a tautomer. - 曰' 曱曱 phosphinic acid (phosphinic deduction (4), diethyl phosphinic acid 'diphenylphosphinic acid, Phenylmethylphosphinic acid,

2226-7326B-PF 18 13618〇9 苯基乙基次膦酸等二烷基（芳基）次膦酸以及其等之酷；甲基膦酸（phosphonic acid)、乙基膦酸、三氟曱基膦酸、苯 ' 基膦酸等烷基（芳基）膦酸以及其等之單酯或二酯；甲基亞 - 次膦酸、乙基亞次膦酸、苯基亞次膦酸等烷基（芳基）亞次膦酸以及其等之酯；亞磷酸曱酯、亞磷酸乙酯 '亞磷酸苯酯' 亞磷酸二甲酯、亞磷酸二乙酯、亞磷酸二苯酯、亞.磷酸三甲酯、亞磷酸三乙酯、亞磷酸三苯酯等亞磷酸單酯、二酯或三酯；磷酸曱酯、磷酸乙酯、磷酸2-乙基己酯、磷 ' 酸辛酯、磷酸異癸酯、磷酸月桂酯、磷酸硬脂醯酯、磷酸異硬脂醯酯、磷酸苯酯、磷酸二甲酯、磷酸二乙酯、鱗酸二-2-乙基己酯、磷酸二異癸酯、磷酸二月桂酯、磷酸二硬脂醯酯、磷酸二異硬脂醯酯、磷酸二苯酯、磷酸三曱酯、磷酸三乙酯、磷酸三異癸酯、磷酸三月桂酯、磷酸三硬脂醯酯、磷酸三硬脂醯酯、磷酸三苯酯等磷酸單酯、二酯或三酯；甲基膦、乙基膦、苯基膦、二曱基膦、二乙基膦、鲁二苯基膦、三甲基膦、三乙基膦、三苯基膦等單-、二-或二-烷基（芳基）膦；曱基二氣膦、乙基二氣膦、苯基二氣膦、二甲基氣膦、二乙基氣膦、二苯基氯膦等烷基（芳基）_膦；氧化甲基膦、氧化乙基膦、氧化苯基膦、氧化二甲基膦、氧化二乙基膦、氧化二苯基膦、氧化三曱基膦、氧化三乙基膦、氧化三笨基膦等單_、二_或三-烷基（芳基）膦；氣化四甲基鐫（phosphnium)、氯化四乙基鱗、氯化四苯基鱗等鹵化四烷基（芳基）鱗；等等。該等有機磷化合物可單獨使用或2種以上併用。該等有機磷化合物中，由於觸媒活性2226-7326B-PF 18 13618〇9 Dialkyl(aryl)phosphinic acid such as phenylethylphosphinic acid and the like; chromanic acid, ethylphosphonic acid, trifluoroantimony Alkyl (aryl) phosphonic acid such as phosphinic acid or phenyl 'phosphonic acid, and monoesters or diesters thereof; methyl phosphinic acid, ethyl phosphinic acid, phenyl phosphinic acid, etc. Alkyl (aryl) phosphinic acid and its esters; decyl phosphite, ethyl phosphite phenyl phosphite dimethyl phosphite, diethyl phosphite, diphenyl phosphite, sub a phosphite monoester, diester or triester such as trimethyl phosphate, triethyl phosphite or triphenyl phosphite; decyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl p-phosphate Isodecyl phosphate, lauryl phosphate, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phthalate, diisophosphate Decyl ester, dilauryl phosphate, distearyl phosphate, diisostearyl phosphate, diphenyl phosphate, tridecyl phosphate, triethyl phosphate, triisodecyl phosphate, phosphoric acid March Phosphate monoester, diester or triester such as ester, tristearyl phosphate, tristearyl phosphate, triphenyl phosphate; methyl phosphine, ethyl phosphine, phenylphosphine, dimercaptophosphine, diethyl Mono-, di- or di-alkyl (aryl) phosphines such as phosphine, ruthenium diphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine; fluorenyl diphosphine, ethyl di Alkyl (aryl)-phosphines such as phosphine, phenyl diphosphine, dimethylphosphine, diethylphosphine, diphenylchlorophosphine; oxidized methylphosphine, oxyethylphosphine, phenylphosphine oxide, Mono-, di- or tri-alkyl (aryl) such as dimethylphosphine oxide, diethylphosphine oxide, diphenylphosphine oxide, tridecylphosphine oxide, triethylphosphine oxide, and tris-phosphoryl oxide Phosphine; vaporized tetraalkyl (aryl) scales such as tetramethylphosphonium chloride, tetraethyl sulphate chloride, tetraphenyl sulphate, etc.; These organophosphorus compounds may be used singly or in combination of two or more. Among these organophosphorus compounds, due to catalyst activity

2226-7326B-PF 19 1361809 问且著色性低，而較佳為烷基（芳基）亞次膦酸、亞磷酸單酯或二酯、磷酸單酯或二酯及烷基（芳基）次膦酸，更佳為烷基（芳基）亞次膦酸、亞磷酸單酯或二酯及磷酸單酯或二酯，特佳為烷基（芳基）亞次膦酸及磷酸單酯或二酯。 %化縮合反應時所用之觸媒使用量，並無特別限定，例如，相對於聚合物（a)，較佳為〇〇〇1至5質量％、更較佳為0. 01至2. 5質量％、再較佳為〇〇1至丨質量％、特佳 ^ 〇.〇5至〇.5質量％。觸媒之使用量未達〇.〇〇ι質量％時， :化縮σ反應之反應率未充分提升。相反地，觸媒之使用量超過5質量%時’所製得之聚合物會著色，或聚合物會交聯，而難以溶融賦形。 $之添加時期’並無特別限定’例如，可於反應;i 期添力:、可於反應中添加，或可為該兩種方式添加。 %化鈿合反應於溶劑存在下進行，而且環化縮合反』時，較佳為併用脫揮步驟。敕躺a 驟此時，可列舉於環化縮反應^ 正體過程併用脫揮步驟、 p入生心，以及不於環化縮合反應ϋ 紅王體併用脫揮步驟，而 1皇於過私之一部分中併用之型裹專。以併用脫揮步騍之方、土丄產铷法，由於於環化縮合反應_之昌產物醇係強制地脫揮去，、’反應平衡有利於生成物側。脱揮步驟意指將滚入咖賓 '殘餘單體等揮發成分，以及導時（、'成m ή κ “ ' 應所生成之副產物醇，於必要了 <减壓加熱條件下，時，所製得聚合物中殘餘：步驟。該去除處理不充分質等而著色，或、發成分多，會發生成形時之變一之泡或銀線等成形不良。2226-7326B-PF 19 1361809 and has low coloring property, and is preferably an alkyl (aryl) phosphinic acid, a phosphite monoester or a diester, a phosphoric acid monoester or diester, and an alkyl (aryl) group. a phosphonic acid, more preferably an alkyl (aryl) phosphinic acid, a phosphite monoester or diester, and a phosphoric acid monoester or diester, particularly preferably an alkyl (aryl) phosphinic acid and a phosphoric acid monoester or Diester. 01至2. 5。 The amount of the catalyst is not particularly limited, for example, the polymer (a) is preferably 〇〇〇1 to 5% by mass, more preferably 0. 01 to 2. 5 The mass%, more preferably 〇〇1 to 丨% by mass, particularly preferably 〇.〇5 to 〇.5% by mass. When the amount of the catalyst used is less than 〇〇.% by mass, the reaction rate of the sigma sigma reaction is not sufficiently improved. On the other hand, when the amount of the catalyst used exceeds 5% by mass, the polymer obtained is colored, or the polymer is crosslinked, and it is difficult to melt and form. The addition period of $ is not particularly limited. For example, it may be added to the reaction; the period i may be added to the reaction, or may be added in both cases. The % chelating reaction is carried out in the presence of a solvent, and in the case of cyclization condensation, it is preferred to use a devolatilization step in combination. At this time, it can be exemplified in the cyclosynthesis reaction, the normal process, and the devolatilization step, p into the green heart, and not in the cyclization condensation reaction, the red body and the devolatilization step, and the Part of the combination used in the package. In combination with the sputum sputum and the earthworm sputum production method, since the cyclization condensation reaction _ _ chang product alcohol is forcibly detached, the reaction equilibrium favors the product side. The devolatilization step means that the volatile component such as the residual monomer of the granule is rolled, and the by-product alcohol which is formed by the time of ', m ή κ ” ', should be used under the condition of heating under reduced pressure. Residue in the obtained polymer: the step of removing the color is not sufficient, and the color is increased, or the amount of the hair component is large, and a molding failure such as a bubble or a silver wire during molding may occur.

2226-7326B-PF 20 1361809 於環化縮合反應整體併用脫揮步… 之裝置並無特別限定者，例如 …所使用較佳係使用包括熱交換器與脫：更有效的施行，係使用揮裝置與擠壓機配置為串㈣，更較佳 =用包括與脫揮槽之脫料置或时通孔之擠使以括與脫揮槽之脫揮裝料之反應處理較佳為15WC、更佳為⑽至糊。c。反應溫 :夕15°。時’核化縮合反應不充份而使殘餘揮發成份艾夕。相反地’反應處理溫度超㉟35〇。。時，發生所製得聚合物之著色或分解。 β使用包括熱交換器與脫揮槽之脫揮裝置時之反應處理壓力較佳為931至1. 33hPa(700至inunHg)、更較佳為798 至66.5hPa(600至50mmHg)。反應處理壓力超過 931hPa( 70 0mmHg)時，容易殘餘含醇之揮發成份。相反地，籲反應處理壓力不達1. 33hPa(lmmHg)時’難以工業上實施。使用附有通孔之擠壓機時，通孔可為1個或複數個，以複數個的方式較佳。使用附有通孔之擠壓機時之反應處理溫度，較佳為1 5 〇至350°C、更佳為200至30(TC。反應溫度不達15(TC時，環化縮合反應不充份而使殘餘揮發成份變多。相反地，反應處理溫度超過350°C時，發生所製得聚合物之著色或分解。使用附有通孔之擠壓機時之反應處理壓力，較佳為931 2226-7326B-PF 21 1361809 至 1· 33hPa(700 至 lmmHg)、更較佳為 798 至 66. 5hPa(6〇〇至50mmHg)。反應處理壓力超過93ihPa(70 0mmHg)時，容易殘餘含醇之揮發成份。相反地，反應處理壓力不達 1.33hPa(lmmHg)時，難以工業上實施。2226-7326B-PF 20 1361809 The apparatus for the cyclization condensation reaction as a whole and the devolatilization step is not particularly limited. For example, the use of a heat exchanger and a de-heating device is more effective, and the device is used. And the extruder is configured as a string (four), more preferably = the reaction treatment including the detachment of the devolatilization tank or the through hole of the devolatilization tank is preferably 15 WC, and the reaction treatment of the devolatilization charge including the devolatilization tank is preferably 15 WC, Good for (10) to paste. c. Reaction temperature: eve 15 °. When the nucleation condensation reaction is not sufficient, the residual volatile component is AI Xi. Conversely, the reaction treatment temperature exceeded 3,535 Torr. . The coloring or decomposition of the resulting polymer occurs. The reaction treatment pressure when using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably 931 to 1.33 hPa (700 to inunHg), more preferably 798 to 66.5 hPa (600 to 50 mmHg). When the reaction treatment pressure exceeds 931 hPa (70 0 mmHg), it is easy to leave a volatile component containing alcohol. On the contrary, when the reaction treatment pressure is less than 1.33 hPa (lmmHg), it is difficult to carry out industrially. When an extruder having a through hole is used, the number of through holes may be one or plural, and it is preferable to use plural. The reaction treatment temperature when using an extruder equipped with a through hole is preferably from 15 Torr to 350 ° C, more preferably from 200 to 30 (TC. The reaction temperature is less than 15 (TC, the cyclization condensation reaction is not charged) In part, the residual volatile component is increased. Conversely, when the reaction treatment temperature exceeds 350 ° C, coloring or decomposition of the obtained polymer occurs. The reaction treatment pressure when using an extruder equipped with a through hole is preferably 931 2226-7326B-PF 21 1361809 to 1·33hPa (700 to lmmHg), more preferably 798 to 66. 5hPa (6〇〇 to 50mmHg). When the reaction treatment pressure exceeds 93ihPa (70 0mmHg), it is easy to residual alcohol The volatile component. Conversely, when the reaction treatment pressure is less than 1.33 hPa (1 mmHg), it is difficult to industrially carry out.

環化縮合反應整體併用脫揮步驟之型態時，如後文所述’嚴格的熱處理條件下所製得之具内酯環之聚合物之物性劣化，較佳係使用前文所述之脫醇反應觸媒、可能之溫和條件下，使用附有通孔之擠壓機施行。再者，於環化縮合反應之整體併用脫揮步驟之型態時，較佳係於聚合步驟製得聚合物（a)與溶劑一起導入環化縮合反應裝置系"匕時，於必要時’亦可再一次經由附有擠壓機等環化縮合反應裝置。脫揮步驟不併用於環化縮合反應過程整體中時，可以僅於過程之—部份中併用之型態進行。例如，⑨製造聚合物u)之裝置、再加熱，必要時―部份併帛脫揮步驟，預先 :二“度之環化縮合反應’之後引進脫揮步驟而同時併衣化合反應，完成反應之型態。月述之環化縮合反應整體併用脫揮步驟如，使用雔土心T ’例吏用又軸擠壓機’力25(rc左右，或於該時所:™—心 , I付之具内酯環聚合物之物性變差。此 2二進：脫揮步驟同時併用環化縮合反應前，預 …又之環化縮合反應可緩和後仃可抑制所製彳H ^ 丨之反應條件，由於斤“具内嶋合物之物性變差而較佳" 2226-7326B-PF ' ' 22 佳之型態為，例如， ^ ± βΗ Γ列舉脫揮步驟於環化縮合反應開始之時間開始，亦即，於取入 , 、&合步驟所製得之聚合物（a)之分子鏈令所存在之羥基盎gt ^ ^ g基，預先環化縮合反應而提升環化細合反應率，接荖，進仃脫揮步驟同時併用環化縮合反應之里態。具體而言仿J如，預先於溶劑存在下、使用釜型反應器進行某涯^ 、又之每化縮合反應至反應率為止，之後以配備脫揮裝置之反廊 …益’例如熱交換器與脫揮槽所成之脫揮裝置、或附有通子丨夕_^广，u 擠堡機等，完成環化縮合反應之型態較佳。特別是於兮 '又態時’存在環化縮合反應用觸媒為更佳。如則所述，聚合步驟所製得之聚合物（a)之分子鏈中所存在之&基與g旨基’預先環化縮合反應而提升環化縮合反應率，接著’進行脫揮步驟同時併用環化縮合反應之方法， j本發明製得具内醋環聚合物之較佳型態。由該型態，製付玻璃轉移溫度更高’環化縮合反應率亦更高，耐熱性優八U %聚合物。此時作為環化縮合反應率之標準，例如’於貫施例所示之動態TG測定中，15〇至3〇吖之範圍内之質量減少率較佳為2%以下，更佳為15%以下再佳為1%以下。 —八脫揮步驟同時併用環化縮合反應之前，預先進行環化縮:反應時可採用之反應器’並無特別限定Μ列如可列舉冋C滅菌鋼（aUtQcUve)、爸型反應器 '熱交換器與脫揮槽所成之脫揮裝置等，再者，脫揮步驟同時併用環化縮合反應亦可使用適合之附有通孔之擠麈機。該等反應器中，較When the cyclization condensation reaction is used in the same manner as in the devolatilization step, the physical properties of the polymer having a lactone ring obtained under the strict heat treatment conditions described later are deteriorated, and it is preferred to use the dealcoholization described above. The reaction catalyst, and possibly mild conditions, is carried out using an extruder equipped with a through hole. Further, in the case where the cyclization condensation reaction is carried out in the same manner as in the devolatilization step, it is preferred that the polymer (a) is introduced into the cyclization condensation reaction system together with the solvent in the polymerization step, when necessary. 'It is also possible to pass through a cyclization condensation reaction device such as an extruder. When the devolatilization step is not used in the cyclization condensation reaction as a whole, it may be carried out only in the form of a part of the process. For example, 9 a device for producing a polymer u), reheating, if necessary, a partial enthalpy devolatilization step, in advance: introducing a devolatilization step after two "degrees of cyclization condensation reaction" while simultaneously combining the reaction to complete the reaction The type of cyclization condensation described in the whole is used in conjunction with the devolatilization step, for example, using a crucible core T 'example and a shaft extruder 'force 25 (circle rc, or at that time: TM-heart, I The physical properties of the lactone ring polymer are deteriorated. This two-folding: the devolatilization step is combined with the cyclization condensation reaction, and the cyclization condensation reaction can be moderated and the ruthenium can inhibit the 彳H ^ 丨The reaction conditions are preferred because the physical properties of the internal chelates are deteriorated, and the preferred form is 2226-7326B-PF ' ' 22 , for example, ^ ± βΗ Γ lists the devolatilization step at the start of the cyclization condensation reaction. At the beginning, that is, the molecular chain of the polymer (a) obtained by the step of taking in, and & combines the hydroxyl group gt ^ ^ g group present, and the cyclization condensation reaction is carried out to enhance the cyclization reaction. The rate, the enthalpy, the enthalpy step, and the cyclization condensation reaction. For example, in the presence of a solvent, a kettle type reactor is used in advance to carry out a certain condensation reaction to a reaction rate, and then a reaction device equipped with a devolatilizer is used, for example, a heat exchanger and The devolatilization device formed by the devolatilization tank, or the condensed condensation reaction is better, and the cyclization condensation reaction is better. More preferably, the catalyst for the condensation reaction is as described above, and the cyclization condensation reaction of the & base and the g-group present in the molecular chain of the polymer (a) obtained by the polymerization step enhances the cyclization condensation. The reaction rate, followed by 'the devolatilization step and the cyclization condensation reaction at the same time, j. The present invention produces a preferred form of the inner vinegar ring polymer. From this type, the glass transition temperature is higher. The condensation reaction rate is also higher, and the heat resistance is better than that of the U.sup.1 polymer. At this time, as a standard of the cyclization condensation reaction rate, for example, in the dynamic TG measurement shown in the example, the range is 15 〇 to 3 〇吖. The mass reduction rate is preferably 2% or less, more preferably 15% or less and preferably 1% or less. The devolatilization step is carried out in advance before the cyclization condensation reaction is carried out, and the cyclization is carried out in advance: the reactor which can be used in the reaction is not particularly limited. For example, 冋C sterilized steel (aUtQcUve), dad type reactor 'heat exchanger The devolatilizer formed by the devolatilization tank, and the devolatilization step may also be used in combination with the cyclization condensation reaction, and a suitable squeezing machine with a through hole may be used.

2226-7326B-PF 23 1361809 佳為南麼滅讀鋼、圣· Φ反康哭金笙反應态。然而，使用附有通孔之擠塵機等反應器時，於溫和通孔條件下允許通孔而調整溫度條件或81筒（b町el)條件、螺旋形狀、螺旋運轉條件等，可進行與高壓滅菌鋼及爸型反應器之反應狀態相同狀態之環化縮合反應。 —脫揮步驟同時併用環化縮合反應之前，預先進行環化2226-7326B-PF 23 1361809 Jiawei South is to destroy the steel, St. Φ anti-Kang, the golden 笙 reaction state. However, when a reactor such as a dust blasting machine with a through hole is used, the through hole can be allowed to be adjusted under a gentle through hole condition, or the condition of the 81 cylinder (b), the spiral shape, the spiral operation condition, etc. can be performed. The cyclization condensation reaction of the autoclaved steel and the dad-type reactor in the same state of reaction. - cyclization is carried out before the devolatilization step is carried out simultaneously with the cyclization condensation reaction

合反應時，例如，可而丨與仏A 了列舉於含有聚合步驟所製得聚合物 ⑷以及溶劑之混合物中’⑴添加觸媒、加熱反應之方法， (")無添加觸媒而加熱反應之方法，以及前述⑴或⑹ 於加麼下進行之方法等。内酉曰化縮合步驟中，導^ 導入級化縮合反應之「含有聚合物（a )以及溶劑之、，0人私 ^ "σ物」，意指為聚合步驟所製得之聚 δ反應混合物本身，或杳+ . 5 $者去除—部分溶劑後，再添加適合 %化縮合反應之溶劑所製得之混合物。脫揮步驟同時併用環化二唯σ反應之刖，預先進行環化 &合反應時可再添加舉甲苯、二Μ 7 b I”、、特別限疋，例如，可列基本等芳香族烴類；甲基乙基酮、甲 “山酮等，類；氯仿、二甲基亞楓該等溶劑可單獨使用或2種南’專專使用之溶劑為同種類之溶劑為佳㈣。使用與聚合步驟所 -甲苯絡酸等加之觸媒’例如可列舉-般所使用之對欺Λ 類觸媒__觸媒、驗性化合物、有機羧酸鹽、碳酸鹽等，男讽物為較佳。觸媒添：’已使用前述之有機磷化合加之時間’並無特別限定，例如可於反In the case of the reaction, for example, hydrazine and hydrazine A are listed in the mixture containing the polymer (4) obtained in the polymerization step and the solvent, '(1) adding a catalyst, heating the reaction, (") heating without adding a catalyst The method of the reaction, and the method of the above (1) or (6), and the like. In the internal deuteration condensation step, the introduction of the stepwise condensation reaction "containing the polymer (a) and the solvent, 0 person private "σ substance" means the polyδ reaction obtained by the polymerization step The mixture itself, or 杳+. 5 $, is removed - part of the solvent, and then a mixture of solvents suitable for the condensation reaction is added. The devolatilization step is carried out simultaneously with the cyclization of the sigma sigma reaction, and the cyclization & ampere reaction may be further carried out by adding toluene, ruthenium 7 b I", and especially to ruthenium, for example, basic aromatic hydrocarbons may be listed. Class; methyl ethyl ketone, methyl "ketone", etc.; chloroform, dimethyl sulfoxide, etc. These solvents can be used alone or two kinds of solvents used in the South 'specially used are the same kind of solvent is better (four). The catalyst used in the polymerization step, such as toluic acid or the like, may be exemplified by the use of a bullying catalyst, a catalyst, an organic compound, a carbonate, or the like. Preferably. Catalyst addition: 'The time when the above-mentioned organic phosphorus compound has been used' is not particularly limited, and for example, it may be reversed.

2226-7326B-PF 24 丄观809 應初期添加、可於反應途中添加媒之添加量，並無特㈣定，例如，=兩者皆添加。觸量’較佳為〇.〇〇…質量％、更佳為/聚合物⑷之質再佳為〇 01 5 η ,所曰。佳為〇.01至2.5質量％、勹υ· 01至0.1質量％、特佳為〇法（i)之加至0.5質量％。方疋加熱溫度以及加熱時間，並盔熱溫度較佐& 、。 .....別限定，例如，加佳為至溫至18 0。0，更佳％ ς n % 時間較佳兔， t佳為5吖至15(TC，加熱季乂佳為1至20小時，更佳為2至未達:t㈤a# + i 〇小時。加熱溫度逆至/皿時，或者加熱時間未達丨降供 + f 裱化縮合反應率氏。相反地，加熱溫度超過18〇。 2 〇丨主 ^者加熱時間超過 20小時，發生樹脂之著色或分解。方法（Η)例如可使用耐壓型爸型反應器等，將驟所製得之聚合物直接加熱。方 Α ' 8* „ ^ „ ^Ul)之加熱溫度或加熱特別限定’例如，加熱溫度較佳為⑽至刚 C ’更佳為mu 150t ’加熱時間較佳為i至2〇小時，更佳為2至1。小時。加熱溫度未達1〇〇。。時’或者加熱時間未達1小時，環化縮合反應率降低。相反地，加熱溫度超過180。。’或者加熱時間超過2〇小時，發生樹脂之f 或分解。任一者方法中，根據條件加壓亦無任何問題。脫揮步驟同時併用環化縮合反應之前，預先進行環化鈿合反應時，溶劑之一部分於反應甲自然揮發亦無任何題。 °2226-7326B-PF 24 丄 809 should be added at the beginning, and the amount of the medium added can be added during the reaction. There is no special (4), for example, = both are added. The amount of contact 'is preferably 〇.〇〇...% by mass, more preferably/the quality of the polymer (4) is better than 〇 01 5 η , 曰. Preferably, it is 0.1 to 2.5% by mass, 勹υ·01 to 0.1% by mass, and particularly preferably 〇 method (i) is added to 0.5% by mass. The heating temperature and heating time of the square, and the thermal temperature of the helmet are better than that of the & ..... Do not limit, for example, Jiajia to the temperature to 18 0. 0, more preferably % ς n % time better rabbit, t is preferably 5 吖 to 15 (TC, heating season is preferably 1 to 20 Hour, more preferably 2 to less than: t (five) a# + i 〇 hours. The heating temperature is reversed to / when the dish is heated, or the heating time is less than 丨供供 + f 裱 condensation reaction rate. Conversely, the heating temperature exceeds 18 〇 2 When the heating time of the main unit is more than 20 hours, the coloring or decomposition of the resin occurs. Method (Η) For example, a pressure-resistant dad type reactor or the like can be used to directly heat the polymer obtained by the step. The heating temperature or heating of 8* „ ^ „ ^Ul) is particularly limited. For example, the heating temperature is preferably from (10) to just C', preferably more than 150 seconds. The heating time is preferably from i to 2 hours, more preferably from 2 to 2. 1. hour. The heating temperature is less than 1〇〇. . When the time or heating time is less than 1 hour, the cyclization condensation reaction rate is lowered. Conversely, the heating temperature exceeds 180. . 'or the heating time exceeds 2 hours, the resin f or decomposition occurs. In either method, there is no problem in pressurizing according to the conditions. In the devolatilization step, before the cyclization condensation reaction is carried out in advance, when the cyclization reaction is carried out in advance, a part of the solvent is naturally volatilized in the reaction, and there is no problem. °

脫揮步驟同時併用環化縮合反應之前，預先進行枣化縮合反應終了時，亦即脫揮步驟開始之前，動態測AThe devolatilization step is performed at the same time as the cyclization condensation reaction, before the end of the jujube condensation reaction, that is, before the start of the devolatilization step, the dynamic measurement A

2226-7326B-PF 25 1361809 至30 〇 C %圍内之質量減少率，較佳為2%以下，更佳 %以下，再佳為1%以下。質量減少率超過2%時，進 :後序脫揮步驟同時併用環化縮合反應，環化縮合反應率提升至相备咼的程度’戶斤製得之具内酯環聚合物之物性變差上述衩化縮合反應進行時，除了聚合物（a)之外，可共存其他熱可塑性樹脂。聚σ步驟所製得聚合物（a)分子鏈中存在之羥基與酯基’於預先環化縮合反應之環化縮合反應率提升至某程度接著，進行脫揮步驟同時併用環化縮合反應型態時，預先進饤環化縮合反應巾所製得之聚合物（分子鏈中存在經基〃 @曰基至少—部分環化縮合反應之聚合物）以及溶別，可直接導入脫揮步驟同時併用環化縮合反應中，必要時可經由單離前述聚合物（分子鏈中存在之羥基與酯基至 ^ 。卩刀環化縮合反應之聚合物）、再添加溶劑等其他處理，而導入脫揮步驟同時併用環化縮合反應。脫揮步驟’不限於與環化縮合反應同時終了，亦可於環化反應終了後時間内終了。具内i旨環聚合物之質量平均分子量較佳為1，〇〇〇至 2, 〇〇〇, 000 ’ 較佳為 5, 〇〇〇至 1，〇〇〇, 〇〇〇，再佳為 1〇, 〇〇〇至 500, 000 ’ 特佳為 50, 000 至 500, 000。具内S旨環聚合物於動態TG測定1 50至300°C範圍内之質置減少率’較佳為1%以下，更佳為0. 5%以下，再佳為 0. 3%以下。2226-7326B-PF 25 1361809 to 30 〇 C% within the mass reduction rate, preferably 2% or less, more preferably less than %, and more preferably less than 1%. When the mass reduction rate exceeds 2%, the subsequent step of the devolatilization step is simultaneously combined with the cyclization condensation reaction, and the cyclization condensation reaction rate is increased to the extent of the preparation of the oxime. The physical properties of the lactone ring polymer obtained by the household are deteriorated. When the above deuteration condensation reaction proceeds, other thermoplastic resins may be present in addition to the polymer (a). The cyclization condensation reaction rate of the hydroxyl group present in the molecular chain of the polymer (a) and the ester group 'in the pre-cyclization condensation reaction is increased to a certain degree, and the devolatilization step is carried out simultaneously with the cyclization condensation reaction type. In the state, the polymer obtained by the pre-advanced fluorene condensation reaction towel (the polymer having at least a partial cyclization condensation reaction in the molecular chain) and the solvent can be directly introduced into the devolatilization step. In the cyclization condensation reaction, if necessary, it can be introduced by removing the polymer (the polymer which is present in the molecular chain and the ester group to the cyclization cyclization condensation reaction), and further adding a solvent. The cyclization condensation reaction is carried out simultaneously with the sulfonation step. The devolatilization step is not limited to the end of the cyclization condensation reaction, and may be terminated after the end of the cyclization reaction. The mass average molecular weight of the inner ring-shaped polymer is preferably 1, from 〇〇〇 to 2, 〇〇〇, 000 ' is preferably 5, 〇〇〇 to 1, 〇〇〇, 〇〇〇, and preferably 1〇, 〇〇〇 to 500,000' is particularly good at 50,000 to 500,000. The 5% or less, more preferably 0.3% or less, is preferably less than or equal to 0.5% by weight.

具内S旨環聚合物於環化縮合反應率高時，可避免成形 2226-7326B-PF 26 1361809 後之成形品中有起泡或銀線之缺點。再者，由於高環化縮合反應率可充分將内酯環構造導入聚合物，所製得^具内酯環聚合物具有充分之高耐熱性。具内酯環聚合物於濃度15質量％之氯仿溶液中時其著色度（YI)較佳為6以下，更較佳為3以下，再佳為2 2 下，特佳為1以下。著色度⑺)超過6時，由於著色而損害透明性，有原本目的之用途無法使用之情況。胃具内i旨環聚合物於熱質量分析⑽中，量減少溫度較佳為33〇t以上，更佳為35(rcj^，再佳為上。熱質量分析⑽中，質量減少溫度為熱安定性之# 標，未達33〇t者，無法發揮充分之安定性。具内酿環聚合物之玻璃轉移溫度㈤較佳4 U5t以上，更=為咖以上，再佳為靴以上’特佳為_ 以上，最佳為14(TC以上。具内酯環聚合物所含殘餘揮 5 ΠΠΩηηη! r; -r- "取刀之總置，較佳為 5,0。0…下’更佳為2，__以下，以下，特佳為1，_以下。殘㈣n ，5〇°PPm 5’__時，成形時由成二成：之總量超過等成形不良原因。 ^而成為者色、發泡、銀線具内醋環聚合物以射 ASTM-D- 1 003 aaj| *出成形所製得成形品，以 1 u㈧為基準之方法蜊以上，更佳為M。/ 王先線穿透率，較佳為85% 為88%以上，再佳為9〇% 透明性之指標，該等未達以線穿透率為之用途無法使用之情況。者’透明性低’有原本目的When the rate of the cyclization condensation reaction is high, the inner ring-shaped cyclic polymer can avoid the disadvantages of foaming or silver wire in the molded article after molding 2226-7326B-PF 26 1361809. Further, since the lactone ring structure can sufficiently introduce the lactone ring structure into the polymer due to the high cyclization condensation reaction rate, the resulting lactone ring polymer has sufficiently high heat resistance. When the lactone ring polymer is used in a chloroform solution having a concentration of 15% by mass, the degree of coloration (YI) is preferably 6 or less, more preferably 3 or less, still more preferably 2 2 or less, particularly preferably 1 or less. When the degree of coloration (7) is more than 6, the transparency may be impaired by the coloring, and the intended use may not be used. In the thermal mass analysis (10), the amount of the ring-reducing polymer is preferably 33 〇t or more, more preferably 35 (rcj^, more preferably. In the thermal mass analysis (10), the mass reduction temperature is heat. The stability of the # standard, less than 33〇t, can not exert full stability. The glass transition temperature of the inner ring polymer (five) is better than 4 U5t, more = more than the coffee, and then better than the boots above Preferably, the optimum is 14 (TC or more. The residue contained in the lactone ring polymer is 5 ΠΠ Ω ηηη! r; -r- " the total setting of the knife, preferably 5,0. 0... More preferably, it is 2, __ or less, and the following is particularly preferably 1, _ or less. Residual (four) n, 5 〇 ° PPm 5'__, the molding is made into two parts: the total amount exceeds the cause of forming defects. The color, foaming, and silver threaded inner vinegar ring polymer are sprayed into ASTM-D-1 003 aaj| *. The molded article obtained by molding is based on 1 u (eight), more preferably M. Wang Xianxian penetration rate, preferably 85% is 88% or more, and even better than 9〇% transparency index, such as the case where the line penetration rate is not available for use. 'There are original purpose

2226-7326B-PF 27 1361809 《光學用平面狀熱可塑性樹脂組合物（A)》本發明之光學用平面狀熱可塑性樹脂組合物係以含有具内酯環聚合物做為主成分為特徵。 . 光學用平面狀熱可塑性樹脂組合物（A)中具内酯環聚合物之含有比例，較佳為50至1〇〇質量％，更佳為6〇至 100質量％，再佳為70至100質量％,特佳為80至1〇〇質量％。光學用平面狀熱可塑性樹脂組合物（A)中具内酯環聚 • 合物之含有比例未達質量％時，無法充分發揮本發明之效果。光學用平面狀熱可塑性樹脂組合物（A)中，亦可含有具内酯環聚合物以外之聚合物（下文中有時稱為「其他聚合物」），作為其他成分。其他聚合物，例如’可列舉聚乙烯、聚丙烯、乙稀_ 丙烯共聚物、聚（4-曱基-1-戊烯）等烯烴聚合物；氯化乙 '歸氯化亞乙稀、氣化乙烯樹脂等齒化乙稀系聚合物；聚 _ 甲基丙烯酸甲酯等丙烯酸系聚合物；聚苯乙烯、苯乙烯一曱基丙烯酸曱酯共聚物、苯乙烯—甲基丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯嵌段共聚物等苯乙烯系聚合物；聚對苯二曱酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二曱酸乙二醇醋等聚醋；尼龍6、尼龍66、尼龍61〇等聚酿胺；聚縮醛’·聚碳酸酯；聚苯醚、聚苯硫醚；聚醚醚酮；聚楓；聚醚楓；聚氧苯曱酯；聚醯胺亞醯胺；配合聚丁二稀系橡膠、丙烯酸系之ABS樹脂或ASA樹脂等橡膠質量聚合物；等等。 2226-7326B-PF 28 光學用平面狀熱可塑性樹之含有比例，較佳為〇至50質量；；物(A)中其他聚合物再佳為0至30質量％、特佳為^更佳為0至40質量％、 ·為0至2〇質量％。本發明之光學用平面狀熱可含有種添加劑& 樹知組δ物（A)亦可 . …“加劑，例如可列舉糸等氧化防止劍，·耐光安定劑 ;^糸系、硫安定劑；玻璃纖难^ ，4女疋劑、熱安定劑等麵基^基苯基）笨并三唾材甚水杨酸苯醋'(U，- 收劑，·近紅外“酮等紫外線吸丙酯、氧，、基）磷酸酯、磷酸三烯氣化銻等難燃劑；陰離子、陽面活性劑等帶電防止劑；無機顏料：離子糸之界色劑；有機填料或無機填料;樹脂:有機=著無機填充劑；可塑劑；滑劑；帶電防：:1，有機填充劑或 # M .^ u 電防止劑，難燃劑；等等。先手用+面狀熱可塑性樹脂有比例，較佳為0至5質旦。/ s物（A)中添加劑之含為….5質量% fW°至2㈣、再佳光學用平面狀熱可塑性樹脂組合物（A)之製造方法，並無特別限定者，例如，可將具内醋環聚合物，與必要時之其他聚合物或添加劑等，使用以往習知之混合方法充分混合，將其成形為平面狀。平面狀 .,, 狀之生心以溥膜狀或薄月狀為佳。本發明中，為了區別薄膜狀之光學用平面狀孰可塑性 ==與薄片狀之光學用平面狀熱可塑性樹脂組合物（A)’疋義薄膜狀之光聲尤子用千面狀熱可塑性樹脂組合物2226-7326B-PF 27 1361809 "Planar thermoplastic resin composition for optical use (A)" The planar thermoplastic resin composition for optical use of the present invention is characterized by containing a lactone ring polymer as a main component. The content ratio of the lactone ring polymer in the planar thermoplastic resin composition (A) for optics is preferably from 50 to 1% by mass, more preferably from 6 to 100% by mass, even more preferably from 70 to 100% by mass, particularly preferably 80 to 1% by mass. In the case where the content ratio of the lactone ring polymer in the planar thermoplastic resin composition (A) is less than 3% by mass, the effects of the present invention are not sufficiently exhibited. In the planar thermoplastic resin composition (A) for optics, a polymer other than the lactone ring polymer (hereinafter sometimes referred to as "other polymer") may be contained as the other component. Other polymers, for example, may be exemplified by olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly(4-mercapto-1-pentene); Tetraethylene polymer such as vinyl resin; acrylic polymer such as poly-methyl methacrylate; polystyrene, styrene-mercapto acrylate copolymer, styrene-methacrylonitrile copolymer, Styrene polymer such as acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Polyacetal; nylon 6, nylon 66, nylon 61 〇 and other polyamines; polyacetal '·polycarbonate; polyphenylene ether, polyphenylene sulfide; polyether ether ketone; poly maple; polyether maple; polyoxygen Phenyl phthalate; polyamidamine; rubber mass polymer such as polybutylene rubber, acrylic ABS resin or ASA resin; 2226-7326B-PF 28 The proportion of the planar thermoplastic tree for optics is preferably 〇 to 50 mass; and the other polymer in the material (A) is preferably from 0 to 30% by mass, particularly preferably ^ 0 to 40% by mass, · 0 to 2% by mass. The planar heat of optics of the present invention may contain a kind of additive & a group of δ substances (A) may also be used as an additive, for example, an oxidation prevention sword such as ruthenium, a light stabilizer, a ruthenium system, and sulphur Agent; glass fiber difficult ^, 4 female bismuth, heat stabilizer, etc. base phenyl) stupid and three saliva, salicylic acid benzene vinegar '(U, - collection, · near-infrared" ketone and other ultraviolet absorption a flammable agent such as propyl ester, oxygen, or phosphoric acid ester, triene gasification ruthenium; an antistatic agent such as an anion or a positive surfactant; an inorganic pigment: an intermediate agent for ionization; an organic filler or an inorganic filler; : organic = inorganic filler; plasticizer; slip agent; charged anti-:: 1, organic filler or # M. ^ u electric preventive agent, flame retardant; The first hand uses a + planar thermoplastic resin in proportion, preferably from 0 to 5 denier. The method of producing the planar thermoplastic resin composition (A) in which the content of the additive in the material (A) is 5% by mass, fW° to 2 (four), and the optical fiber is not particularly limited, and for example, The inner vinegar ring polymer, if necessary, other polymers or additives, is sufficiently mixed by a conventional mixing method to form a flat shape. The flat shape, the shape of the heart is preferably a membranous or thin moon. In the present invention, in order to distinguish the film-like optical planarity plasticity == and the sheet-like optical planar thermoplastic resin composition (A), the film-like photoacoustic syrup uses a thousand-faced thermoplastic resin. combination

2226-7326B-PF 29 (A)為厚度未達35〇以m，而薄片狀之光學用平面狀熱可塑性樹脂組合物（A)為厚度35〇/z ^以上。溥瞑狀之光學用平面狀熱可塑性樹脂組合物（A)之厚度較佳為1…上未達350 " m，更佳為1Mm以上未達 350 “。厚度未達1//m時，無法表現充分的機械強度，進行延伸時容易發生斷裂。溥片狀之光學用平面狀熱可塑性樹脂組合物（A)之厚度較佳為350 /ζπι至l0mm，更佳為咖㈣至5mm。厚度超過l〇mm時，難以獲得均一的厚度。本發明之光學用平面狀熱可塑性樹脂組合物（a)為具有高透明性，全光穿透率較佳為8〇%以上，更佳為㈣以上，再佳為90%以上，特佳為92%以上。本發明之光學用平面狀熱可塑性樹脂組合物（A)以 ASTM-D-882-61T為基準敎抗張強度時，較佳為麗3以上、未達lOOMPa，更佳為30MPa以上、未達1〇〇胸。抗張強度未達lOMPa時，無法表現充分之機械強度。相反地，抗張強度超過lOOMPa時，加工性變差。本發明之光學用平面狀熱可塑性樹脂組合物(A)以 ASTM-D-882-61T為基準測定延伸率時，較佳為1%以上。延伸率之上限並無特別限定者，通常，較佳為igq%以下。延伸率未達1 %時，欠缺勒性。本發明之光學用平面狀熱可塑性樹脂組合物⑴以 ASTM-D-882-61T為基準測定抗張禪性率時，較佳〇.5Gpa 以上，更佳為IGPa以上，再佳為2Gpa以上。抗張彈性率2226-7326B-PF 29 (A) is a thickness of less than 35 Å in m, and the sheet-like optical planar thermoplastic resin composition (A) has a thickness of 35 Å/z or more. The thickness of the planar thermoplastic resin composition (A) for the optical shape of the braid is preferably less than 350 " m, more preferably 1 Mm or more and less than 350". When the thickness is less than 1/m, It is not possible to exhibit sufficient mechanical strength and is liable to break when stretched. The thickness of the planar thermoplastic resin composition (A) for sheet-like optics is preferably from 350 / ζ π to l0 mm, more preferably from coffee (four) to 5 mm. When it exceeds 10 mm, it is difficult to obtain a uniform thickness. The planar thermoplastic resin composition (a) for optics of the present invention has high transparency, and the total light transmittance is preferably 8% or more, more preferably (4). More preferably, it is 90% or more, and particularly preferably 92% or more. When the planar thermoplastic resin composition for optical use of the present invention (A) is based on ASTM-D-882-61T, the tensile strength is preferably Li 3 or more, less than 100 MPa, more preferably 30 MPa or more, less than 1 〇〇 chest. When the tensile strength is less than 10 MPa, sufficient mechanical strength cannot be expressed. Conversely, when the tensile strength exceeds 100 MPa, the workability is deteriorated. The planar thermoplastic resin composition for optical use of the present invention (A) is ASTM-D When -882-61T is used for the measurement of the elongation, it is preferably 1% or more. The upper limit of the elongation is not particularly limited, and usually, it is preferably igq% or less. When the elongation is less than 1%, the rigidity is insufficient. The planar thermoplastic resin composition for optical use of the invention (1) is preferably 〇5 Gpa or more, more preferably IGPa or more, and more preferably 2 GPa or more, based on ASTM-D-882-61T. Elasticity rate

2226-7326B-PF 30 1361809 之上限，並無特別限定者，通常，較佳為2〇Gpa以下。抗張彈性率未達〇.5GPa時，無法表現充分之機械強度。本發明之光學用平面狀熱可塑性樹脂组合物（A)，根據目的需要，亦可積層塗布帶電防止層、黏著劑層、接著層、易接著層、抗眩光、光觸媒層等防污層、反射防止f、硬塗層 '紫外線遮蔽層、熱線遮蔽層、電磁波遮蔽層、氣體障礙層等各種功能性塗覆層，本發明之光學用平面狀熱可塑性樹脂組合物（A)中，經各單獨功能性塗覆層塗布之材料可藉由黏著劑或接著劑積層為積層體。各層之積層順序並無特別限定，積層方法亦無特別限定。紫外線遮蔽層，係為防止較紫外線遮蔽層更下層之基材層或印刷層等紫外線劣化材料之紫外線劣化而設置者。紫外線遮蔽層之分子量為U00以下之紫外線吸收劑，可配合於丙烯酸系樹脂、聚I系樹脂、說系樹脂等熱可塑性樹脂’或熱硬化性、濕氣硬化性、紫外線硬化性、電子束硬化性等硬化性樹脂中使用者’特別是由耐候性之觀點而言，以日本專利第3081 508號公報、第34〇416〇號公報、第2835396號公報中，所揭示之聚合單體混合物（該單體混合物必需含有具紫外線吸收性骨架單體）所製得之丙烯酸系聚合物為佳。市售商品而言，可列舉「如咖⑽ UV-G13」或「Halshybriduv — G3〇1」（上述商品為日本觸媒公司製造）、「ULS-935LH」（-方社油脂工業公司製造）等。熱線遮蔽層’例如，為.防止顯示裝置之發光所伴隨產生之近紅外線（特別是70〇111„至12〇〇nm)造成周圍機器之錯The upper limit of 2226-7326B-PF 30 1361809 is not particularly limited, and is usually preferably 2 〇 Gpa or less. When the tensile modulus is less than .5 GPa, sufficient mechanical strength cannot be exhibited. The planar thermoplastic resin composition (A) for optics of the present invention may be coated with an anti-fouling layer such as a charging prevention layer, an adhesive layer, an adhesive layer, an easy-adhesion layer, an anti-glare, and a photocatalyst layer, and may be laminated as needed. Various functional coating layers such as f, a hard coat layer, an ultraviolet shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier layer are prevented, and the optical planar plastic resin composition (A) of the present invention is individually used. The material coated with the functional coating layer may be laminated as a laminate by an adhesive or an adhesive. The order of lamination of the layers is not particularly limited, and the lamination method is not particularly limited. The ultraviolet shielding layer is provided to prevent ultraviolet deterioration of the ultraviolet-degraded material such as the base layer or the printing layer which is lower than the ultraviolet shielding layer. The ultraviolet shielding layer has a molecular weight of less than U00, and can be blended with a thermoplastic resin such as an acrylic resin, a poly-based resin or a resin, or a thermosetting resin, a moisture curing property, an ultraviolet curing property, or an electron beam curing. The polymerizable monomer mixture disclosed in Japanese Patent No. 3081 508, No. 34 〇 416 、, and No. 2835396 (in particular, from the viewpoint of the weather resistance). It is preferred that the monomer mixture contain an acrylic polymer obtained by having a UV absorbing matrix monomer. For example, "Mr. (10) UV-G13" or "Halshybriduv - G3〇1" (the above-mentioned products are manufactured by Nippon Shokubai Co., Ltd.), "ULS-935LH" (manufactured by Fukusei Oil & Fats Co., Ltd.), etc. . The heat ray shielding layer ', for example, prevents the near-infrared rays (especially 70 〇 111 „ to 12 〇〇 nm) accompanying the illuminating of the display device from causing the fault of the surrounding machine.

2226-7326B-PF 31 1361809 誤動作而設置。熱線遮蔽層可使用有機系或無機系之熱線遮蔽物質配合於丙烯酸系樹脂、聚酯系樹脂、氟系樹脂等熱可塑性樹脂’或熱硬化性、濕氣硬化性、紫外線硬化^、電子束硬化性等硬化性樹脂甲使用者。有機系之敎線遮蔽物質以献菁色素或二亞敍系、斯夸林（SquaryUum)系等具有於近紅外線區域吸收之物質為限，並無特別限定者，根據用途，可與仆啉（Porphyrin)系或花青系色素等具有於可見光區域（400 S 700_)吸收之物f，丄種或2種以上互相組合使用。無機系之熱線遮蔽物質，例如，可列舉金屬、金屬氮化物、金屬氧化物等’由對分散媒體之溶解性、耐候性之觀點而言，較宜使用金屬氧化物之微粒子。全屬氣化物較佳為氧化鋼系、氧化辞系，由透明性之觀點而言，平均粒徑為0. 1 A m以下者為佳。黏接著劑層，可列舉丙烯糸姓+ “ 内締系樹脂、丙烯酸酯樹脂、或 =之共聚物、苯乙稀-丁二婦共聚物、聚異戊二烯橡膠、2226-7326B-PF 31 1361809 Set by malfunction. The heat ray shielding layer can be blended with an organic or inorganic heat ray shielding material in a thermoplastic resin such as an acrylic resin, a polyester resin or a fluorine resin, or a thermosetting property, a moisture curing property, an ultraviolet curing method, or an electron beam curing. Sexually curable resin A user. The organic ray-line shielding material is not particularly limited as long as it is absorbed in the near-infrared region, such as a cyanine dye, a smectite, or a Squary Uum, and may be combined with servoline depending on the use. The Porphyrin) or the cyanine dye has a substance f which is absorbed in the visible light region (400 S 700_), and is used in combination of two or more kinds. Examples of the inorganic heat ray shielding material include a metal, a metal nitride, a metal oxide, etc. From the viewpoint of solubility to a dispersion medium and weather resistance, fine particles of a metal oxide are preferably used. The gas is preferably an oxidized steel system or an oxidized system. From the viewpoint of transparency, the average particle diameter is preferably 0.1 or less. The adhesive layer may be exemplified by an acrylic resin + "internal resin, acrylate resin, or copolymer of styrene, styrene-butadiene copolymer, polyisoprene rubber,

烯橡膠等橡膠類，聚乙烯醚系1氧M H :酿亞胺系、氛基丙稀酸物"妾著劑等，其等可單獨：或可配合交聯劑、黏著付與劑。由光學特性、耐光性、 =明性之觀點而言，丙烯酸垸基s旨單體作為之 ::丙：系樹脂較佳’添加芳香族系黏著付與劑而調二 =著=平面狀熱可塑性樹脂組合物⑴之折射3 例:二==時’黏著劑之前述熱線遮蔽物質，声，由作為二#素或化青素色素之功能性黏著劑 θ 先子積層體之薄層化、生產性之觀點而言為有A rubber such as an olefin rubber, a polyvinyl ether-based 1 oxygen M H : an acrylamide-based, an acryl-based acrylic acid & the like, and the like may be used alone or in combination with a crosslinking agent or an adhesive. From the viewpoints of optical properties, light resistance, and brightness, acrylic acid s-based monomer is used as:: C: the resin is preferably 'added an aromatic adhesive agent and adjusted two == flat heat Refraction of the plastic resin composition (1): For example: when the second ==, the heat-shielding substance of the adhesive, the sound, is thinned by the functional adhesive θ of the bismuth pigment or the phthalocyanine pigment. Productive point of view

2226-7326B-PF 32 丄利的。 . 1磁波遮蔽層’例如，為防止由顯示裝置之發光所伴隨產生之電磁波而對個體或電子機器之壞影響所設置者。電、波遮蔽層’包含銀、鋼、氧化銦、氧化鋅、氧化姻锡、 ^，録錫等金屬或金屬氧化物之薄膜。該等薄膜可利用真二热鍍法、離子塗覆法、賤鐘法、⑽法'電紫化學蒸鐘等以彺么知之乾式塗布法製造。電磁波遮蔽層最常使用者 •為氧化銦錫(簡稱為「IT0」）之薄膜，亦可適合將具有網眼狀孔之銅薄膜、或介電體層與金屬層於基材上交互積層為積層體。介電體曾可列舉氧化姻、氧化辞等透明金屬氧化物等’金屬層-般為銀或銀合金。積層體，通常由介電體層開始積層，而積層3至13層左右間之奇數層之方式積層。、反射防止層，抑制表面之反射，防止螢光燈等外來光對表面之映入。反射防止層包含金屬氧化物、敦化物、矽 >化物、测化物、碳化物、氮化物、硫化物等無機物薄膜時，包含丙烯系樹脂、氟樹脂等折射率不同之樹脂之單層或多層之積層者。亦可使用日本專利特開2〇〇3_2928〇5號公報揭示之含有無機系化合物以及有機系化合物之複合微粒子之薄膜所積層者。抗眩光層係為了擴展視角，散|L透過光而設置。係將氧化石夕、蜜胺樹脂、丙稀系樹脂等微粉體加以墨水化，使用以往習知之塗布法’塗布於其他功能層上，經熱或光硬化而形成。亦可將經抗眩光處理之薄膜貼附於其他功能性 2226-7326B-PF 33 1361809 層薄膜上。硬塗層係將二氧化矽系硬化性樹脂、含有機聚合物複 5微粒子之硬化性樹脂、脲烷丙烯酸酯、環氧丙烯酸酯、夕s能丙烯酸酯等丙烯酸酯以及光聚合起始劑，熔解或分政於有機溶劑之塗布液，使用以往習知之塗布法，於本發2226-7326B-PF 32 丄利. A magnetic wave shielding layer is provided, for example, for preventing a bad influence on an individual or an electronic device caused by electromagnetic waves generated by the light emission of the display device. The electric and wave shielding layer 'includes a film of a metal such as silver, steel, indium oxide, zinc oxide, oxidized sulphur tin, ^, tin, or a metal oxide. These films can be produced by a dry dip coating method using a true two-hot plating method, an ion coating method, a cesium clock method, a (10) method, an electro violet chemical vapor clock, and the like. The most common user of the electromagnetic wave shielding layer is a film of indium tin oxide (referred to as "IT0"), which is also suitable for laminating a copper film having a mesh-like hole or a dielectric layer and a metal layer on a substrate. body. The dielectric layer may be a silver metal or a silver alloy, such as a transparent metal oxide such as an oxidized or oxidized metal. The laminate is usually laminated by a dielectric layer and laminated by an odd number of layers between 3 and 13 layers. The anti-reflection layer suppresses the reflection of the surface and prevents the external light such as a fluorescent lamp from being reflected on the surface. When the antireflection layer contains an inorganic thin film such as a metal oxide, a ruthenium compound, a ruthenium compound, a test compound, a carbide, a nitride or a sulfide, a single layer or a plurality of layers of a resin having a refractive index different from a propylene resin or a fluororesin may be contained. The layerer. A film comprising a composite fine particle containing an inorganic compound or an organic compound disclosed in Japanese Laid-Open Patent Publication No. Hei. The anti-glare layer is provided to spread the light in order to expand the viewing angle. A fine powder such as a oxidized stone, a melamine resin or an acrylic resin is inked and applied to another functional layer by a conventional coating method, and is formed by heat or light hardening. The anti-glare film can also be attached to other functional 2226-7326B-PF 33 1361809 film. The hard coat layer is a cerium oxide-based curable resin, a curable resin containing an organic polymer-containing 5 fine particles, an acrylate such as urethane acrylate, epoxy acrylate, or s-s-acrylate, and a photopolymerization initiator. Melting or dividing into a coating liquid of an organic solvent, using a conventional coating method in the present invention

明之光學用平面狀熱可塑性樹脂組合物（A)上，最好於最外層之位置，塗布、乾燥、光硬化而形成。二氧化矽系硬化性樹脂為具有矽氧烷鍵結之樹脂，例如，可列舉三烧氧基矽烷以及四烷氧基矽烷或其等烷基化物之部分水解物，甲基三烷氧基矽烷以及苯基三烷氧基矽烷之混合物之經水解者’膠體狀（C〇ll〇dial)矽充填之有機烷氧基矽烷之部分水解縮合物等。市售商品而言，例如可列舉「Si cod〗」（第八化學工業公司製造）、「T〇s Gard 51〇」及「MHC85M (以上為GE東芝Silic〇n公司製造）、「s〇l 肝了別及「Sol Gard NP730」及「Sol Gard RF0831」（以上為 e 本Dalcroshamlock(音譯）公司製造）等。有機聚合物複名微粒子，意指於無機微粒子表®，有冑聚合物固定複合寿機微粒子’以於含該複合無機微粒子之硬化性樹脂形:表面保護層’而達到使表面硬度向上提升等。複合無機微粒子及其製法之細節，例如日本專利特開平號、In the planar thermoplastic resin composition (A) for optical use, it is preferably formed by coating, drying, or photocuring at the position of the outermost layer. The cerium oxide-based curable resin is a resin having a siloxane coupling, and examples thereof include a partial a hydrolyzate of a trisoxy decane and a tetraalkoxy decane or an alkylate thereof, and a methyl trialkoxy decane. And a partially hydrolyzed condensate of a mixture of phenyltrialkoxy decane and a hydrolyzed 'C〇ll〇dial 矽 filled organoalkoxydecane. For example, "Si cod" (manufactured by the 8th Chemical Industry Co., Ltd.), "T〇s Gard 51", and "MHC85M (above, manufactured by GE Toshiba Silicon Co., Ltd.), "s〇l" The liver is different from "Sol Gard NP730" and "Sol Gard RF0831" (the above is manufactured by e Dalcroshamlock). The organic polymer naming microparticles means that the inorganic microparticles are sized, and the conjugated polymer-fixed composite microparticles are used to form a surface of the hardened resin containing the composite inorganic microparticles: a surface protective layer. . Details of composite inorganic microparticles and their preparation methods, such as Japanese Patent Laid-Open,

報、特时9韻57號純、㈣平u_m467號公= 所揭不者。含有複合無機微粒子之硬化性樹脂亦無㈣限定者，例如可列舉蜜胺樹脂 '脲燒樹脂.、⑨氧樹脂咖)、多官能丙稀系樹脂等。多官能丙婦系樹脂可列舉 2226-7326B-PF 34 1361809 多元醇丙烯酸輯、聚酯丙烯酸酯、脲烷丙烯酸酯、環氧丙稀自9等相'爿曰。含有複合無機微粒子之硬化性樹脂之市售商口口：例如可列舉「U-dabul C3300」及「u-dabul C3600」 (音譯）（以上，日本觸媒公司製造）等。〈光學用保護薄膜> 本發明之光學用平面狀熱可塑性樹脂組合物（A)之一Newspaper, special time 9 rhyme 57 pure, (four) flat u_m467 public = not revealed. The curable resin containing the composite inorganic fine particles is not limited thereto, and examples thereof include a melamine resin 'urea resin resin, a 9-oxygen resin coffee', and a polyfunctional acrylic resin. The polyfunctional propylene-based resin may be exemplified by 2226-7326B-PF 34 1361809 polyol acrylate, polyester acrylate, urethane acrylate, and epoxy acrylate. For example, "U-dabul C3300" and "u-dabul C3600" (above, manufactured by Nippon Shokubai Co., Ltd.), etc., may be mentioned as a commercial product of a sclerosing resin containing a composite inorganic fine particle. <Optical Protective Film> One of the planar thermoplastic resin compositions (A) for optics of the present invention

較佳形態為光學用保護薄膜(以下稱為「本發明之光學用保護薄膜」）。本發明之光學用保護薄膜薄臈，並無特別限定者，較佳用偏光板之保護薄膜等。亦可護用薄膜。限定為透明光學元件之保護具體例可列舉液晶顯示裝置將相位差薄膜兼作為光學保膜本發明之光學用保護薄膜可為未延伸薄膜或延伸薄本發明之光學用保護薄膜為未延伸薄膜時，平面方向佳為未達20nm’更較佳為未達l〇nm。本發明之光學用保護薄膜為延伸薄膜時，平面方向之相位差較佳為2。至500nin f +面方向之灵孝乂佳為50至400nm。本發明之光學用保護薄膜為延伸薄膜時，擁有特定相位差（例如A/2以及λ 、子擁有特疋相能。於該情況Τ，作為具内『〜人/相位差薄膜之功 m -曰衣1合物製造時所使用之罝體，較佳係使用上述式(3) 碎所使用之早 (f基）丙稀酸s卜光學 f基）丙烯酸及/或中其他聚合物，較佳錢可._丨脂組合物⑴. 用3丙烯系聚合物者。A preferred embodiment is an optical protective film (hereinafter referred to as "the optical protective film of the present invention"). The optical protective film of the present invention is not particularly limited, and a protective film of a polarizing plate or the like is preferably used. It can also be used as a protective film. Specific examples of the protection of the transparent optical element include a liquid crystal display device and a retardation film as an optical film. The optical protective film of the present invention may be an unstretched film or an extended film. The optical protective film of the present invention is an unstretched film. The plane direction is preferably less than 20 nm', more preferably less than 10 nm. When the optical protective film of the present invention is a stretched film, the phase difference in the planar direction is preferably 2. To the 500nin f + face direction, the filial piety is 50 to 400 nm. When the protective film for optics of the present invention is a stretched film, it has a specific phase difference (for example, A/2 and λ, and the sub-phase has a characteristic phase energy. In this case, as a work of "man/phase difference film m" The carcass used in the manufacture of the coating composition is preferably an early (f-based) acrylic acid s-acrylic acid and/or other polymer used in the above formula (3).佳钱可. _ 丨组合 composition (1). Use 3 propylene polymer.

2226-7326B-PF 35 本么明之光學用保護薄膜，相位差於R Q Π .. ’反長之依存性小， 59_之相位差一各波長之相位佳為〇9皇之比（R/Re)，較 9至U，更較佳為〇·95至1.卜本發明之光學保護薄膜。。之相…與入射…相位;;=小，人射角佳為未達2〇nm，更較佳為未達i〇nm。 U。），較本發明之光學用保護薄佳為H以上，更較佳為2H以上/又阿’錯筆硬度較本發明之光學用保護薄膜之製造方法 ’例如，將具内I旨環聚合物，必要時之:·別限疋加劑等，使用以往習知之^ 他聚合物或添而製得。亦可為延伸售/° '加以混合’成形薄膜狀刀了為延伸溥臈或未延伸薄膜。薄膜成形的方法’可使用以往習例如可列舉溶液_法__ = 法，法（c“）、壓縮成形擠^壓延溶液鑄模法（溶液塑开… ㈣，專膜成形方法中，以塑形法）、熔融擠壓法特佳。溶液鑄模法（溶液塑形法）所使用之氯仿、二氯甲燒等氯系溶媒；甲苯、二例如可列舉溶媒；甲醇、乙醇、異㈣、 Y本、苯等芳香族甲基二氧乙醇、乙其_.▲丁醇等醇系溶媒；醯胺、二甲A 土一虱乙醇、丁基二氧乙醇、二甲美甲 m 亞楓、二氧環己烷、環己酮、四氫。“土酮、甲基乙基綱、醋酸乙酿、二乙驗.等/風夫喃、丙單獨使用或2種以上併用。.軸，4#。該等溶媒可進行溶液鑄模法（溶2226-7326B-PF 35 This is an optical protective film with a phase difference of RQ Π .. 'The dependence of the reverse length is small, the phase difference of 59_ is the phase of each wavelength is preferably 〇9 皇 ratio (R/Re ), from 9 to U, more preferably from 95 to 1. The optical protective film of the present invention. . The phase ... and the incident phase;; = small, the angle of the human is preferably less than 2 〇 nm, more preferably less than i 〇 nm. U. It is preferable that the optical protective film of the present invention is H or more, more preferably 2H or more, and the method of producing the optical protective film of the present invention is as follows. If necessary: • Do not limit the addition of additives, etc., using conventional polymers or additions. It is also possible to use a stretched/° 'mixed' formed film-like knife as an extended or unstretched film. The method of forming a film can be exemplified by a solution such as a solution_method_method, a method (c"), a compression forming extrusion calendering solution casting method (solution molding) (4), in a film forming method, to shape Method), melt extrusion method is particularly preferable. Chlorine-based solvent such as chloroform or methylene chloride used in the solution casting method (solution shaping method); toluene, for example, a solvent; methanol, ethanol, iso(tetra), Y-ben An alcoholic solvent such as aromatic methyl dioxyethanol such as benzene or an alcoholic acid such as B. _. butanol; guanamine, dimethyl A, ethanol, butyl dioxyethanol, dimethyl melon m yam, dioxane Hexane, cyclohexanone, and tetrahydrogen. "Zhone, methyl ethyl, acetic acid, diacetic acid, etc. / fengfuran, propyl alone or in combination of two or more. .Axis, 4#. These solvents can be solution molded (dissolved)

2226-7326B-PF 心去）所使用之裝置，例如可 36 1361809 列舉輥筒式鑄模機、帶式•模機、旋塗機等。熔融擠壓法可列舉押出模頭法（T die)、吹塑法 (Wlat10n)等，此時’吹塑法之成形溫度，較佳為⑸至 350 C ’更較佳為200至300°C。，例如進行延伸之方法，可適用以往習知之延伸方法可使用單軸延伸、依次雙軸延伸、同步雙軸延伸等2226-7326B-PF heart to the device used, for example, 36 1361809, such as roller type molding machine, belt type mold machine, spin coater, etc. The melt extrusion method may be a die die method (T die), a blow molding method (Wlat 10n) or the like. In this case, the forming temperature of the 'blow molding method is preferably from (5) to 350 C', more preferably from 200 to 300 ° C. . For example, the method of extending can be applied to the conventional extension method. Single-axis extension, sequential biaxial extension, synchronous biaxial extension, etc. can be used.

…延伸較佳為於接近薄膜原料之聚合物之玻璃轉移溫度進行。具體之延伸溫度，較佳為（玻璃轉移溫度_3〇艺）至（玻璃轉移溫度+1G(KC)，更較佳為（玻璃轉移溫度-2(rc )至（玻 =轉移溫度+80。〇。延伸溫度未達(玻璃轉移溫度_3〇。〇時’無法獲得充份之延伸倍率。相反地，延伸溫度超過（玻璃轉移溫度+100 t )時伸0 樹脂為流動而無法進行安定的延以面積比定義延伸倍率，較佳為M至25倍，更較佳為1.3至10倍。延伸率未達hl倍時，無法獲得由於延伸之韌性提升。相反地，延伸倍率超過25倍時，無法確認延伸倍率提升的效果。延伸速度（一方向），較佳為10至20,000%/min，更較佳為100至1 0,000%/min。延伸速度未達1〇%/min時獲得充份延伸倍率之時間相當耗費，而是製造成本增高。才I 反地，延伸速度超過20,000%/min時，發生延伸薄膜斷裂。為了安定化薄膜之光學等向性及機械特性，可於延伸處理後進行熱處理（退火（annealing))等。 <光學薄膜> 2226-7326B-PF 37 1361809 進行延伸之方法，可適用以往習知之延伸方法，例如可使用單軸延伸'依次雙軸延伸、同步雙軸延伸等。該等 ’ 延伸方法中’就相位差薄膜而言，較佳為單軸延伸。 - 延伸溫度 '延伸倍率、延伸速度，與前述光學用保護薄膜之延伸溫度、延伸倍率、延伸速度相同。為了安定化薄膜之光學等向性及機械特性，可於延伸處理後進行熱處理（退火（annealing)等。 φ 本發明之相位差薄膜，必要時，亦可於表面電暈 (C〇r〇na)處理。特別是薄膜表面施加塗覆加工等表面處理時’或以黏著劑積層（laminate)別的薄膜時，為提升相互之在著〖生’較佳進行薄膜表面之電暈處理。本發明之相位差薄膜，可積層於偏光板。本發明之相位差薄膜亦可使用作為偏光板之保護薄膜。本發明之視角補償薄膜，相位差波長之依存性小，於 5 9 0nm之相位差卩p盘欠，士曰、差肋”各波長之相位差R之比（R/Re) 為〇. 9至1· 2，更較佳為〇 95至丨卜本發明之視角補償薄膜，表面硬度高，錯筆硬度較佳為Η以上，更較佳為2H以上。本發明之視角補償薄膜者，例如，無特別限定玲衣象5物，必要時之其他聚加劑等，使用以往習知 θ μ 之扣&方法加以混合，成形薄膜妝而製得。亦可為延伸薄膜或未延伸薄膜。膜狀 =膜成形溫度.、薄膜成形方法、與前膜中薄膜成形溫度、薄膜成形方法相同。保4屢The extension is preferably carried out at a glass transition temperature of the polymer close to the film material. The specific extension temperature is preferably (glass transition temperature _3 〇 art) to (glass transition temperature +1 G (KC), more preferably (glass transition temperature -2 (rc) to (glass = transfer temperature + 80).延伸. The extension temperature is not reached (glass transition temperature _3 〇. 〇 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The stretching ratio is defined by the area ratio, preferably M to 25 times, more preferably 1.3 to 10 times. When the elongation is less than hl times, the toughness due to elongation cannot be obtained. Conversely, when the stretching ratio exceeds 25 times The effect of the extension ratio increase cannot be confirmed. The extension speed (one direction) is preferably 10 to 20,000%/min, more preferably 100 to 10,000%/min, and the charge is obtained when the extension speed is less than 1%/min. The time for stretching is quite expensive, but the manufacturing cost is increased. Only when the elongation speed exceeds 20,000%/min, the elongation film breaks. In order to stabilize the optical isotropic and mechanical properties of the film, it can be extended. After heat treatment (anneal (anneal) Ing)), etc. <Optical Film> 2226-7326B-PF 37 1361809 The method of stretching can be applied to a conventional extension method, for example, uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, etc. can be used. In the 'extension method', it is preferable that the retardation film is uniaxially stretched. - The elongation temperature, the stretching ratio, and the stretching speed are the same as the stretching temperature, the stretching ratio, and the stretching speed of the optical protective film. The optical isotropic and mechanical properties of the film may be subjected to heat treatment (annealing) or the like after the stretching treatment. φ The retardation film of the present invention may be treated by surface corona (C〇r〇na) if necessary. In particular, when a surface treatment such as coating processing is applied to the surface of the film, or when another film is laminated with an adhesive, the corona treatment of the film surface is preferably performed in order to enhance the mutual phase of the film. The film can be laminated on the polarizing plate. The retardation film of the present invention can also be used as a protective film for the polarizing plate. The viewing angle compensation film of the present invention has a small dependence on the phase difference wavelength. The ratio of the phase difference R (R/Re) of each wavelength of the girth and the difference rib is 〇. 9 to 1.2, more preferably 〇95 to 丨b. The viewing angle compensation film of the invention has a high surface hardness, and the erroneous pen hardness is preferably Η or more, more preferably 2H or more. The viewing angle compensation film of the present invention, for example, is not particularly limited to five objects, and if necessary, other poly Additives and the like are prepared by mixing the conventional θ μ buckle & method, and forming a film makeup. It may be an extended film or an unstretched film. Film shape = film forming temperature, film forming method, and front film The film forming temperature and the film forming method are the same. Insurance 4

2226-7326B-PF 39 1361809 。·仃、伸之方法’可適用以往習知之延伸方法，例如可使用單轴延伸' 依次雙袖延伸、同步雙軸延伸等。該等延伸方法中，就視角補償薄膜而言’較佳為單抽延伸。延伸溫度、延伸倍率、延伸速度，與前述光學用保護 4膜之延伸溫度、延伸倍率、延伸速度相同。為了安定化薄膜之光學等向性及機械特性可於延伸匆理後進行熱處理（退火（anneaUng)等。 <光學薄片> 2明之光學用平面狀熱可塑性樹脂組合物⑴之再片」）、他形態為光學薄片（以下稱為「本發明之光學薄本發明之光學薄片限定為耐埶膜，並無㈣及先學特性優異之薄擴η、 &佳為擴政板(以下稱為「本發明之，）、導光板(以下稱為「本發明之導光板」）。發明之光學薄片為擴散板時，並含有本發明之呈內西t jm ”構成除了柯脂成分乃之具内西曰j衣聚合物以外，可盥板構成相同之構成。 ’、 0之擴散本::之光學薄片為導光板時，其構成除了 =明之具_聚合物以外，可與以往：構成相同之構成。等先板本發明之光學薄片，平面方，更較為未達1〇M。相位差車父佳為未達以上月之光子4片，表面硬度高’錯筆硬度較佳為H 乂上更較佳為2H以上。圭為Η .2226-7326B-PF 39 1361809. The method of 仃, stretching can be applied to conventional extension methods, such as uniaxial extension, sequential double sleeve extension, simultaneous biaxial extension, and the like. In the stretching method, it is preferable that the viewing angle compensation film is a single drawing extension. The stretching temperature, the stretching ratio, and the stretching speed are the same as the stretching temperature, the stretching ratio, and the stretching speed of the optical protective film. In order to stabilize the optical isotropic properties and mechanical properties of the film, heat treatment (annealing, annealing, etc.) can be performed after the extension of the film. <Optical sheet> 2 Re-slice of the planar thermoplastic resin composition (1) for optical use) In the form of an optical sheet (hereinafter referred to as "the optical sheet of the present invention, the optical sheet of the present invention is limited to a ruthenium-resistant film, and there is no (4) and a thin expansion of the first-class characteristics, and a good expansion board (hereinafter referred to as In the "invention", a light guide plate (hereinafter referred to as "the light guide plate of the present invention"). When the optical sheet of the invention is a diffusion sheet, the present invention contains the inner west t jm constituting a composition other than the curd component. In addition to the Neissin j-coated polymer, the ruthenium plate can be configured in the same manner. When the optical sheet of the 0 is a light guide plate, the composition can be different from the conventional one: The same composition. The first sheet of the optical sheet of the invention, the plane side, is less than 1 〇 M. The phase difference is that the photo is not up to 4 photons of the previous month, and the surface hardness is high, and the hardness of the wrong pen is preferably H. More preferably 2H or more Guyana is Η.

2226-7326B-PF 40 1361809 本發明之光學薄片’耐熱性特高’衛氏軟化點(Vlcat softening temperature)較佳為 ii〇°c 以 h a ^ ec以上。上，更較佳為12〇本發明之光學薄片之製造方法’並無特別限定者，例如，將具内醋環聚合物，必要時之其他聚合物或添加劑等，使用以往習知之混合方法加以混合，成形薄片狀而裳得。溥片成形方法’可適用以往習知之薄片成形方法且體而言，例如可列舉擠塵成形、射出成形、吹塑成形、：煉成形等。 :片成形之成形溫度較佳為15〇至35〇t，更佳為2〇。主 J U (J c ° :發明之擴散板較佳含有有機充填劑及/或無機充填2226-7326B-PF 40 1361809 The optical sheet of the present invention has a high heat resistance, and the Vlcat softening temperature is preferably ii 〇 °c or more. More preferably, the method for producing the optical sheet of the present invention is not particularly limited. For example, an internal vinegar ring polymer, if necessary, other polymers or additives, etc., may be used by a conventional mixing method. Mix, form a sheet and get it. The sheet forming method can be applied to a conventional sheet forming method, and examples thereof include dust forming, injection molding, blow molding, and refining molding. The forming temperature of the sheet forming is preferably from 15 Å to 35 Torr, more preferably 2 Å. Main J U (J c °: the diffusion plate of the invention preferably contains organic filler and/or inorganic filling

劑作為添加劑D 有機充填劑及/或無機充填劑之使用量，相對於具内醋 :二物’有機充填劑及/或無機充填劑之合劑量較佳為 1二質量%，更佳為°.°5至4"量%，再佳為。」劑，^ i 填劑及/或無機充填透羊擴政率、強度、剛性、熱變形溫度專特性之平衡優異之擴散板。有機充填劑，例如可列舉聚合物及聚合物交聯物粒子。㈣Γ用聚合物交聯物粒子作為有機充填劑時，聚合物交聯物粒子之粒徑較佳為，更佳為05至5〇 // m 〇聚胺基甲酸酯有機充填劑，例如可列舉丙稀系樹脂、The amount of the agent as the additive D organic filler and/or the inorganic filler is preferably 12% by mass, more preferably the combined dose of the organic emulsifier and the organic filler and the inorganic filler. .5 to 4"%, better. Agent, ^ i Filling and / or inorganic filling Through the sheep expansion rate, strength, rigidity, heat distortion temperature, the balance of the special characteristics of the diffusion plate. Examples of the organic filler include a polymer and a polymer crosslinked particle. (4) When the polymer crosslinked particles are used as the organic filler, the particle diameter of the polymer crosslinked particles is preferably, more preferably, it is 05 to 5 Å / / m 〇 polyurethane organic filler, for example, List propylene resin,

2226-7326B-PF 41 1361809 聚虱乙烯、聚苯乙烯、聚丙烯腈、聚醯胺、聚矽氧烷類、氟樹脂等。該等有機充填劑可單獨使用或2種以上併用。無機充填劑例如可列舉二氧化矽'二氧化矽氧化鋁、矽藻土 '氧化鋁 '碳酸鈣、氧化鈦、氧化鎂、輕石粉、輕石球、氫氧化鋁、氫氧化鎂、鹼性碳酸鎂 '白雲石 (dolomite)、硫酸鈣、鈦酸鉀、碳酸鋇、硫酸鋇、亞硫酸鈣、滑石、石灰、雲母、石棉、玻璃片、玻璃珠、石夕酸妈、蒙脫石（montmorillonite)、膨潤土（bent〇nHe)、石墨、氧化紹粉、硫化鋇等。該等無機充填劑可單獨使用或2種以上併用。該等無機充填劑中，特以碳酸鈣、氧化鈦、氧化紹、三氧化石夕、二氧化石夕氧化紹、滑石 '礙酸鎖為佳。無機充填劑之質量平均粒徑為〇· 5至5〇 # m，更佳為^ 至30 # m。無機充填劑之質量平均粒徑於上述範圍内時，質量平均粒徑為大時，所製得之光擴散板之全光線穿透率低，擴散穿透率變高’可適合使用作為顯示器、明暗作業 (glaZlng)、遮蔽板、照明器具等之擴散板。相反地，無機充填劑之質量平均粒徑，質量平均粒徑為小時，所製得之光擴散板之全光線穿透率高，擴散穿透率變滴，可適合使用於大型顯示器之螢幕等用途。使用本發明之擴散板，根據以往習知之方法，可為液曰曰”.、員示裝置之擴散溥片及其等所使用之背光單元 (backlight unit)。本發明之導光板，較佳於側面以外之一平面具有光反射防止層。本發明之道止4 ,,.... ^么λ <導先板，如上述者，於側面以外之一2226-7326B-PF 41 1361809 Polyethylene, polystyrene, polyacrylonitrile, polyamine, polyoxyalkylene, fluororesin, etc. These organic fillers may be used alone or in combination of two or more. Examples of the inorganic filler include cerium dioxide 'cerium oxide alumina, diatomaceous earth 'alumina' calcium carbonate, titanium oxide, magnesium oxide, pumice powder, pumice ball, aluminum hydroxide, magnesium hydroxide, and basic carbonic acid. Magnesium 'dolomite, calcium sulfate, potassium titanate, barium carbonate, barium sulfate, calcium sulfite, talc, lime, mica, asbestos, glass flakes, glass beads, ashes, montmorillonite Bentonite (bent〇nHe), graphite, oxidized powder, strontium sulfide, etc. These inorganic fillers may be used singly or in combination of two or more. Among these inorganic fillers, calcium carbonate, titanium oxide, oxidized sulphate, sulphur trioxide, sulphur dioxide, and talc are particularly preferred. The mass average particle diameter of the inorganic filler is 〇·5 to 5〇 # m, more preferably ^ to 30 # m. When the mass average particle diameter of the inorganic filler is within the above range, when the mass average particle diameter is large, the obtained light diffusing plate has a low total light transmittance and a high diffusion transmittance, and can be suitably used as a display. Diffusion plate for shading operations (glaZlng), shielding panels, lighting fixtures, etc. On the contrary, the mass average particle diameter of the inorganic filler and the mass average particle diameter are small, and the obtained light diffusing plate has a high total light transmittance, and the diffusion transmittance is dripped, and can be suitably used for a screen of a large display or the like. use. According to the conventionally known method, the diffusion plate of the present invention may be a liquid raft, a diffusion slab of the device, and the like, and a backlight unit used in the present invention. One of the planes other than the side surface has a light reflection preventing layer. The method of the present invention is 4, ..., ^ λ < guide plate, as described above, one of the sides

2226-7326B-PF 42 1361809 平面具有光反射功能之微細凹凸形狀時ϋ射防止層較佳於具有光反射功能之微細凹凸形狀之面之相反面。光反射防止層，與一般光學元件之光反射防止層相同，以於入光面具有防止可見光等光反射之功能之層為限，並無特別限定者，例如，可列舉無機薄膜、透明樹脂膜等。曰使用本發明之導光板，根據以往習知之方法可為液晶顯示裝置之導光板及其等所使用之前光單元 (frontlight unit)。《光學用平面狀熱可塑性樹脂組合物（B)》本發明之光學用平面狀熱可塑性樹脂組合物⑻為含有具内醋環聚合物其其他熱可塑性樹脂之光學用平面狀：可塑性樹脂組合物，其特徵為玻璃轉移溫度為12〇它以上1 相當於平面方向厚度l〇Mm之相位差為2〇咖以下線穿透率為85%以上。王尤光學用平面狀熱可塑性樹脂組合物⑻中所使用之並他熱可塑性樹脂’於具内酷環聚合物為推合薄 ” 要發揮玻璃轉移溫度為120t以上，面^ ’只、十面方向厚产 100以m之相位差為20nm以下，全光線穿锈f 又瓦芽透率為85%以上之性能者皆可’並不限定特別種類，由穴択具有透明性及耐熱性、低相位差、優異機械強度之性能之光學薄膜點而言，以熱力學相溶之熱可塑性樹脂較佳。 ..光學用平面狀熱可塑性樹脂組合物（Β)中具内酉旨物以及其他熱可塑性樹脂含有比例’較 ° 乂佳為60至99 : 1至 2226-7326B-PF 43 1361809 4〇質量％，更佳為70至97: 3至3〇質量％，再佳為⑽至郎.5至20質量％。光學用平面狀熱可塑性樹脂組合物⑻ 中具内醋環聚合物之含有比例未達6〇質量％時，無法充分發揮本發明之效果。其他熱可塑性樹脂，例如，可列舉聚乙烯、聚丙烯、乙烯-丙稀共聚物、聚（4-甲基—卜戍稀）等稀煙聚合物；氣化乙烯、氣化亞乙烯、氣化乙烯樹脂等齒化乙烯系聚合物；聚甲基丙烯酸甲醋等丙烯酸系聚合物；聚苯乙烯、苯乙烯— 甲基丙稀酸甲醋共聚物、苯乙稀—甲基丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯嵌段共聚物等苯乙烯系聚合物；聚對苯二甲酸乙二醇醋、聚對苯二甲酸丁二醇_、聚萘二甲酸乙二醇醋等聚醋；尼龍6 '尼龍66、尼龍61〇等聚醯胺；聚縮醛；聚碳酸酿；聚笨醚、聚笨硫醚；聚喊醚酮；聚碉；聚雜；聚氧苯甲西旨；聚醯胺亞醢胺；配合聚丁二稀系橡膠、丙稀酸系之ABS樹脂或ASA樹脂等橡膠質量聚等等。橡膠聚合物，其表面以具有與具内醋環聚合二之組成之接枝（gra⑴部份為佳，而由薄膜狀時透明性提升. 之觀點而言’橡膠聚合物之平均粒子徑較佳為刚⑽以下’更佳為70nm以下。2226-7326B-PF 42 1361809 When the plane has a fine uneven shape of a light reflecting function, the radiation preventing layer is preferably opposite to the surface of the fine uneven shape having a light reflecting function. The light-reflecting layer is not limited to a layer having a function of preventing light reflection such as visible light on the light-incident surface, and is not particularly limited, and examples thereof include an inorganic film and a transparent resin film. Wait.曰 With the light guide plate of the present invention, the front light unit of the liquid crystal display device and the like can be used according to a conventional method. <<Planar thermoplastic resin composition for optical use (B)>> The planar thermoplastic resin composition for optical use (8) of the present invention is an optical flat sheet containing another thermoplastic resin having an internal vinegar ring polymer: a plastic resin composition It is characterized in that the glass transition temperature is 12 〇. It is 1 or more. The phase difference corresponding to the thickness of the plane direction l 〇 Mm is 2 〇 or less and the line penetration rate is 85% or more. Wang Youguang uses the thermoplastic resin resin (8) used in the planar thermoplastic resin composition (8) to make it thin and thin in the inner ring-shaped polymer. To achieve a glass transition temperature of 120t or more, the surface ^ 'only, ten sides In the direction of the production of 100 m in phase difference of 20 nm or less, the total light wear rust f and the wattage penetration rate of 85% or more of the performance can be 'not limited to special types, from the hole has transparency and heat resistance, low The thermosensitive resin which is thermodynamically compatible with the optical film of the phase difference and the excellent mechanical strength is preferable. The optical thermoplastic resin composition (光学) for optical has an internal entanglement and other thermoplasticity. The resin content ratio is preferably from 60 to 99: 1 to 2226-7326B-PF 43 1361809 4〇% by mass, more preferably 70 to 97: 3 to 3〇% by mass, and further preferably (10) to lang. 5 to 20 When the content ratio of the internal vinegar ring polymer is less than 6% by mass in the planar thermoplastic resin composition (8) for optical use, the effect of the present invention cannot be sufficiently exhibited. Other thermoplastic resins include, for example, polyethylene. , polypropylene, B - styrene copolymer, poly(4-methyl-dioxadiene) and other dilute-smoke polymers; gasified ethylene, vaporized vinylene, gasified vinyl resin and other toothed vinyl polymers; polymethyl methacrylate Acrylic polymers; polystyrene, styrene-methyl methacrylate copolymer, styrene-methacrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer, etc. Polymer; polyethylene terephthalate vinegar, polybutylene terephthalate _, polyethylene naphthalate vinegar and other polyester vinegar; nylon 6 'nylon 66, nylon 61 〇 and other polyamines; Polyacetal; polyacetal; polyether ether, polystyrene sulfide; polyetheretherketone; polyfluorene; polyheteropoly; polyoxybenzoic acid; polyamidamine; combined with polybutylene rubber, C Dilute acid-based ABS resin or ASA resin, such as rubber mass, etc. Rubber polymer, the surface of which has a graft with the composition of the internal vinegar ring polymerization (gra (1) part is better, and the film is transparent) From the viewpoint of improvement, the average particle diameter of the rubber polymer is preferably just below (10), and more preferably 70 nm or less.

與具内酉旨環聚合物與熱力學相容之熱可塑性樹脂，為具有氰化乙烯系單體單元以及芳香族乙婦系單體單元之共聚物，具體而言，可列舉丙烯腈-笨乙烯共聚物、或聚氣：烯樹脂、甲基丙稀酸醋類含有5。質量%以上之聚合物。节等熱可塑性樹脂中’使用丙婦腈—笨乙缔共聚物，容易製得… 2226-7326B-PF 44 1361809 玻璃轉移溫度為12〇t以上，相當於平面方向厚度l〇〇^m 之相位差為2〇nm以下，全光線穿透率為85%以上之光學薄膜。再者，與具内醋環聚合物為熱力學相溶之熱可塑性樹脂，可測定其昆合所得之熱可塑性樹脂組合物之玻璃轉移溫f而加以確認。具體而言，根據示差掃描熱量測定儀所 :丨定之玻璃轉移溫度’為具内酯環聚合物與其他熱可塑性樹脂之混合物所僅觀測之一點而稱為熱力學相溶性。其他熱可塑性樹脂使用丙埽腈—苯乙稀共聚物時，其製造：法可使用乳化聚合法或懸濁聚合法、溶液聚合法、整體聚合法(bulkP〇lymerizati〇n)等，由所製得之光學用平 =熱可塑性樹脂組合物⑻之透明性及光學特性之觀點而$，較佳係使溶液聚合法或整體聚合法。本發明之光學用平面狀熱可塑性樹脂組 t!種種添加劑。添加劑，例如可列舉受阻紛系、鱗系、 :、專乳化防止劑；耐光安定劑、耐後安定劑專安定劑;玻璃纖維、碳纖維等補強材苯:二 2 _經基-5-甲基苯基）苯并三〇坐、2 本西曰（2’ , L基一本甲酉同算势夕卜線吸收劑；近紅外線吸收劑 T W、外 m匕广t ，臭丙基）磷酸酯、磷酸二婦丙自曰、乳化錄等難燃劑；* 之界面活性劑等帶電防μ μ 險離子 '非離子系 Μ寺帶電防止劑；無機顏料等著色劑；有機填料或盎機填 "4木料劑或無機填充劑；可塑劑，有機真充等箄。劑’ ▼電防止劑；難燃劑；光學用平面狀埶可朔，地也nt 劑之含塑性树脂組合物⑻中添加The thermoplastic resin which is compatible with the thermodynamics of the inner ring polymer is a copolymer having a vinyl cyanide monomer unit and an aromatic vinyl monomer unit, and specifically, an acrylonitrile-stupid ethylene Copolymer, or polygas: olefin resin, methyl acrylate vinegar contains 5. More than 100% by mass of polymer. In the thermoplastic resin such as the section, the use of acrylonitrile-stuppycopolymer is easy to obtain... 2226-7326B-PF 44 1361809 The glass transition temperature is 12 〇t or more, which corresponds to the phase thickness l〇〇^m An optical film having a difference of 2 〇 nm or less and a total light transmittance of 85% or more. Further, the thermoplastic resin which is thermodynamically compatible with the internal vinegar ring polymer can be confirmed by measuring the glass transition temperature f of the thermoplastic resin composition obtained by the kneading. Specifically, according to the differential scanning calorimeter, the glass transition temperature of 丨 is called thermodynamic compatibility by observing only one point of a mixture of a lactone ring polymer and another thermoplastic resin. When a acrylonitrile-styrene copolymer is used as the other thermoplastic resin, the method can be produced by using an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, or a bulk polymerization method (bulkP〇lymerizati〇n). From the viewpoint of transparency and optical characteristics of the flat thermoplastic resin composition (8), it is preferred to use a solution polymerization method or a monolith polymerization method. The planar thermoplastic resin group for optics of the present invention is a variety of additives. The additives may, for example, be hindered, scaly, or: special emulsification inhibitor; light stabilizer, post-stabilizer specific stabilizer; glass fiber, carbon fiber and other reinforcing materials benzene: 2 2 _ thiol-5-methyl Phenyl)benzotriazine, 2 Benxi (2', L-based, one-on-one, the same as the absorption agent; near-infrared absorber TW, external m匕guang t, odor propyl) phosphate , Phosphoric acid dipropyl citrate, emulsified recording and other flame retardants; * Surfactant and other anti-μ μ dangerous ions 'non-ionic Μ 带带带 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 无机无机无机无机无机无机无机无机无机无机无机无机无机无机; 4 wood agent or inorganic filler; plasticizer, organic charge and so on. Agent' ▼Electrical preventive agent; flame retardant; optical flat sheet 埶朔, ground also nt agent containing plastic resin composition (8) added

2226-7326B-PF 45 1361809 有比例，較佳為〇至5質量％、更佳為〇至旦為0至0. 5質量％。 ^ 光學用平面狀熱可塑性樹脂組合物（B)之製造方法，、無特別限定者，例如，可將具内酯環聚合物以仙並久共他熱可塑性樹脂，以及必要時脂添加劑等，#用 "·' 蜊哥便用以住習知之混人方法充分混合，將其成形為平面狀。+面狀之形：狀或薄片狀為佳。 ^ <光學薄膜> 本發明之光學用平面狀熱可塑性樹脂組合物⑻之一較佳形態為光學薄膜（以下稱為「本發明之光學薄膜」）。本發明之光學薄膜，為可於各4 1 、合種九學用途中完全發捏必要特性之光學薄膜。本發明之光學薄膜’玻璃轉移溫度為12〇。〇以上較佳為125°C以上，更佳為13〇。〇以上。本發明之光學薄膜，相當於平面方向厚度⑽“之相位差較佳為20m以下，更佳為1〇nm以下。、本發明之光學薄膜，全光線穿透率為85%以上，較佳為87%以上，更佳為go%以上。本發明之光學薄膜，相位差 <八射角依存性小，入射角之相當於平面方向®声1nn" 。门与度100以m之相位差與入射角 4。。之相當於平面方向厚度1〇〇“之相位差r“之差 (R〇-R。）’較佳為2〇叩以下，更較佳為10nm以下。本發明之光學薄膜，厚度較佳盔子罕乂佳為1 // m以上、未達5 0 0 更佳為l〇#m以上、未这Μη" r* 禾連川0#m。厚度未達時，5质量%。 2226-7326B-PF 45 1361809 has a ratio, preferably 〇 to 5% by mass, more preferably 〇旦 to 0. 0% by mass. ^ A method for producing a planar thermoplastic resin composition (B) for optical use, and, for example, a lactone ring polymer may be used as a synthetic resin, and if necessary, a fat additive, etc. #用"·' 蜊哥 is used to live in a well-mixed method of mixing, forming it into a flat shape. + Shape of the face: Shape or flaky shape is preferred. <Optical Film> One of the planar thermoplastic resin compositions (8) for optical use of the present invention is preferably an optical film (hereinafter referred to as "the optical film of the present invention"). The optical film of the present invention is an optical film which can fully pinch the necessary characteristics in each of the four-in-one applications. The optical film of the present invention has a glass transition temperature of 12 Å. Preferably, the enthalpy is 125 ° C or more, and more preferably 13 。. 〇 Above. In the optical film of the present invention, the phase difference (10) in the plane direction is preferably 20 m or less, more preferably 1 nm or less. The optical film of the present invention has a total light transmittance of 85% or more, preferably 87% or more, more preferably more than go%. The optical film of the present invention has a phase difference <eight angle dependence dependence, and the incident angle corresponds to the plane direction ® sound 1 nn". The gate and the degree of phase difference of 100 m and The difference (R〇-R.) of the incident angle 4 corresponding to the thickness of the plane in the plane direction is preferably 2 Å or less, more preferably 10 nm or less. The optical film of the present invention. The thickness of the helmet is better than 1 / m or more, less than 5 0 0 is better than l 〇 #m above, not this Μ quot quot r r r r r r r r r r r r r r r r r r r r r r r r r r r r r

2226-7326B-PF 46 丄允1809 、、表現充刀之機械強度，進行延伸時容易發生斷裂。本發明之光學薄膜以ASTM-D-882-61T為基準測定抗張強度時，較佳為1⑽Pa以上、未達lOOMPa，更佳為30MPa • 、未達10〇MPa。抗張強度未達l〇MPa時，無法表現充分之機械強度。相反地，抗張強度超過丨〇〇MPa時，加工性變差。本發明之光學薄膜以ASTM-D-882-61T為基準測定延 φ 伸率時，杈佳為1 %以上，更佳為3%以上。延伸率之上限並 …、特別限疋者，通常，較佳為10 0 %以下。延伸率未達1 % 時’欠缺韌性。本發明之光學薄膜以ASTM-D-882-6 1T為基準測定抗張彈性率時，較佳〇_5GPa以上，更佳為1GPa以上，再佳為2Gpa以上。彳几張彈性率之上限，並無特別限定者，通常，較佳為20Gpa以下。抗張彈性率未達〇 5Gpa時’無法表現充分之機械強度。鲁纟發明之光學薄膜之製造方法，並無特別限定者，例如，可將具内酯環聚合物以及其他熱可塑性樹脂，以及必要時之添加劑等，使用以往習知之混合方法充分混合，作為預備之熱可塑性樹脂組合物，製造光學薄膜。該熱可塑性樹脂組合物之製造方法，例如可採用〇mni mixer等混合機預混合（pre-blend)後，將所得混合物擠壓混煉之方法。此時，擠壓混煉用混煉機，並無特別限定者，例如，可使用單軸擠壓機、雙軸擠壓機等擠..壓機，或加壓捏合機 (kneader)等以往習知之混煉機β 2226-7326B-PF 47 1361809 任一 ΓΓ之方法，可使用以往習知之薄膜成形方法之厂堅法、壓=可列舉溶液鑄模法（溶液塑形法）、炫融擠別H檯“成形法等。該等薄膜成形方法中，特冷液铸模法（溶液塑形法）、 ’ 亦可佶田J·火叫！次兩1土。此時，〜述之預先擠塵混煉亦可將具内酷Ρt W畑，.且D物，時之添力：“及其他熱可塑性樹脂，以及必要加m "刀別溶解於溶液而成為均一混合液後，施驟”&法(溶液塑形法)或熔融擠壓法之薄膜成形步溶液鑄模法（溶液塑形法）所使用之溶媒，例如可列舉溶媒;甲醇、乙醇異:：、二甲苯、苯等芳香族曱基二氧乙醇乙其，、正丁醇、2,等醇系溶媒；醯胺、二甲A亞獮一了基-乳乙知、二甲基甲甲基亞楓、二乳環己燒、環己酉同、四氫。夫喃、丙，、甲基乙基酮、醋酸乙醋、二乙峻；等等。該等溶媒可早獨使用或2種以上併用。、了進行溶液鑄模法(溶液塑形法)所使用之裝置，例如可列舉輥筒式鑄模機、帶式鑄模機、旋塗機等。 .熔融擠壓法可列舉押出模頭法σ die)、吹塑法 (lnnation)等’此時’吹塑法之成形溫度，較佳為15〇至 350C ’更較佳為200至3〇〇°c。使用押出模頭法（Tdle)成形薄臈時，可將習知之單軸擠壓機或雙軸擠遂機之前端部附加押出模頭（Μ小將經薄膜狀擠壓之薄膜製得捲曲輥狀薄膜。此時，適宜調整捲2226-7326B-PF 46 丄1809, the mechanical strength of the filling knife is displayed, and it is easy to break when extending. When the tensile strength of the optical film of the present invention is measured in accordance with ASTM-D-882-61T, it is preferably 1 (10) Pa or more, less than 100 MPa, more preferably 30 MPa • and less than 10 MPa. When the tensile strength is less than 10 MPa, sufficient mechanical strength cannot be expressed. On the contrary, when the tensile strength exceeds 丨〇〇 MPa, the workability deteriorates. When the optical film of the present invention has an elongation at break based on ASTM-D-882-61T, it is preferably 1% or more, more preferably 3% or more. The upper limit of the elongation and, in particular, the limit, usually, preferably 10% or less. When the elongation is less than 1%, the lack of toughness. When the optical film of the present invention is measured for tensile modulus based on ASTM-D-882-6 1T, it is preferably 〇 5 GPa or more, more preferably 1 GPa or more, and still more preferably 2 GPa or more. The upper limit of the modulus of elasticity is not particularly limited, and is usually preferably 20 GPa or less. When the tensile modulus is less than 5 GPa, it is not able to exhibit sufficient mechanical strength. The method for producing the optical film of the invention of Rugao is not particularly limited. For example, a lactone ring polymer, another thermoplastic resin, and, if necessary, an additive may be sufficiently mixed by a conventional mixing method as a preparation. The thermoplastic resin composition is used to produce an optical film. The method for producing the thermoplastic resin composition can be, for example, a method in which a mixture obtained by pre-blending with a mixer such as a 〇mni mixer is extruded and kneaded. In this case, the kneading and kneading mixer is not particularly limited. For example, a single-axis extruder, a twin-screw extruder, or the like may be used, such as a press or a kneader. Conventional kneading machine β 2226-7326B-PF 47 1361809 Any method of using the conventional film forming method can be used, such as a solution molding method, a solution molding method (solution molding method), and a squeezing and squeezing method. H stage "forming method, etc.. In these film forming methods, the special cold liquid casting method (solution shaping method), 'can also be called Putian J. Fire called! The next two soils. At this time, ~ pre-squeeze the dust Mixing can also be used to cool the inside, and D, when adding: "and other thermoplastic resins, and the need to add m " knife does not dissolve in the solution to become a homogeneous mixture, the process" The solvent used in the film forming step solution molding method (solution shaping method) of the & method (solution shaping method) or melt extrusion method may, for example, be a solvent; methanol, ethanol::, xylene, benzene, etc. Anthracene-based dioxyethanol, its n-butanol, 2, and other alcohol-based solvents; indoleamine, dimethyl A-anthracene-based Milk, dimethyl dimethyl sulfoxide, dimethyl ketone, hexamethylene hydride, tetrahydro ketone, propyl ketone, methyl ethyl ketone, ethyl acetate vinegar, diethylene sulphate; These solvents may be used alone or in combination of two or more. The apparatus used for the solution casting method (solution shaping method) may, for example, be a roll type molding machine, a belt type molding machine, a spin coater or the like. The melt extrusion method may be a forming temperature of the 'blow molding method σ die), a blow molding method, or the like, and is preferably 15 to 350 C', more preferably 200 to 3 °. c. When the thin raft is formed by the Tdle method, the front end of the conventional uniaxial extruder or the twin-shaft squeezing machine may be additionally extruded from the die (the small film will be crimped by the film-like extruded film) Roll-shaped film. At this time, it is suitable to adjust the volume.

2226-7326B-PF 48 1361809 曲輥之溫度，施加於擠壓方向延伸’亦可以單軸延進行。施加於與擠壓方向垂直之方向延伸薄膜步驟，二使用依次雙軸延伸、同步雙軸延伸等步驟。2226-7326B-PF 48 1361809 The temperature of the curved roll, applied to the extrusion direction, can also be uniaxially stretched. The step of extending the film in a direction perpendicular to the extrusion direction is performed, and the steps of sequentially biaxial stretching, simultaneous biaxial stretching, and the like are used.

本發明之光學薄膜’可為未延伸薄膜，亦可為膜。延伸_，可為單軸延伸薄膜，亦可為雙軸延伸薄膜：雙轴延伸薄膜時’可為同步雙軸延料，亦可為依次料延伸者。經雙軸延伸時，機械強度提升之薄膜之性能提1。本發明之光學薄膜，與其他熱可塑性樹脂混合，而可^制延伸時相位差之增大，可保持光學等向性。，延伸較佳為於接近薄膜原料之熱可塑性樹脂組合物之玻璃轉移溫度進行。具體之延伸溫度’較佳為（玻璃轉移溫度—3(TC)至（玻璃轉移溫度+丨⑽它），更較佳為（玻璃轉移溫度-20°C)至（玻璃轉移溫度+㈣艺）。延伸溫度未達（破璃轉移溫度-3(TC )時，無法獲得充份之延伸倍率。相反地延伸溫度超過（玻螭轉移溫度+1〇0。(：）時，樹脂為流動而無法進行安定的延伸。以面積比定義延伸倍率，較佳為1. 1至2 5倍，更較佳為1. 3至1 〇倍。延伸率未達丨丨倍時，無法獲得由於延伸之動性提升。相反地，延伸倍率超過25倍時，無法確認延伸倍率提升的效果。延伸速度（一方向），較佳為〇至20,000%/min，更較佳為100至l〇,〇〇〇%/min。延伸速度未達時，獲得充份延伸倍率之時間相當耗費，.而是製造成本增高。相反地’延伸速度超過20,000%/min時，發生延伸薄膜斷裂。 2226-7326B-PF 49 丄361809 為了安定化薄膜之光學等向性及機械特性，可於延伸處理後進行熱處理（退火（annealing))等。實施例以下，將列舉實施例更具體說明本發明，惟本發明不受下述實施例所限制，亦可於前、後述之要旨適合所得之範圍内另加適當變化而實施，該等之任—者皆包含於本發明知技術範圍。又，下文中，便利起見，「質：「份」^記述，「公升」單以「升」記述。製造例1至4、實施例1至19及比較例i至2係對應本發明之光學用平面狀熱可塑性樹脂組合物（A)，製造例5 及6貫施例2 0至2 2及比較例3係對應本發明之光學用平面狀熱可塑性樹脂組合物（B)。〈聚合反應率、聚合物組成分析〉聚合反應時之反應率及聚合物中特定單體單元之含有率係使用氣相層析（gas chromatography) (GC 17，島津製作所製造）’測定所得之聚合反應混合物中未反應單體量而求出。動二熱重里法>(動態 tg ; dynamic thermogravimetry) 將聚合物（或聚合物之溶液或粒狀物）全部溶解或稀釋於四氣°夫°南後’投入於過剩之己烷或曱醇中進行再沉澱，所取出之沉殿物進行真空乾燥33hpa)，8〇它，3 小時以上）而去除揮發成分，所得之白色固形狀樹脂以下述方法（動態TG)分析。The optical film 'of the present invention' may be an unstretched film or a film. The extension _ can be a uniaxially stretched film or a biaxially stretched film: when the biaxially stretched film is used, it can be a synchronous biaxially stretched material, or can be a material extension. When biaxially stretched, the performance of the film with improved mechanical strength is increased by one. The optical film of the present invention is mixed with other thermoplastic resins to maintain an increase in phase difference during stretching and to maintain optical isotropic properties. The stretching is preferably carried out at a glass transition temperature of the thermoplastic resin composition close to the film raw material. The specific extension temperature 'is preferably (glass transition temperature - 3 (TC) to (glass transition temperature + 丨 (10) it), more preferably (glass transition temperature -20 ° C) to (glass transition temperature + (four) art) When the elongation temperature is not reached (the glass transition temperature -3 (TC), the sufficient extension ratio cannot be obtained. Conversely, the extension temperature exceeds (the glass transition temperature is +1 〇 0. (:), the resin is flowing and cannot be Performing the extension of the stability. The extension ratio is defined by the area ratio, preferably from 1. 1 to 25 times, more preferably from 1. 3 to 1 〇. When the elongation is less than 丨丨, the movement due to the extension cannot be obtained. Conversely, when the stretching ratio exceeds 25 times, the effect of the stretching ratio increase cannot be confirmed. The stretching speed (one direction), preferably 〇 to 20,000%/min, more preferably 100 to 1 〇, 〇〇〇 %/min. When the stretching speed is not reached, the time for obtaining the sufficient stretching ratio is quite expensive, but the manufacturing cost is increased. Conversely, when the stretching speed exceeds 20,000%/min, the elongation film breakage occurs. 2226-7326B-PF 49丄361809 In order to stabilize the optical isotropic and mechanical properties of the film, The heat treatment (annealing) and the like are carried out after the stretching treatment. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples, and may be applied to the above and the following. And the scope of the present invention is included in the scope of the present invention. Further, in the following, for convenience, "quality: "parts" ^ description, "liters" is "liter" The production examples 1 to 4, the examples 1 to 19, and the comparative examples i to 2 correspond to the optical planar thermoplastic resin composition (A) of the present invention, and the production examples 5 and 6 are applied to the examples 20 to 2. 2 and Comparative Example 3 correspond to the planar thermoplastic resin composition (B) for optical use of the present invention. <Polymerization reaction rate, polymer composition analysis> Reaction rate at the time of polymerization reaction and content ratio of specific monomer units in the polymer The gas chromatography (GC 17, manufactured by Shimadzu Corporation) was used to determine the amount of unreacted monomers in the obtained polymerization mixture. The second thermogravimetry (dynamic tg; dynamic thermogravimetry) The polymer (or the solution or granule of the polymer) is completely dissolved or diluted in the THF or decyl alcohol for reprecipitation, and the removed sediment is vacuum dried for 33 hpa. ), 8 〇, 3 hours or more) to remove volatile components, and the obtained white solid shaped resin was analyzed by the following method (dynamic TG).

測定裝f :動態熱重熱差分析儀（Thermo Plus2 2226-7326B-PF 50 1361809 TG-8120，dynamic TG，Regaku 公司製造）測定條件：樣品量5至l〇mg 升溫速度：10°C/min 氣體環境：氮氣流20 0mL/min 方法：階段狀等溫控制法（由601至5〇〇»c的範圍内，控制於質量減少速度值0. 005%/s以下）〈内酯環構造之含有比例〉首先，將源自所得聚合物組成之所有經基以甲醇脫醇時所產生之質㈣少為基準’於動態定中，由質量減少:開始前t 150。。至聚合物分解開始前之3〇〇。。為止的脫醇反應所造成的質量減少，求出脫醇反應率。。亦即，具有内醋環聚合物之動態TG測定中，進行由至300 C之間質$減少率之測定，所得之實測值作為實：質量減少率⑴。另外，由該聚合物之組成，包含於該聚口物.、且成之全部蛵基為參與内酯環形成用之減少率（㈣，其組合物i觸料反應所假 =生而計算出之質量減少率），作為理論質量減少率 (Y)。又，更且锻太^ 體而έ ，理論質量減少率（Y)為聚合物中且有參與脫醇反應之姓j, τ ^ …構4 (规基）的原料單體之莫耳比可由該聚合物組兴斗比亦即醇計算式：中原料單體之含㈣計算。該等值之脫 (實測貝$減少率⑴/理論質量減少率（Υ)) 代入其值求出，以百分比⑻表示，得到脫醇反應率。Measurement f: Dynamic thermogravimetric analyzer (Thermo Plus 2 2226-7326B-PF 50 1361809 TG-8120, dynamic TG, manufactured by Regaku Corporation) Measurement conditions: sample amount 5 to l 〇 mg Heating rate: 10 ° C / min Gas environment: nitrogen flow 20 0mL/min Method: Stage-like isothermal control method (from 601 to 5〇〇»c, controlled by mass reduction speed value below 0.005%/s) <Lactone ring structure Content ratio > First, all the radicals derived from the obtained polymer composition are based on the mass (four) produced when methanol is dealcoholated, and are based on dynamics, which is reduced by mass: t 150 before starting. . 3 前 before the start of decomposition of the polymer. . The mass of the dealcoholization reaction is reduced, and the dealcoholization reaction rate is determined. . That is, in the dynamic TG measurement with the internal vinegar ring polymer, the measurement of the mass reduction rate from 300 C was performed, and the obtained measured value was taken as the actual mass reduction rate (1). In addition, the composition of the polymer is included in the polymer, and all of the sulfhydryl groups are involved in the reduction of the formation of the lactone ring ((4), and the composition i is reacted by the false reaction = calculated The mass reduction rate) is the theoretical quality reduction rate (Y). Moreover, the forging is too large, and the theoretical mass reduction rate (Y) is the molar ratio of the raw material monomer in the polymer and having the dehydration reaction, and the molar ratio of the raw material monomer of the τ ^ ... 4 (regular basis) can be The polymer group is also calculated as the alcohol calculation formula: the content of the raw material monomer (4). The value of the equivalent value (measured by the reduction rate of the shell (1) / the rate of reduction of the theoretical mass (Υ)) is obtained by substituting the value thereof, and expressed as a percentage (8) to obtain a dealcoholization reaction rate.

2226-7326B-PF 51 1361809 因此，進行僅以該脫醇反應率所設定之内醋環化者，呈有參與内醋環化構造（經基）之原料單體之該聚合物組成/中含 '有量（質量比）’與脫氫反應率相乘，可算出該聚合物組成 . 中内酯環構造所占有之含有比例。以後文所述之製造例i作為例子，計算粒狀物中内醋環構造之含有比例。求出該論質量減少率（γ)，曱醇分子量為32，2-(羥甲基）丙烯酸甲酯分子量為116，由於2一（羥 _ 甲基）丙烯酸甲醋之聚合物中之含有率（質量比）為組成上之25.0質量％，成為（32/116)χ25.0与6.90質量％。另外，動態TG所測定之實測質量減少率（又）為〇.22質量％。該數值代入上述脫醇計算式，成為1-(〇.22/6.90)与0.968，脫醇反應率為96. 8%。因此，聚合物僅以該脫醇反應率單位進行既定之内酯環化者，將2-(羥甲基）丙烯酸曱酯於該聚合物之含有率（25. 0質量％)，成乙脫醇反應率 (9 6. 8%=0. 96 8)，則該聚合物中内酯環構造之含有比例為 • 24. 2(25. 0x0. 968)質量％。以後文所述之製造例5作為例子，計算粒狀物中内酯環構造之含有比例。求出該論質量減少率（γ )，甲醇分子量為32，2-(羥甲基）丙烯酸甲酯分子量為116，由於2-(經甲基）丙烯酸曱酯之聚合物中之含有率（質量比）為組成上之20.0質量％，成為（32/116)x20.0与5.52質量％。另外，動態T G所測定之實測質量減少率（X )為〇. 1 7質量％。該數值代入上述脫醇計算式，成為1-(0.17/5.52)与0.969，脫醇反應率為9 6 · 9 %。因此，聚合物僅以該脫醇反應率單位 2226-7326B-PF 52 1361809 進行既定之内醋環化者，將2_(羥曱基）丙烯酸曱醋於該聚合物之含有率（20· 〇質量％)，成乙脫醇反應率 (9 6. 9%=〇_ 969)，則該聚合物中内酯環構造之含有比例為 19. 4(20. 0x0. 969)質量％。 <質量平均分子量> 聚合物之質量平均分子量，使用凝膠滲透層析（Gpc系列，東索公司製造），以苯乙烯為基準換算求出。 <炼融流速 > (melt fl〇w rate) 熔融流速，以JIS-K6874為基準，試驗溫度24〇艺，載種10kg而測定。 <聚合物之熱分析> ♦合物之熱分析，使用微差掃描熱分析儀（DSC_823〇， Rigaku(音譯）公司製造），樣品約1〇mg，於昇溫速度丨〇。〇 /min'氮氣流50mL/min之條件下進行。玻璃轉移溫度（Tg) 以ASTM-D-3418為基準，以中點值（mid_range)法求出。 <表面硬度> 薄臈之表面硬度，以JIS K-5400為基準，使用鉛筆引伸式驗機，測定錯筆硬度。 <光學特性> 折射率異向性（延遲（retardation) : Re)，係使用相位差測定裝置（K0BRA-21ADH，王子計測機器公司製造），測定相位差。使用濁度計（NDH-1001DP，曰本電色工業公司製造），測定全透光率及霾度。使用卜溴萘作為中間液.，使用阿貝折射計（M-M2，Atago公司製造），測定折射率及阿 2226-7326B-PF 53 1361809 貝數（Abbe’ s number) ° <機械特性> 薄膜之抗拉強度、延伸率、抗拉率，係以 ASTMU82-61T為基準而測定。其次，將說明具内酯環聚合物之製造例《製造例1》於配備攪拌裝置、溫度計、冷卻管、氮氣導管之容量 30L之爸型反應器中，饋入9, 〇〇〇g之曱基丙稀酸甲❿ 籲（匪A)、L 00〇g之2一（羥甲基）丙烯酸甲酯（MHMA)、1〇, 〇〇〇之4-甲基-2-戊酮（甲基異丁基酮，MIBK)、5g之正_ 丁一'燒基硫醇’於其中通入氮氣，升溫至1 〇 5 °c ’於回流之同時添加作為聚合起始劑之5. Og之碳酸第三丁基過氧醋異内酯（kayacarbonC音譯名）BIC-75，KayakuAkzo 公司製造），同時於4小時間滴加1 〇. 〇g之碳酸第三丁基過氧自旨異丙酉旨及230g之MIBK所成之溶液，於回流下，約1 〇5至12(Tc φ 進行溶液聚合，另經過4小時進行熟成。所製得之聚合物中’加入3Og之磷酸硬脂醯酯/破酸二硬脂醯酯混合物（Phos 1 ex A-18，堺化學工業公司製造），於回流下’以9 0至1 2 0 °C、5小時間進行環化縮合反應。其次’將所得之聚合物溶液’以料管溫度2 6 0 °C、回轉數 lOOrpm、減壓度 13.3 至 400hPa(10 至 300mmHg)、後通孔數1個、前通孔數4個之通孔型螺旋雙轴擠壓機 (必=29. 75mm ’ L/D = 30) ’以樹脂量換算，而以2. Okg/h之速度導入該擠壓機内，再進行環化縮合反應與脫揮而擠 2226-7326B-PF 54 1361809 壓’製得具内醋環聚合物之透明粒狀物。所製得之聚内酯環聚合物進行動態TG測定，測得〇. 35 . 質量％之質量減少。該具内酯環聚合物，質量平均分子量為 I 56,000，熔融流速為3.9g/l〇min，玻璃轉移溫度為123 。。。《製造例2》於配備授拌裝置、溫度計、冷卻管、氣氣導管之容量 30L之釜型反應器中，饋入8, 5〇〇g之·Α、l 5〇〇g之 lO’OOOg之MIBK、5g之正—十二烷硫醇，於其中通入氮氣，幵溫至105C，於回流下，添加作為聚合起始劑之l〇之碳酸第三丁基過氧化酯異丙酯之同時，⑨4小時期間滴加10. 〇g之碳酸第三丁基過氧化酯異丙酯與23〇g之所成溶液，於回流下、約1〇5至12(rc中進行溶液聚合，再進行4小時熟成。所製得聚合物中，加入6〇〇g之醋酸，於回流下、約 _ 90至12(TC中進行環化縮合反應5小時。其次將所製得聚合物溶液之，於製造例丨相同之通孔型螺旋雙軸劑壓機内進行％化縮合與脫揮，而擠壓製得具内酯環聚合物之透明粒狀物。所製仔之聚内酯環聚合物進行動態TG測定，測得〇. 35 質量%之質量減少。該具内酯環聚合物，質量平均分子量為 ’ 000熔融抓速為3. 9g/l〇min，玻璃轉移溫度為127 t。2226-7326B-PF 51 1361809 Therefore, the inner vine cyclization set only by the dealcoholization reaction rate, the polymer composition of the raw material monomer participating in the internal vinegar cyclization structure (transfer group) The 'quantity (mass ratio)' is multiplied by the dehydrogenation reaction rate to calculate the polymer composition. The content of the lactone ring structure is occupied. As an example, a production example i described later is used to calculate the content ratio of the internal vinegar ring structure in the granular material. The mass reduction rate (γ) was determined, the molecular weight of sterol was 32, and the molecular weight of methyl 2-(hydroxymethyl) acrylate was 116, due to the content of the polymer of 2-(hydroxy-methyl) methacrylate. (mass ratio) was 25.0% by mass of the composition, and was (32/116) χ 25.0 and 6.90% by mass. In addition, the measured mass reduction rate (again) measured by the dynamic TG was 〇.22% by mass. The hexamination reaction rate was 96.8%. Therefore, the polymer is only subjected to the predetermined lactone cyclization in the unit of the dealcoholization reaction rate, and the content of the 2-(hydroxymethyl) decyl acrylate in the polymer (25. 0% by mass) is converted into ethylene. The content ratio of the lactone ring structure in the polymer is 2. 24. 2 (25. 0x0. 968)% by mass. Production Example 5, which will be described later, is taken as an example to calculate the content ratio of the lactone ring structure in the granular material. Determine the mass reduction rate (γ), the molecular weight of methanol is 32, the molecular weight of methyl 2-(hydroxymethyl)acrylate is 116, and the content (quality) in the polymer of 2-(methyl methacrylate) The ratio is 20.0% by mass of the composition, and is (32/116) x 20.0 and 5.52% by mass. Further, the measured mass reduction rate (X) measured by the dynamic T G was 〇1.7% by mass. This value was substituted into the above-described dealcoholization formula to obtain 1-(0.17/5.52) and 0.969, and the dealcoholization reaction rate was 9 6 · 9 %. Therefore, the polymer is only subjected to the predetermined vinegar cyclization in the unit of the dealcoholization reaction rate 2226-7326B-PF 52 1361809, and the content of the bismuth hydroxyacetate in the polymer (20·〇 mass) % (2. 0x0. 969)% by mass. The content of the lactone ring structure in the polymer is 19.4 (20. 0x0. 969) by mass. <Mass average molecular weight> The mass average molecular weight of the polymer was determined by gel permeation chromatography (Gpc series, manufactured by Tosoh Corporation) on the basis of styrene. <Smelting flow rate > (melt fl〇w rate) The melt flow rate was measured on the basis of JIS-K6874, the test temperature was 24 ,, and 10 kg of the seed was carried. <Thermal analysis of the polymer> The thermal analysis of the compound was carried out using a differential scanning calorimeter (DSC_823®, manufactured by Rigaku Co., Ltd.), and the sample was about 1 〇mg at a temperature increase rate. The 〇 /min' nitrogen stream was carried out under the conditions of 50 mL/min. The glass transition temperature (Tg) was determined by the mid-range method based on ASTM-D-3418. <Surface hardness> The surface hardness of the crucible was measured using a pencil extension tester based on JIS K-5400 to measure the hardness of the erroneous pen. <Optical characteristics> The refractive index anisotropy (retardation: Re) was measured using a phase difference measuring device (K0BRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.). The total light transmittance and the twist were measured using a turbidimeter (NDH-1001DP, manufactured by Sakamoto Denshoku Industries Co., Ltd.). Using brom bromide as an intermediate liquid, an Abbe refractometer (M-M2, manufactured by Atago Co., Ltd.) was used to measure the refractive index and A226-7326B-PF 53 1361809 Beneficial number (Abbe's number) ° <Mechanical characteristics> The tensile strength, elongation, and tensile strength of the film were determined based on ASTMU82-61T. Next, a production example "manufacturing example 1" having a lactone ring polymer will be described in a dad-type reactor equipped with a stirring device, a thermometer, a cooling pipe, and a nitrogen gas line of 30 L, and fed to 9, 〇〇〇g Methyl acrylate (❿A), L 00〇g of 2-methyl(hydroxymethyl)acrylate (MHMA), 1〇, 4-methyl-2-pentanone (methyl) Og的碳酸碳酸。 The isobutanone, MIBK), 5g of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Tert-butyl peroxyacetate (Kayacarbon C transliteration) BIC-75, manufactured by Kayaku Akzo Co., Ltd.), while adding 1 于 at 4 hours. 〇g of dimethyl butyl peroxygenate And a solution of 230 g of MIBK, under reflux, about 1 〇 5 to 12 (Tc φ is solution polymerized, and further matured in 4 hours. In the obtained polymer, '3Og of stearyl phosphate/ A mixture of bis-stearyl phthalate (Phos 1 ex A-18, manufactured by Sigma Chemical Industry Co., Ltd.), cyclized and condensed at 90 °C to 120 ° C for 5 hours under reflux Next, 'the obtained polymer solution' is at a tube temperature of 260 ° C, a number of revolutions of 100 rpm, a degree of pressure of 13.3 to 400 hPa (10 to 300 mmHg), a number of back through holes, and a number of front through holes of four. Through-hole type spiral double-axis extruder (must = 29.75mm 'L/D = 30) 'In the amount of resin, and introduced into the extruder at a rate of 2. Okg / h, and then cyclization condensation reaction With the devolatilization 2226-7326B-PF 54 1361809 press to produce a transparent granule with a polymer of vinegar ring. The obtained polylactone ring polymer was measured by dynamic TG and measured 〇. 35 . The mass of % is reduced. The lactone ring polymer has a mass average molecular weight of I 56,000, a melt flow rate of 3.9 g/l 〇 min, and a glass transition temperature of 123. [Manufacturing Example 2" is equipped with a mixing device and a thermometer. In the reactor of the cooling tube and the gas-gas pipeline with a capacity of 30 L, the MIBK of lO'OOOg of 5,5〇〇g·Α, l 5〇〇g, and the n-dodecyl mercaptan of 5g are fed. , nitrogen gas was introduced thereinto, the temperature was raised to 105 C, and under reflux, the same was added as the polymerization initiator. At the time of 94 hours, a solution of 10. 〇g of butyl butyl peroxycarbonate and 23 〇g was added dropwise, and solution polymerization was carried out under reflux at about 1 〇 5 to 12 (rc). The mixture was aged for 4 hours. 6 gram of acetic acid was added to the obtained polymer, and a cyclization condensation reaction was carried out for 5 hours under reflux at about _90 to 12 (TC). Next, the obtained polymer solution is subjected to % condensation and devolatilization in a through-hole type spiral biaxial press machine of the same manufacturing example, and extruded to obtain a transparent granular material having a lactone ring polymer. . The prepared polylactone cyclic polymer was subjected to dynamic TG measurement, and the mass reduction of 35.35 mass% was measured. The polymer having a lactone ring having a mass average molecular weight of ' 000 has a melt rate of 3. 9 g/l 〇 min and a glass transition temperature of 127 t.

《製造例3》 2226-7326B-PF 55 1361809 於製造例1中，除了變更MMA的量為8,000g、MHMA的量為2, 0 0Og以外，進行與製造例1相同之反應’製得具内 • 酯環聚合物之透明粒狀物。 . 所製得之聚内酯環聚合物進行動態TG測定，測得〇· 64 質量％之質量減少。該具内酯環聚合物’質量平均分子量為 144, 000，熔融流速為9. 2g/l〇min，玻璃轉移溫度為131 〇C。《製造例4》於配備攪拌裝置、溫度計、冷卻管、氮氣導管之容量 3 0L之爸型反應器中，饋入7, 5〇〇g之匪A、2, OOOg之MHMA、 500g之甲基丙烯酸、i0,000g之MIBK、25g之正-十二烷硫醇’於其中通入氮氣，昇溫至1 〇5°C，於回流下，添加作為聚合起始劑之1 0 . 〇 g之碳酸第三丁基過氧化酯異丙醋之同時’於4小時期間滴加i 〇, Og之碳酸第三丁基過氧化醋異丙自旨與230g之MIBK所成溶液’於回流下、約105至120 • °c中進行溶液聚合，再進行4小時熟成。取出一部份所製得聚合物溶液，進行動態TG之測定，測得0 · 5 9質量％之質量減少。所製得聚合物，於製造例1相同之通孔型螺旋雙軸劑壓機内，進行環化縮合與脫揮，而擠壓製得具内酯環聚合物之透明粒狀物。口Production Example 3 2226-7326B-PF 55 1361809 In the production example 1, the same reaction as in Production Example 1 was carried out except that the amount of MMA was changed to 8,000 g and the amount of MHMA was 2,0O0g. • Transparent granules of ester ring polymers. The obtained polylactone ring polymer was subjected to dynamic TG measurement, and the mass reduction of 〇·64 mass% was measured. The lactone ring polymer had a mass average molecular weight of 144, 000, a melt flow rate of 9. 2 g/l 〇 min, and a glass transition temperature of 131 〇C. "Manufacturing Example 4" In a dad-type reactor equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas line of a volume of 30 L, a MHMA of 7.5, 2 OOOg, a MHMA of 500 g, and a methyl group of 500 g were fed. Acrylic acid, i0,000 g of MIBK, 25 g of n-dodecyl mercaptan, into which nitrogen gas was introduced, and the temperature was raised to 1 〇 5 ° C, and under reflux, 10 0 as a polymerization initiator was added. At the same time as the third butyl peroxy ester isopropyl vinegar, i 〇 was added dropwise during 4 hours, and the solution of Og carbonated third butyl peroxy acetonate to 230 g of MIBK was refluxed, about 105 Solution polymerization was carried out at 120 ° ° C and then matured for 4 hours. A part of the obtained polymer solution was taken out, and the measurement of dynamic TG was carried out, and the mass reduction of 0.59% by mass was measured. The obtained polymer was subjected to cyclization condensation and devolatilization in a through-hole type spiral biaxial press machine of the same manner as in Production Example 1, and extruded to obtain a transparent granular material having a lactone ring polymer. mouth

所製得之聚内酯環聚合物進行動態TG測定，測得〇 28 質里％之質量減少。該具内酯環聚合物，質量平均分子量為 I 86,000,熔融流速為7.2g/l〇min，玻璃轉移溫度為139 2226-7326B-PF °c。《製造例5》於配備授拌袈置、溫度計、冷卻管、氮氣導管之容旦二之爸型反應器中，饋入8, _g之，、2, 〇峋之二里，_g之匯，…二烧硫醇，於其中通入氮氣，汁溫至1G5°C，於回流下，添加作為聚合起始劑之5.〇g之蚊酸第三丁基過氧化酯異丙酯之同時，於4小時期間滴加 10. Og之碳酸第二丁基過氧化酯異丙酯與23〇g之们ΒΚ所成溶液，於回流下、約⑽i 12代中進行溶液聚合，再進行4小時熟成。所製得聚合物中，加入30g之磷酸硬脂醯酯/磷酸二硬脂醯酯之混合物，於回流下、約9〇至12(rc中進行環化縮合反應5小時。其次，將所製得聚合物溶液之，於製造例 1相同之通孔型螺旋雙軸劑壓機内，進行環化縮合與脫揮，而擠壓製得具内酯環聚合物之透明粒狀物。所製得之聚内酯環聚合物進行動態TG測定，測得0. 1 7 質量％之質量減少。該具内酯環聚合物，質量平均分子量為 1 33，000，熔融流速為6· 5g/1 0miη，玻璃轉移溫度為131 〇C。《製造例6》於配備攪拌裝置、溫度計、.冷卻管、氮氣導管之容量 30L之蚤型反應器中，饋入8, 000g之MMA、2, 000g之MHMA' 1 0, 000g之甲苯、5g之三（2,4-二-第三丁基苯基）磷酸酯 (ADEKA STAB 2112，旭電化公司製造），於其中通入氮氣’ 2226-7326B-PF 57 1361809 昇溫至1 oo°c，於回流下，添加作為聚合起始劑之i丨g之異壬酸第二戊基過氧化酯（RUPER〇CUSE 57〇 (音譯），吉富公司製造）之同時，於2小時期間滴加22g之異壬酸第三戊基過氧化酯與219g之曱苯所成溶液，於回流下、約 1 00至1 20 C中進行溶液聚合，再進行4小時熟成。所製得聚合物中，加入10g之磷酸硬脂醯酯/磷酸二硬脂醯酯之混合物，於回流下 '.約85至12〇<t中進行環化縮合反應5小時。其次，將所製得聚合物溶液之，於製造例 1相同之通孔型螺旋雙軸劑壓機内，進行環化縮合與脫揮，而擠壓製得具内酯環聚合物之透明粒狀物。所製得之聚内酯環聚合物進行動態TG測定’測得〇ιι 質量％之質量減少。該具内酯環聚合物，質量平均分子量為 146, 000，熔融流速為u. 3g/1〇min，玻璃轉移溫度為〇C。《實施例1》於製造例1所製得之粒狀物，使用2〇mm必之具有螺旋之雙軸擠壓機，於寬150_之衣架式τ型模頭（C0a卜hanger T type die)熔融擠壓，製作厚度約1〇〇#m之薄膜。所製彳于薄膜之光學特性及機械特性之評估結果，示於表1及表2。《實施例2至4》使用製造例2至4所製得之各粒狀物，與實施例j相同之方式’製作厚度約1 〇〇 # m之薄膜。所製得溥膜之光學特性及機械特性之評估結果，示於The obtained polylactone ring polymer was subjected to dynamic TG measurement, and the mass % of 〇 28 was measured to be reduced. The lactone ring polymer had a mass average molecular weight of I 86,000, a melt flow rate of 7.2 g/l 〇 min, and a glass transition temperature of 139 2226-7326 B-PF °c. "Manufacturing Example 5" is fed into a dad-type reactor equipped with a mixing device, a thermometer, a cooling pipe, and a nitrogen duct, and fed into a _g, a sig, a sigma, a sigma, a second-burning mercaptan, in which nitrogen gas is introduced, the juice is heated to 1 G 5 ° C, and under reflux, 5 g of butyl isopropyl peroxy methacrylate as a polymerization initiator is added. A solution of 10. Og of dibutyl peroxydicarbonate isopropyl ester and 23 g of ruthenium was added dropwise during 4 hours, and solution polymerization was carried out under reflux for about 10 days, and then aged for 4 hours. . To the obtained polymer, 30 g of a mixture of stearyl phosphate/distearyl phosphate was added, and a cyclization condensation reaction was carried out for 5 hours under reflux at about 9 Torr to 12 (second time). The obtained polymer solution was subjected to cyclization condensation and devolatilization in the same through-hole type spiral biaxial press as in Production Example 1, and extruded to obtain a transparent granule having a lactone ring polymer. The polylactone cyclic polymer was subjected to dynamic TG measurement, and the mass of 0.17 mass% was measured. The lactone ring polymer had a mass average molecular weight of 133,000 and a melt flow rate of 6.5 g/1. 0miη, glass transition temperature is 131 〇C. "Manufacturing Example 6" In a reactor of 30 liter capacity equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas conduit, MM of 8,000 g, 2,000 g is fed. MHMA' 1 0 000 g of toluene, 5 g of tris(2,4-di-t-butylphenyl) phosphate (ADEKA STAB 2112, manufactured by Asahi Kasei Co., Ltd.), into which nitrogen '2226-7326B-PF was introduced 57 1361809 heating to 1 oo °c, under reflux, adding i丨g as the polymerization initiator, the second pentyl peroxidation (RUPER〇CUSE 57〇 (transliteration), manufactured by Jifu Company), while adding 22g of a solution of the third pentyl peroxydecanoate and 219g of benzene in a period of 2 hours, under reflux, about 1 Solution polymerization is carried out at 00 to 1 20 C, and further aging is carried out for 4 hours. To the obtained polymer, 10 g of a mixture of stearyl phosphate/distearyl phosphate is added under reflux, which is about 85 to 12 The cyclization condensation reaction was carried out for 5 hours in 〇<t. Next, the obtained polymer solution was subjected to cyclization condensation and devolatilization in the same through-hole type spiral biaxial press machine of the same manner as in Production Example 1. The transparent granules having a lactone ring polymer were obtained by extrusion. The obtained polylactone ring polymer was subjected to dynamic TG measurement to determine the mass of 〇% by mass. The lactone ring polymer, quality The average molecular weight is 146, 000, the melt flow rate is u. 3g / 1 〇 min, and the glass transition temperature is 〇 C. [Example 1] The granules obtained in Production Example 1 have a spiral of 2 〇 mm. The twin-screw extruder is melt-extruded in a 150_ coat hanger type τ-type die (C0a hanger T type die) A film having a thickness of about 1 Å #m was produced. The evaluation results of the optical properties and mechanical properties of the film produced are shown in Tables 1 and 2. "Examples 2 to 4" were produced using Production Examples 2 to 4. For each of the granules, a film having a thickness of about 1 〇〇# m was produced in the same manner as in Example j. The evaluation results of the optical properties and mechanical properties of the obtained ruthenium film are shown in

2226-7326B-PF 58 1361809 表1及表2。《比較例1》使用聚碳酸酯（Panl i te L-l 225Y，帝人化成公司製造），與實施例1相同之方式，製作厚度約i 00 " m之薄膜。所製得薄膜之光學特性及機械特性之評估結果，示於表1及表2。表12226-7326B-PF 58 1361809 Table 1 and Table 2. Comparative Example 1 A film having a thickness of about i 00 " m was produced in the same manner as in Example 1 using polycarbonate (Panl i te L-l 225Y, manufactured by Teijin Chemicals Co., Ltd.). The evaluation results of the optical properties and mechanical properties of the obtained film are shown in Tables 1 and 2. Table 1

由表1及表2可了解，實施例丨至4之薄膜八内自曰環之聚合物所形成，透明性高折射率低It can be understood from Tables 1 and 2 that the films of Examples 丨 to 4 are formed of a polymer of the inner ring of the ring, and the transparency is high and the refractive index is low.

能=低，光學等向性高，抗張強度及抗張彈性率及^面: 度向，延伸率低。、相對於此’比較例i之薄膜’由於以聚碳酸醋所形成，透明性咼，折射率高，光學等， ▲ ^ ^ 寻门性低抗張強度及抗張彈平及表面硬度低，延伸率高》Energy = low, high optical isotropic, tensile strength and tensile modulus and surface: degree, low elongation. Compared with the film of Comparative Example i, which is formed of polycarbonate, has transparency, high refractive index, optical, etc., ▲ ^ ^ low-resistance tensile strength, tensile flatness and low surface hardness. High elongation rate

2226-7326B-PF 59 1361809 3有具内酯環之聚合物作為主成分之光學用平面狀熱可塑性樹脂組合物(A) ’除了透明性及耐熱性之外’ 光學特性或機械特性皆優異，於各種光學用途中可知能充分的發揮特性。《實施例5》貫施例1所製得之薄膜貼合於包含聚乙烯醇之偏光膜之兩面而製得偏光板。將該偏光板於直交偏光（crossed niC〇1S)下重疊，觀察光之遺漏，未觀察到重疊部分之光的遺漏（亮點）。所製得之偏光板之概略圖示於第丨圖。第丨圖令，i 表示偏光板’ 2及3表示保護薄膜。《實施例6》洋精2226-7326B-PF 59 1361809 3 The planar thermoplastic resin composition (A) having a polymer having a lactone ring as a main component is excellent in optical properties or mechanical properties except for transparency and heat resistance. It is known that various optical applications can fully exhibit characteristics. <<Example 5>> A film obtained in Example 1 was bonded to both faces of a polarizing film containing polyvinyl alcohol to prepare a polarizing plate. The polarizing plate was superposed under crossed polarized light (crossed niC〇1S), and the omission of light was observed, and no omission (brightness) of light in the overlapping portion was observed. A schematic diagram of the prepared polarizing plate is shown in the figure. In the second diagram, i indicates that the polarizing plates '2 and 3' indicate a protective film. "Embodiment 6"

μ施例1所製得之薄膜，使用雙軸延伸試驗機（東機製作所製造），於15(rc，以〇.lm/min之延伸速度軸延伸1. 5倍，製得厚度45 # ^之延伸薄膜。The film obtained by the method of Example 1 was obtained by using a biaxial extension tester (manufactured by Toki Seisakusho Co., Ltd.) at a stretching speed of 1.5 rc/min. The stretch film.

所製得之延伸薄膜之機械特性之評估結果，示於表2。該延伸薄膜貼合於包含聚乙烯醇之偏光膜之兩面而製得偏光板。將該偏光板於直交偏光（cr〇ssed nic〇丨）下重疊，觀察光之遺漏，未觀察到重疊部分之光的遺漏（亮點）。《實施例7》使用製造例3所製得之具内g旨環聚合物之粒狀物，與實施例1相同方式，製作厚度200 /zm之薄膜。該薄膜使用雙軸延伸試驗機（東洋精機製作所製造），於i 5〇〇c，以 0· lm/min之延伸速度，單軸延伸5倍，製得厚度mThe evaluation results of the mechanical properties of the obtained stretched film are shown in Table 2. The stretched film was bonded to both sides of a polarizing film containing polyvinyl alcohol to prepare a polarizing plate. The polarizing plate was overlapped under criss-seded light (cr〇ssed nic〇丨), and the omission of light was observed, and no omission (brightness) of the overlapping portion of light was observed. <Example 7> A film having a thickness of 200 /zm was produced in the same manner as in Example 1 except that the pellet of the ring-shaped polymer obtained in Production Example 3 was used. The film was produced by using a biaxial stretching tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at i 5 〇〇c at a stretching speed of 0·lm/min and uniaxially extending 5 times to obtain a thickness m.

2226-7326B-PF 60 13*61809 之延伸薄膜。所製得之延伸薄膜之機械特性之評估結果，示於表2。測定該延伸薄膜於波長45〇nm及波長59〇nm之平面方向之相位差’為95nm及93nm。《比較例2》以聚碳酸醋（panlite L_1225Y，帝人化成公司製造）作為原料，使用雙軸延伸試驗機（東洋精機製作所製造），與實施例7相同方式，於】5(rc，以〇lm/D|in之延伸速度，又軸延伸1.5倍，製得厚度約15〇nm之延伸薄膜。測定該延伸薄膜於波長45〇nm及波長⑽⑽之平面方向之相位差，為42〇nu 375nme 州《實施例8》 1 霄施例6所製得之延伸薄膜貼合於包含聚乙烯醇之偏光膜之一面，實施例7所製得之延伸薄膜貼合於另一面而製得偏光板。該偏光板與實施例6所製得之偏光板於直交偏光（C_edni⑶⑷下重疊，觀察光之遺漏重疊部分之光的遺漏（亮點）。《實施例9》使用製造例3所製得之具内醋環聚合物之粒狀物，盘實施例1相同方式，製作厚度約2叫m之薄膜。該薄膜使用雙軸延伸試驗機（東洋精機製作所製造），於140t，以〇上細之延伸速度，單轴延伸U倍，製得厚度126"2226-7326B-PF 60 13*61809 extended film. The evaluation results of the mechanical properties of the obtained stretched film are shown in Table 2. The retardation angle of the stretched film in the plane direction of a wavelength of 45 Å and a wavelength of 59 Å was measured to be 95 nm and 93 nm. Comparative Example 2 Polycarbonate (panlite L_1225Y, manufactured by Teijin Chemicals Co., Ltd.) was used as a raw material, and a biaxial stretching tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used. The same manner as in Example 7 was carried out, and 5 (rc, 〇lm) The extension speed of /D|in is extended by 1.5 times to obtain an extended film having a thickness of about 15 〇 nm. The phase difference of the extended film at a wavelength of 45 〇 nm and a wavelength (10) (10) is measured, which is 42 〇 nu 375nme state <<Example 8>> 1 The stretched film obtained in Example 6 was applied to one side of a polarizing film containing polyvinyl alcohol, and the stretched film obtained in Example 7 was bonded to the other side to prepare a polarizing plate. The polarizing plate and the polarizing plate obtained in Example 6 were overlapped by the orthogonal polarized light (C_edni (3) (4), and the omission (brightness) of the light in the overlapping portion of the light was observed. Example 9 The vinegar prepared by the production example 3 was used. The pellet of the cyclic polymer was formed into a film having a thickness of about 2 m in the same manner as in Example 1. The film was produced by a biaxial stretching tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 140 t, at a fine extension speed of the crucible. Uniaxial extension U , To obtain a thickness of 126 "

之延伸薄膜。所製得之延伸薄膜於波長59。⑽之平面方向相位差為146nm。 2226-7326B-PF 61 比較例1所製得之機製作所製造），^14()ρ 延驗機（東洋精軸延伸 C，以O.lm/min之延伸速度，單 T丄.3倍，製俱厘电伸薄膜於… "m之延伸薄膜。所製得之延波長59°nm之平面方向相位差為297nm。所：得之兩種延伸薄膜’將該二薄膜之光軸為貼合，製得視角補償薄膜。《貫施例1 〇》 r 2 g之丙烯馱-"'五赤蘚醇六乙酯、2g之丙烯酸五赤二〜乙S|、°.5g之光聚合起始劑(Irgacure 9G7，日本 geigy公司製造），溶解於衝之二甲苯調製紫外線硬：型硬塗覆樹脂，使用棒式塗布機，塗布於實施例6 所製侍之延伸薄膜。溶媒乾燥後’以高壓水銀燈進行紫外冰…、射形成厚度5/zm之硬塗層。於該硬塗層上塗布硬 :覆所使用之反射防止劑(Cyt〇p，旭硝子公司製造)，形成厚度0.1//m之低折射率層，而製得反射防止薄膜。所製得之反射防止薄膜之反射率，於波長、55〇_為 0·80%。《實施例11》於實施例1所製薄膜之-面，以乾燥厚度為3//m而塗布下述所調配之紫外線遮蔽層，於12(rc乾燥】分鐘。再者，與紫外線反射層之相反側，以乾燥厚度為2〇 # m而塗布下述所調配之黏著劑層，於12(TC乾燥！分鐘。所製得積層體之表面硬度為4 Η。於波長3 5 0 nm之穿透率為〇 %。穿透率係以分光光度計（UV-3100，島津製作所製造）測定。 2226-7326B-PF 62 1361809 〈紫外線遮蔽層〉紫外線遮蔽性丙烯系樹脂（Ha 1 shybr id UV-G1 3，曰本 . 觸媒公司製造）：100份 . 異氰酸自曰硬化劑（Desmodur N3200，住化BayerThe stretch film. The resulting stretch film was at a wavelength of 59. (10) Plane direction The phase difference is 146 nm. 2226-7326B-PF 61 manufactured by the machine made by Comparative Example 1), ^14()ρ continuation machine (Toyo Fine shaft extension C, with an extension speed of O.lm/min, single T丄.3 times, The electro-stretching film is made of ... "m extended film. The phase difference of the plane direction of the wavelength of 59°nm is 297nm. The two kinds of extended film 'the optical axis of the two films are posted The viewing angle compensation film is obtained. "Continuous Example 1 〇" r 2 g of propylene 驮-" 'five erythritol hexaethyl acrylate, 2 g of acrylic acid five erythro-diethyl S|, °. 5g photopolymerization The initiator (Irgacure 9G7, manufactured by Geigy Co., Ltd., Japan) was dissolved in xylene to prepare an ultraviolet hard: hard coat resin, which was applied to the stretched film prepared in Example 6 using a bar coater. 'Ultra-high-pressure mercury lamp is used for ultraviolet ice... to form a hard coat layer having a thickness of 5/zm. The hard coat layer is coated with a hard anti-reflectant (Cyt〇p, manufactured by Asahi Glass Co., Ltd.) to form a thickness of 0.1/. a low refractive index layer of /m to produce a reflection preventing film. The resulting reflection prevents the reflectance of the film at a wavelength of 5 5〇_为0·80%. [Example 11] The ultraviolet shielding layer prepared below was applied to the surface of the film prepared in Example 1 at a dry thickness of 3/m, at 12 (rc drying). In addition, on the opposite side of the UV-reflecting layer, the adhesive layer prepared as follows was applied at a dry thickness of 2 〇 #m, at 12 (TC dry! minutes. The surface hardness of the laminated body obtained was 4穿透. The transmittance at a wavelength of 350 nm is 〇%. The transmittance is measured by a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). 2226-7326B-PF 62 1361809 <UV shielding layer> UV shielding Acrylic resin (Ha 1 shybr id UV-G1 3, 曰本. Manufactured by Catalyst): 100 parts. Isocyanate self-curing hardener (Desmodur N3200, Sumiy Bayer

Urethane公司製造）：3份醋酸丁酯：37份〈黏著劑層〉 ^ 丙烯酸正丁酯/丙烯酸/曱基丙烯酸2-羥乙酯=93/6/1 之共聚物（質量平均分子量（JJW)800, 〇〇〇，玻璃轉移溫度-48 °C ’贈酸乙醋溶液’不揮發成份約4〇%) : ι〇〇份異氰自文自日硬化劑（Coronet L，日本polyurethane工業公司製造）：1份醋酸丁酯：1 〇〇份《實施例12》於實施例1所製薄膜之一面，以乾燥厚度為丨〇 # m而 Φ 塗布下述所調配之熱線遮蔽層，於12〇〇c乾燥3分鐘。所製得積層體之表面硬度為5H。於波長871nm之穿透率34%，波長l〇90mn之穿透率30%。穿透率係以分光光度計 (UV-3100，島津製作所製造）測定。〈熱線遮蔽層〉丙烯酸黏著劑（Hal shybri d IR-G205，日本觸媒公司製造）_ 10 0份狀菁系色素（Ex color-IR-12，日本觸媒公司製造）：Urethane company): 3 parts of butyl acetate: 37 parts <adhesive layer> ^ n-butyl acrylate / acrylic acid / 2-hydroxyethyl methacrylate = 93 / 6 / 1 copolymer (mass average molecular weight (JJW) 800, 〇〇〇, glass transfer temperature -48 °C 'Give ethyl vinegar solution 'non-volatile content about 4%%): ι〇〇 part of isocyanide self-curing agent (Coronet L, made by Japan Polyurethane Industrial Co., Ltd.) ): 1 part of butyl acetate: 1 part of "Example 12" On one side of the film prepared in Example 1, the heat-shielding layer prepared as follows was applied at a dry thickness of 丨〇#m and Φ, at 12〇〇c dry for 3 minutes. The surface layer of the resulting laminate had a surface hardness of 5H. The transmittance at a wavelength of 871 nm is 34%, and the transmittance at a wavelength of 10 〇 90 nm is 30%. The transmittance was measured by a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). <Hot line shielding layer> Acrylic adhesive (Hal shybri d IR-G205, manufactured by Nippon Shokubai Co., Ltd.) _ 10 0 parts Cyanine-based pigment (Ex color-IR-12, manufactured by Nippon Shokubai Co., Ltd.):

0. 3份 2226-7326B-PF 63 1361809 二亞敍（di immonium)系色素（IRG-022，日本化藥公司製造）：0. 3份甲基異丁基酮：50份《實施例1 3》於實施例1所製薄膜之一面，以乾燥厚度為3以m而塗布下述所調配之硬塗層，於1301乾燥2分鐘。所製得之積層體以溫度25°C、溼度60%RH，2小時調濕後，以25〇g/cm2 之載重，使用鋼鐵質絲絨（steel wo〇l)(型號·· #〇〇〇〇)磨擦塗覆面，完全未發現有損傷。〈硬塗層之組成〉熱硬化型矽硬塗覆劑（sol Guard NP730，日本 Dacroshamrock(音譯）公司製造）：ι〇〇份異丙醇：100份《實施例1 4》0. 3 parts 2226-7326B-PF 63 1361809 Di immonium pigment (IRG-022, manufactured by Nippon Kayaku Co., Ltd.): 0.3 parts of methyl isobutyl ketone: 50 parts "Example 1 3 On one of the films prepared in Example 1, the hard coat layer prepared below was applied to a dry thickness of 3 m, and dried at 1301 for 2 minutes. The obtained laminate was conditioned at a temperature of 25 ° C and a humidity of 60% RH for 2 hours, and then used a steel velvet (steel wo〇l) with a load of 25 〇g/cm 2 (model·· #〇〇〇〇) The coated surface was rubbed and no damage was found at all. <Composition of hard coat layer> Thermosetting type hard coater (sol Guard NP730, manufactured by Dacroshamrock, Japan): ι 〇〇 isopropyl alcohol: 100 parts "Example 1 4"

,於實把例1所製薄膜之一面，依序積層下述所調配之硬塗層、低折射率層。亦即，塗布下述硬塗覆劑，於剛 °c乾燥1分鐘後，以高壓水銀燈照射2嶋心2之紫外線 "in之硬塗層。其次，於該硬塗而硬化塗布層，形成厚度層上塗布下述所調配之低折射率塗覆劑，力硬化】 J時形成厚度〇· 1 " m之低折射率層。所製得薄膜之反射率於波長550nm為〇. 25%。所製得薄膜之彎折性、对濕熱性、耐熱性反射率之評估結果示於表〈硬塗覆劑之調製〉混合二- 五赤蘚醇六丙烯酸酯（Light acrylateOn the one surface of the film prepared in Example 1, the hard coat layer and the low refractive index layer which were prepared as described below were sequentially laminated. Namely, the following hard coating agent was applied, and after drying for 1 minute at a temperature of ° C, a hard coat of 2 Å 2 of ultraviolet rays was irradiated with a high pressure mercury lamp. Next, the coating layer is hardened by the hard coating, and the low-refractive-index coating agent prepared as described below is applied to the thickness layer to form a low-refractive-index layer having a thickness of 〇·1 " m. The reflectance of the film produced was 〇. 25% at a wavelength of 550 nm. The results of the evaluation of the bending property, the heat absorbing property, and the heat resistance of the obtained film are shown in the table. <Preparation of hard coating agent> Mixed bis-pentaerythritol hexaacrylate (Light acrylate)

2226-7326B-PF 64 1361809 DPE-6A，共榮化學公司製造）8g，以及五赤蘚醇三丙烯酸酯 (Light acrylate PE-3A，共榮化學公司製造）2g，溶解於 - 甲基乙基酮40g之溶液中，添加溶解於甲基異丁基酮2g之2226-7326B-PF 64 1361809 DPE-6A, manufactured by Kyoei Chemical Co., Ltd.) 8g, and 5g of erythritol triacrylate (Light acrylate PE-3A, manufactured by Kyoei Chemical Co., Ltd.), dissolved in -methyl ethyl ketone In 40 g of the solution, 2 g of methyl isobutyl ketone was added.

光聚合起始劑（Irgacure 907，Ciba SpecUnty ChemicaU 公司製造）0. 5 g之溶液，調製硬塗覆劑。〈低折射率塗覆劑之調製〉於備配攪拌機、溫度計、冷卻管之容量3〇〇mL之四口燒瓶中’饋入四甲氧基矽烷144.5g、7·-甲基丙烯醯基丙基二甲氧基矽烷 23· 6g、水 19. 〇g、曱醇 3〇. 〇g、Amberl ist 15(〇rgano公司製造陽離子交換樹脂）5.〇g，於65„c攪拌2 小時反應《反應混合物冷卻至室溫後，以蒸餾塔取代冷卻管，將其設置連接冷卻管及設置流出口，於常壓下、2小時期間升溫至燒瓶内溫為80X；為止，維持相同溫度至甲醇不再流出為止。其次，於2.67xl〇kPa之壓力下，於90°C 之溫度，維持至曱醇不再流出為止，再進行反應。接著， Φ 冷卻至至溫後，濾除Amber 1 i st 1 5，製得數平均分子量 1，800之聚合性聚矽氧烷。其次，於配備有攪拌機、滴下口、溫度計、冷卻管、氮氣導入口之容量1L燒瓶中，饋入作為有機溶劑之醋酸正丁醋26〇g’導入氮氣，一邊攪拌，一邊升溫至燒瓶内溫ιι〇 °c為止。其次，將上述所製得之聚矽氧烷l2g、甲基丙烯酸第三丁酯19g、丙烯酸丁酯94g、甲基丙烯酸2_羥乙酯 67g、曱基丙稀酸全氟辛基乙醋（Light 6以^ fm_i〇8，共榮化學公司製造)48g、2, 2，一偶氮雙(2_甲基丁腈）2A photopolymerization initiator (Irgacure 907, manufactured by Ciba SpecUnty Chemica U Co., Ltd.) of 0.5 g of a solution was prepared to prepare a hard coating agent. <Preparation of low-refractive-index coating agent> In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube of 3 〇〇mL, 'tetramethyl decane 144.5 g, 7-methyl methacrylate Dimethoxy decane 23·6g, water 19. 〇g, sterol 3〇. 〇g, Amberl ist 15 (cation exchange resin manufactured by 〇rgano) 5. 〇g, stirred at 65 „c for 2 hours. After the reaction mixture was cooled to room temperature, the cooling tube was replaced by a distillation column, and the mixture was connected to a cooling tube and an outlet was placed, and the temperature was raised to 80 X under normal pressure for 2 hours; the same temperature was maintained until methanol was not maintained. Then, it flows out again. Next, it is maintained at a temperature of 90 ° C under a pressure of 2.67 x 1 kPa until the sterol does not flow out, and then the reaction is carried out. Then, after cooling to Φ, the Amber 1 i st is filtered off. 1 5, a polymerizable polyoxyalkylene having a number average molecular weight of 1,800 was obtained. Next, an acetic acid as an organic solvent was fed into a 1 L flask equipped with a stirrer, a dropping port, a thermometer, a cooling tube, and a nitrogen introduction port. Just vinegar 26 〇 g' introduced nitrogen, while stirring, The temperature was raised to the inside temperature of the flask, i.e., 2 g of the polyoxyalkylene obtained above, 19 g of the third butyl methacrylate, 94 g of butyl acrylate, and 67 g of 2-hydroxyethyl methacrylate. Mercaptopropionic acid perfluorooctylacetic acid (Light 6 to ^ fm_i〇8, manufactured by Kyoei Chemical Co., Ltd.) 48g, 2, 2, azobis(2-methylbutyronitrile) 2

2226-7326B-PF 65 冷液於3小時期間由滴下口滴下。滴下後於鋼溫度繼續授拌1小時後，每30分鐘添加六壬酸第三丁基過氧化-2-乙自旨〇.lg，添加2 :欠，再進行2小時加熱聚合，製得數平均刀子里12, 〇〇〇、質量平均分子量27,刪之有機聚合物溶解於醋酸τ 丁 t — 夂正丁 8a之浴液。所得之溶液之固形份 48.2%。一其次，於配備攪拌機、2個滴下口（a與b)、溫度計之容量500mL之四口燒瓶中，饋入醋酸正丁醋2_、甲醇响，調整内溫為40t。其次，於燒瓶内，一邊攪拌，— 邊將上述所得之有機聚合物之醋酸正丁醋溶液10g、四氫夫南30g、醋酸正丁酯5g之混合液（原料液（八））由滴下口 a將25%氨水5g、去離子水1〇g、甲醇叫之混合液（原料液⑻)由滴下口 2小時間滴下。滴下後，以蒸館塔取代冷卻f ’將其設置連接冷卻管及設置流出口於 4〇kPa之壓力下，升溫至燒瓶内溫為lOOt為止，蒸餾去除氨、甲醇、醋酸正丁雖直到固形份為3〇%為止，製得無機粒子與有機粒子之比㈣7〇/3〇之混合物。該混合物中無機粒子之平均粒子徑為2 3. 9nm。平均粒子徑以下述方法測定。其次，將上述製得之無機粒子與有機聚合物之混合物 9g，Desmodur N3200 (住化 Bayer Urethane 公司製造之異氣酸醋硬化劑)〇.3g、二—十二统酸二正丁醋錫化合物 0. 0 0 3g、甲基異丁基酮丨丨〇g混合，調製低折射率塗覆劑。〈低折射率塗覆劑中無機粒子與有機聚合物之比例〉2226-7326B-PF 65 The cold liquid was dripped from the dropping port during 3 hours. After the dropping, the mixture was further stirred at the steel temperature for 1 hour, and then, after 30 minutes, tributyl hexanoic acid peroxy-2-ethylperoxide was added, and the addition of 2: owed, followed by heating for 2 hours to obtain a number average In the knife, 12, 〇〇〇, mass average molecular weight of 27, the organic polymer is dissolved in the bath of acetic acid tau t- 夂丁 butyl 8a. The solid solution of the resulting solution was 48.2%. Then, in a four-necked flask equipped with a stirrer, two dropping ports (a and b), and a thermometer having a capacity of 500 mL, acetic acid n-butyl vinegar 2, methanol was fed, and the internal temperature was adjusted to 40 t. Next, while stirring in the flask, a mixture of 10 g of the organic polymer obtained in the n-butyl vinegar solution, 30 g of tetrahydrofuran, and 5 g of n-butyl acetate (raw material (8)) was dropped from the dropping port. a 5 g of 25% ammonia water, 1 〇g of deionized water, and a mixture of methanol (raw material liquid (8)) were dropped from the dropping port for 2 hours. After dripping, replace the cooling f' with a steaming tower, connect it to the cooling pipe and set the outlet at a pressure of 4 kPa, and raise the temperature until the internal temperature of the flask is lOOt. Distill off ammonia, methanol, and acetic acid until solid. A mixture of inorganic particles and organic particles (4) of a mixture of 7 Å/3 Å was prepared in a ratio of 3% by weight. The average particle diameter of the inorganic particles in the mixture was 23.9 nm. The average particle diameter was measured by the following method. Next, a mixture of the above-prepared inorganic particles and an organic polymer is 9 g, Desmodur N3200 (a gas sulphuric acid hardener manufactured by Bayer Urethane Co., Ltd.), 3 g, and a di-n-butyl succinate compound. 0. 0 0 3g, methyl isobutyl ketone oxime g was mixed to prepare a low refractive index coating agent. <The ratio of inorganic particles to organic polymer in low refractive index coating agent>

2226-7326B-PF 66 :低折射率塗覆劑，於133xl0kpa之厂£力下厲劑令無機粒子之含有量以灰份作為低折射率塗覆〈平均粒子徑〉、使用上述所製4之無機粒子與有機聚合物之混合物以醋酸正丁醋 qq^接雄 ^ . 稀釋之溶液，以穿透式電子顯微鏡攝衫，言買取任1〇〇個粒子直徑，其平均作為粒子徑。〈耐濕熱性〉於80 C、相對座度95%RH之高溫高濕環境中放置複 =臈U00小時，以與前述相同之分光光度計測定放刖後所使用之二亞.銨色素之極大吸收波長。，〇9。⑽)之穿透2求出放置前後穿透率差’以下述基準評估塗膜中色素女疋性。再者’進行nsK5彻之網眼膠帶剝離試驗，鳥1，000小時放置後塗布薄膜之基材密合性，以下述基準評估剝離試驗後之塗膜狀態。 " 色素安定性：〇.忒驗則後色素之極大吸收波長之穿透率變化 1% 逆 △:試驗前後色素之極大吸收波長之穿透率變化達以上，不達3% 0 X.試驗前後色素之極大吸收波長之穿透率變化達㈣以上 ° 基材密合性：〇：無異常2226-7326B-PF 66 : Low-refractive-index coating agent, under the force of 133x10kpa, the content of inorganic particles is coated with ash as low refractive index (average particle diameter), using the above-mentioned 4 The mixture of inorganic particles and organic polymer is mixed with n-butyl vinegar acetate qq^. The diluted solution is taken as a penetrating electron microscope, and the average particle diameter is taken as the particle diameter. <Heat and heat resistance> Placed in the high-temperature and high-humidity environment of 80 C and 95% RH relative to the seat, 复U00 hours, and the same spectrophotometer as described above was used to measure the maximum amount of the diammonium pigment used after the release. Absorbing wavelength. , 〇 9. (10)) Penetration 2 was used to determine the difference in penetration before and after placement. The pigmentation in the coating film was evaluated on the basis of the following criteria. Further, the nsK5 clear mesh tape peeling test was carried out, and the substrate adhesion of the coated film was set after the bird was placed for 1,000 hours, and the state of the coating film after the peeling test was evaluated based on the following criteria. " Pigment stability: 〇. After the test, the penetration rate of the maximum absorption wavelength of the pigment changes by 1%. Inverse △: the transmittance of the maximum absorption wavelength of the dye before and after the test changes by more than 3%. 0 X. Test The transmittance of the maximum absorption wavelength of the pigment before and after is changed to (4) or more. The substrate adhesion: 〇: no abnormality

2226-7326B-PF 67 1361809 x :剝離〈耐熱性> 塗淖薄膜於loot環境中放置1，000小時，以與前述相同之分光光度計，測定放置前後所使用之二亞錄色素之極大吸收波長（l，〇90mn)之穿透率，求出放置前後穿透率差，以T述基準評估塗膜中色素安定性。色素安定性· 〇：試驗前後色素之極大吸收波長之穿透率變化不達 1% △:試驗前後色素之極大吸收波長之穿透率變化達以上，不達3% X ·.試驗前後色素之極大吸收波長之穿透率變化達以上〈彎折性〉塗布薄膜以JIS K5600(2004年版）為基準進行彎折試鲁驗，評估塗臈之彎折部份之龜裂、破璃等異常產生之軸心直徑，以下述基準評估。車由心直徑小意指塗膜之弯折性優異》〇：良好（軸心直徑為6mm以下） △:接近良好（軸心直徑為8mm以上，1 〇職以下） X :不良（軸心直徑為1 2mm以上）〈反射率〉與薄膜之反射防止膜側相反側之面，以鋼鐵絲織將其粗面化，再以黑色墨水塗布，使用分光光度計，2226-7326B-PF 67 1361809 x : Peeling <Heat resistance> The film was placed in a loot environment for 1,000 hours, and the maximum absorption of the ditope pigment used before and after the placement was measured by the same spectrophotometer as described above. The transmittance of the wavelength (l, 〇90mn) was determined, and the difference in transmittance before and after the placement was determined, and the stability of the pigment in the coating film was evaluated on the basis of T. Pigment stability · 〇: The penetration rate of the maximum absorption wavelength of the pigment before and after the test does not change by 1% △: The transmittance of the maximum absorption wavelength of the dye before and after the test changes by more than 3% X ·. The transmittance of the maximum absorption wavelength is changed to the above <bending property> The coated film is subjected to a bending test based on JIS K5600 (2004 edition), and the abnormality such as cracks and broken glass of the bent portion of the coating is evaluated. The diameter of the shaft was evaluated on the basis of the following criteria. The small diameter of the car means that the coating film is excellent in bending property. 〇: Good (shaft diameter is 6 mm or less) △: It is close to good (axial diameter is 8 mm or more, 1 or less) X: Poor (axial diameter) (1 2 mm or more) <Reflectance> The surface opposite to the anti-reflection film side of the film is roughened by steel wire, coated with black ink, and a spectrophotometer is used.

2226-7326B-PF 68 1361809 島津製作所製造）測定於反射防止膜之入射角5。之鏡面反射光譜，反射率以顯示最小值之波長及其反射率最小值而求出。2226-7326B-PF 68 1361809 manufactured by Shimadzu Corporation) The incident angle 5 measured by the antireflection film was measured. The specular reflection spectrum, the reflectance is obtained by showing the minimum wavelength and the minimum reflectance.

耐熱性（loot) 1，000小時後 1，000小時後Heat resistance (loot) 1,000 hours later 1,000 hours later

於貫施例12所製得薄膜之熱線遮蔽層之相反側，依序積層育實施例14相同之硬塗層、低折射率層。如此製作具有反射防制性與熱線遮蔽性之複合薄膜。所製得之複合薄膜，於波長55〇ηΠι之反射率為〇 25%，波長871nm之穿透率為34% ’波長l 090nm之穿透率為3〇%。而穿透率係以分光光度計（UV-3100，島津製作所製造）測定。《實施例16》於實施例1所製得薄膜之一面，將如下所述，以攪拌機攪拌所製付之塗料’以所製得光擴散層之乾燥厚度為j 5 # m加以塗布’硬化。所製得之擴散薄膜於背光單元 (baCkHght Unit)(第2圖）之導光板側之相反側組合形成光擴散層，該背光單元放置於6〇<t之恆溫槽中，觀察72 小時後光擴散溥片彎曲之有無，巾完全無彎曲。於第2圖On the opposite side of the heat ray shielding layer of the film obtained in Example 12, the same hard coat layer and low refractive index layer as in Example 14 were sequentially laminated. Thus, a composite film having reflection prevention property and heat ray shielding property was produced. The composite film thus obtained had a reflectance of 〇 25% at a wavelength of 55 〇ηΠ, a transmittance of 34% at a wavelength of 871 nm, and a transmittance of 3〇% at a wavelength of 090 nm. The transmittance was measured by a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). [Example 16] On one side of the film obtained in Example 1, the coating material prepared by stirring with a stirrer was coated and hardened by the dry thickness of the obtained light-diffusing layer being j 5 # m. The prepared diffusion film is combined to form a light diffusion layer on the opposite side of the light guide plate side of the backlight unit (Fig. 2), and the backlight unit is placed in a thermostat of 6 〇<t, after observing for 72 hours The light-diffusing cymbal is bent or not, and the towel is completely curved. In Figure 2

中’ 11表不導光板’ 12表示擴散薄片（擴散薄膜），13表 2226-7326B-PF 69 1361809 示反射薄片，14表示螢光管，15表示反射器。彎曲之有無，係將背光單元之燈光點著，以光擴散表面之亮度不均之產生與否而判定。〈光擴散層之組成〉丙埽酸黏著劑（RUB Methylium Clear (音譯），大曰成精化工業公司製造）：100份丙烯系樹脂系小粒（NT-2，日本油脂公司製造，平均粒 _ 子徑5/z m) : 14份膠質化矽氡烷（Snotick (音譯），日產化學公司製造，平均粒子徑〇. 〇 15 # m) : 2 0份《實施例1 7》貫轭例3所製得之具内酯環聚合物之粒狀物射出成形，製作15〇mmxl50mmx3_之薄片狀成形品。The '11-surface light guide plate' 12 indicates a diffusion sheet (diffusion film), 13 table 2226-7326B-PF 69 1361809 shows a reflection sheet, 14 indicates a fluorescent tube, and 15 indicates a reflector. The presence or absence of bending is caused by the light of the backlight unit being lit, and the brightness unevenness of the light diffusing surface is determined whether or not the brightness is uneven. <Composition of Light-Diffusion Layer> Propionate Adhesive (RUB Methylium Clear, manufactured by Otsuka Seiki Chemical Co., Ltd.): 100 parts of propylene resin-based pellets (NT-2, manufactured by Nippon Oil & Fats Co., Ltd., average grain _ Sub-path 5/zm) : 14 parts of colloidal decane (Snotick (transliteration), manufactured by Nissan Chemical Co., Ltd., average particle diameter 〇. 〇15 # m) : 20 parts "Example 1 7" yoke example 3 The pellets of the lactone ring polymer obtained were injection-molded to prepare a sheet-like molded article of 15 mm x 150 mm x 3 mm.

所裝仔之薄片狀成形品，全光線穿透率為⑽，靈為〇·3%，波長590nm之相位差為8nm。《實施例18》合物之粒狀物射出成 5mm，最小厚度為2mm 貫施例3所製得之具内酯環聚形裝作200職x200_，最大厚度為之楔形導光板。使用所製得之椒形实本也 - 撰小導先板，製作如第2圖所示之負早凡。第2圖申，n盔道丄』月 , n , 為導先板，12表示擴散薄片（擴影胰），13表示反射薄 ,^ A 14表不螢光管，15表示反射突《貫施例1 9》 nt 於8 0份製造例3 β 所I付之具内酯環聚合物之粒狀The sheet-like molded article of the package had a total light transmittance of (10), a 〇·3%, and a phase difference of 8 nm at a wavelength of 590 nm. The granules of the "Example 18" compound were ejected to a thickness of 5 mm and a minimum thickness of 2 mm. The lactone ring having the polyester content prepared in Example 3 was set to 200 positions x 200 Å, and the maximum thickness was a wedge-shaped light guide plate. Using the prepared pepper-shaped real version - also write a small guide plate, making the negative as shown in Figure 2. Figure 2, n helmets 丄』 month, n, is the guide plate, 12 is the diffusion sheet (expanding pancreas), 13 is the reflection thin, ^ A 14 is not fluorescent tube, 15 is the reflection protrusion Example 1 9 " nt in 80 parts of the production example 3 β I have a lactone ring polymer granular

2226-7326B-PF 70 中，熔融混練20份之丙烯酸系微粒子(Ερ〇 —順音譯），曰本觸媒公司製造）後，射出成形，製作15〇眶15〇_ x3mm之薄片狀成形品。所製得薄月狀成形品，全光線穿透率為85%，霾為 75% ’具有作為擴散板之充分特性者。《實施例20》 “製造例5所製得之具内酯環聚合物之粒狀物與丙烯腈 -苯乙烯（AS)樹脂（T〇y〇-AS AS20，東洋苯乙稀公司製造），以具内，環聚合物/AS樹脂=9〇/1〇之質量比使用單軸擠壓機(0’關)混鍊，製得熱可塑性樹脂組合物之透明粒狀物。所製得之熱可塑性樹脂組合物之玻璃轉移溫度為127 C。 …該熱可塑性樹脂組合物溶解於甲基乙基明，以溶液禱杈法，製作厚度為60“之未延伸薄膜。於溫度ι〇。。。，以延伸速纟〇.lm/min，單轴延伸該薄们5倍，製得厚产為50" m之延伸薄膜。該等又不、评，專膜延伸薄膜之光學特性之坪估結果示於表4。《實施例21》 =與實施例2。同樣地’以具内醋環聚合物/as樹脂 :。/20之質量比’使用單輛擠壓機混鍊，製得熱可塑性樹 1 曰組合物之透明粒狀物。所製得之熱可塑性樹脂組合物之破璃轉移溫度為125°C。使用該熱可塑性樹脂組合物，與實施例2〇才目同之方式’製作厚度為50…未延伸薄膜。此外，將該薄膜於In the 2226-7326B-PF 70, 20 parts of the acrylic fine particles (manufactured by Sakamoto Co., Ltd.) were melt-kneaded and then injection-molded to prepare a sheet-like molded article of 15 〇眶 15 〇 x 3 mm. The thin moon-shaped molded article was obtained, and the total light transmittance was 85%, and the enthalpy was 75% ‘having sufficient characteristics as a diffusion plate. <<Example 20>> "The granules having a lactone ring polymer obtained in Production Example 5 and an acrylonitrile-styrene (AS) resin (T〇y〇-AS AS20, manufactured by Toyo Phenyl Ethylene Co., Ltd.), A transparent granule of a thermoplastic resin composition was obtained by mixing a chain with a uniaxial extruder (0' off) in a mass ratio of a ring polymer/AS resin = 9 Å / 1 Torr. The glass transition temperature of the thermoplastic resin composition was 127 C. The thermoplastic resin composition was dissolved in methyl ethylamine, and a 60" thick unstretched film was produced by a solution prayer method. At the temperature ι〇. . . , with a speed extension of .lm/min, uniaxially extending the thinner by 5 times, and producing a stretch film of 50" m. The results of the evaluation of the optical properties of the film extension film are shown in Table 4. <<Example 21>> = and Example 2. Similarly, the inner vinegar ring polymer/as resin:. A mass ratio of /20 was mixed with a single extruder to obtain a transparent granule of the thermoplastic tree 1 曰 composition. The resulting glass transition temperature of the thermoplastic resin composition was 125 °C. Using this thermoplastic resin composition, a film having a thickness of 50...unstretched was produced in the same manner as in Example 2'. In addition, the film is

2226-7326B-PF 71 Ι3ύ1809 與實施例20同樣的條件下，單轴延伸1. 5倍，製得厚度為 45απι之延伸薄膜。該等未延伸薄膜、延伸薄膜之光學特 . 性之評估結果示於表4。 . 《實施例22》製造例6所製得之具内酯環聚合物之粒狀物與丙稀腈 -苯乙烯（入3)樹脂（5171〇〇1^(音譯）（1〇43783，旭化成公司製造），以具内酯環聚合物/AS樹脂=90/10之質量比，使用鲁單軸擠壓機混鍊，製得熱可塑性樹脂組合物之透明粒狀物。所製得之熱可塑性樹脂組合物之玻璃轉移溫度為12 8 °C。使用§亥熱可塑性樹脂組合物，與實施例2 〇相同之方式’製作厚度72 v m之未延伸薄膜《將該薄膜於與實施例 20同樣之條件下，單軸延伸h 5倍，製得厚度為55〆m之延伸溥膜。6亥專未延伸薄膜、延伸薄膜之光學特性之評估結果示於表4。鲁《比較例3》使用製造例5所製得之具内酯環聚合物之粒狀物，以溶液鑄模法，製作厚度為50# m之未延伸薄膜。將該薄膜於與實施例20同樣之條件下’單轴延# 15倍，製得厚度為4〇/zm之延伸薄膜。該等未延伸薄膜、延伸薄膜之光學特性之評估結果示於表4。 2226-7326B-PF 72 1361809 表4 光學用平面狀熱可塑性樹脂組合物(Β) 厚度 ("ΠΊ) 玻璃轉移溫度（°C) 平面方向之相當於 100//m之相位差 (nm) 全光線穿透率(％) 實施例20 未延伸薄膜 60 127 0.5 93.5 延伸薄膜 50 2.8 93.0 實施例21 未延伸薄膜 50 125 1.0 —膜 45 5.3 92.9 η方&例22 未延伸薄膜 72 128 0.5 92.8 延伸薄膜 55 1.7 93.0 比較例3 未延伸膜 50 131 1.2 93.0 延伸薄膜 40 33.5 93.1 由表4可知，實施例2〇、2i及22之薄膜，由於在具内醋壤聚合物中配合丙烯腈-苯乙烯（AS)樹脂，於平面方向之相位差與延伸前後無大變化，於設定之範圍内（20nm以下）獲知。再者，配合AS樹脂，玻璃轉移溫度及全光線穿透率亦無大變化’無損及具内酯環聚合物原本具有之透明性及耐熱性。相對於此，未配合AS樹脂，雖然透明性及耐熱性優 •異但於經延伸時’平面方向之相位差變大，不適於光學用途。因此’含有具内g旨環之聚合物以及與前述聚合物為熱力學性相溶之熱可塑性樹脂組合物作為主成分之光學用平面狀熱可塑性樹脂組合物⑻，除了優異之透明性及耐熱性之外，可知於光學等向性亦優異。產業上可利用性本發明之光學用, 面狀熱可塑性樹脂組合物，可適合2226-7326B-PF 71 Ι3ύ1809 Under the same conditions as in Example 20, uniaxially extending 1.5 times, an extended film having a thickness of 45απι was obtained. The evaluation results of the optical properties of the unstretched film and the stretched film are shown in Table 4. [Example 22] A granule having a lactone ring polymer prepared in Production Example 6 and an acrylonitrile-styrene (into 3) resin (5171〇〇1^(transliteration) (1〇43783, Asahi Kasei) The company manufactures a transparent granule of a thermoplastic resin composition by using a mixture of a lactone ring polymer/AS resin = 90/10 in a mass ratio of a uniaxial extruder to obtain a transparent granule. The glass transition temperature of the plastic resin composition was 12 8 ° C. An unstretched film having a thickness of 72 vm was produced in the same manner as in Example 2, using the ○Her thermoplastic resin composition, and the film was formed in the same manner as in Example 20. Under the condition, the uniaxially stretched h 5 times, the extended ruthenium film with a thickness of 55 〆m was obtained. The evaluation results of the optical properties of the 6 hai special unstretched film and the stretched film are shown in Table 4. Lu "Comparative Example 3" The pellet of the lactone ring polymer obtained in Production Example 5 was subjected to a solution casting method to prepare an unstretched film having a thickness of 50 # m. The film was subjected to the same conditions as in Example 20 to be uniaxially stretched. #15倍, an extension film having a thickness of 4 〇/zm is produced. The unstretched film, extension The evaluation results of the optical properties of the film are shown in Table 4. 2226-7326B-PF 72 1361809 Table 4 Planar thermoplastic resin composition for optical (Β) Thickness ("ΠΊ) Glass transition temperature (°C) Phase difference (nm) at 100//m Total light transmittance (%) Example 20 Unstretched film 60 127 0.5 93.5 Stretch film 50 2.8 93.0 Example 21 Unstretched film 50 125 1.0 - Film 45 5.3 92.9 η square &Example 22 Unstretched film 72 128 0.5 92.8 Extended film 55 1.7 93.0 Comparative Example 3 Unstretched film 50 131 1.2 93.0 Extended film 40 33.5 93.1 As can be seen from Table 4, the films of Examples 2, 2i and 22 were The acrylonitrile-styrene (AS) resin is blended in the vinegar-earth polymer, and the phase difference in the plane direction does not change greatly before and after the extension, and is within the set range (below 20 nm). Further, with AS resin, glass transfer There is no significant change in temperature and total light transmittance'. It does not impair the transparency and heat resistance of the lactone ring polymer. In contrast, the AS resin is not blended, although the transparency and heat resistance are excellent. extend 'The phase difference in the planar direction is large, and it is not suitable for optical use. Therefore, 'the planar heat of optics containing a polymer having an inner ring and a thermoplastic resin composition which is thermodynamically compatible with the polymer as a main component. In addition to the excellent transparency and heat resistance, the plastic resin composition (8) is also excellent in optical isotropic properties. INDUSTRIAL APPLICABILITY The optical, planar thermoplastic resin composition of the present invention can be suitably used.

2226-7326B-PF 73 1361809 於例如液晶顯示裝置及電漿顯示 b5 _ DO 、有機el顯示裝置蓉承面顯不器或紅外線感應器、光裝置專千分子材粗# 反導專中使用作為光學用高材科。特別是適合於光學用保護薄膜、光學薄膜、光學薄以以^。子屬膜先【圖式簡單說明】第1圖係於實施例5所製作之偏光板之概略圖。2226-7326B-PF 73 1361809 For example, liquid crystal display device and plasma display b5 _ DO, organic EL display device Rong Cheng surface display or infrared sensor, optical device special molecular material coarse # anti-conducting special use as optical Use high material. In particular, it is suitable for optical protective films, optical films, and optical thinners. Sub-film first [Simplified description of the drawings] Fig. 1 is a schematic view of a polarizing plate produced in Example 5.

第2圖係於實施例1 6及18所製作之背光單元之概略【主要元件符號說明】 2〜保護膜； 11 ~導光板； 13〜反射薄片； 15〜反射板。 1〜偏光膜； 3〜保護膜； 12〜擴散薄片（擴散薄膜）；〜螢光管；搴Fig. 2 is a schematic view of a backlight unit manufactured in Examples 16 and 18 [Description of main components] 2 to a protective film; 11 to a light guide plate; 13 to a reflective sheet; 15 to a reflection plate. 1 ~ polarizing film; 3 ~ protective film; 12 ~ diffusion sheet (diffusion film); ~ fluorescent tube;

2226-7326B-PF 742226-7326B-PF 74

Claims

1361809 —第_爾碎告本丨 101年1月4曰修正替十、申請專利範圍： 1，一種光學用平面狀熱可塑性樹脂成型體，其為延伸成型體’其特徵為：含有50〜100質量％之具有如下式（1)所不之内醋環構造之含有内酯環的聚合物1361809 - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ a polymer containing a lactone ring having an internal vinegar ring structure of the following formula (1)

L式甲，K、R&R3互相獨立地表示氫原子或碳數1至2〇之有機殘基；又，有機殘基可含有氧原子]。 2.如申請專利範圍第1項所述之光學用平面狀熱可塑 —性樹脂成型體，其為延伸薄膜。 • 3·如申請專利範圍第2項所述之光學用平面狀熱可塑性樹脂成型體，其係光學用保護薄膜。 4. 如申請專利範圍3項所述之光學用平面狀熱可塑性 φ樹月曰成型體，其係使用於偏光板之保護薄膜。 5. 如申請專利範圍第3項所述之光學用平面狀熱可塑性樹脂成型體，其於平面方向之相位差為2〇至5〇〇nm。 6. 如申請專利範圍第4項所述之光學用平面狀熱可塑性树月曰成型體’其於平面方向之相位差為2〇至5〇〇nm。 7. 如申請專利範圍第5項所述之光學用平面狀熱可塑性樹脂成型體，其係發揮相位差薄膜之功能。 8. 如申請專利範圍第6項所述之光學用平面狀熱可塑性樹脂成型體，其係發揮相位差薄膜之功能。 2226-7326B-PF1 1361809 第096119940號 1〇1年1月4日修 9_如申請專利範圍第2項所述之光學用平面狀熱可塑性樹月曰成型體’其係光學薄膜，且於平面方向之相位差為 - 20 至 500nm。 • 10.如申請專利範圍第9項所述之光學用平面狀熱可塑性樹脂成型體’其係相位差薄膜。 11. 如申請專利範圍第9項所述之光學用平面狀熱可塑性樹脂成型體，其係視角補償薄膜。 12. 如申請專利範圍第1項所述之光學用平面狀熱可籲塑性樹脂成型體，其係光學薄片，且於平面方向之相位差不足20nm。 13·如申請專利範圍第12項所述之光學用平面狀熱可塑性樹脂成型體，其係擴散板。 14. 如申凊專利範圍第12項所述之光學用平面狀熱可塑性樹脂成型體，其係導光板。 15. 如申請專利範圍第1項所述之光學用平面狀熱可 • 塑性樹脂成型體’其中疊積有一層或一層以上之機能性塗佈層。 16. 如申請專利範圍第15項所述之光學用平面狀熱可塑性樹脂成型體’其中該機能性塗佈層包括紫外線遮斷層、紅外線遮斷層、黏著劑層、反射防止層、硬殼層、光擴散層、電磁波遮斷層、或抗眩光層。 17. —種偏光板，係使用申請專利範圍第4項所述之使用於偏光板之保護薄膜。 18. 一種液晶顯示裝置，係包含申請專利範圍第17項 2226-7326B-PF1 76 [Ϊ3618.09 第096Π9940號〗〇丨年1月4日修正替換頁所述之偏光板。 1 9. 一種液晶顯示裝置，係包含申請專利範圍第1項所 . 述之光學用平面狀熱可塑性樹脂成型體。L-form, K, R& R3 independently of each other represent a hydrogen atom or an organic residue having 1 to 2 carbon atoms; in addition, the organic residue may contain an oxygen atom]. 2. The planar planar thermoplastic resin-molded article for optical use according to claim 1, which is an extended film. The optical planar thermoplastic resin molded body according to the second aspect of the invention, which is an optical protective film. 4. The planar planar thermoplastic φ sap structure according to the invention of claim 3, which is used for a protective film of a polarizing plate. 5. The planar thermoplastic resin molded body for optics according to claim 3, which has a phase difference of from 2 Å to 5 Å in the plane direction. 6. The planar heat-sensitive plastic tree-shaped tantalum molded article for optical use according to claim 4, wherein the phase difference in the planar direction is 2 〇 to 5 〇〇 nm. 7. The planar planar thermoplastic resin molded body for optics according to claim 5, which functions as a phase difference film. 8. The planar planar thermoplastic resin molded body for optical use according to claim 6, which functions as a retardation film. 2226-7326B-PF1 1361809 No. 096119940 No. 096, 1st, 1st, 1st, 1st, 9th, 1st, 2nd, 2nd, 1st, 2nd, 1st The phase difference of the directions is - 20 to 500 nm. 10. The planar thermoplastic resin molded article for optical use according to claim 9 is a retardation film. 11. The planar thermoplastic resin molded article for optics according to claim 9, which is a viewing angle compensation film. 12. The planar planar heat-expandable plastic resin molded body according to claim 1, which is an optical sheet and has a phase difference of less than 20 nm in the planar direction. The planar thermoplastic resin molded body for optics according to claim 12, which is a diffusion plate. 14. The planar thermoplastic resin molded body for optics according to claim 12, which is a light guide plate. 15. The planar planar heat-sensitive plastic molded body for optical use according to claim 1 wherein one or more functional coating layers are laminated. 16. The planar thermoplastic resin molded body for optics according to claim 15, wherein the functional coating layer comprises an ultraviolet shielding layer, an infrared shielding layer, an adhesive layer, an antireflection layer, a hard shell layer, A light diffusion layer, an electromagnetic wave shielding layer, or an anti-glare layer. 17. A polarizing plate which is a protective film for use in a polarizing plate as described in claim 4 of the patent application. 18. A liquid crystal display device comprising the polarizing plate described in the Patent Application No. 17 2226-7326B-PF1 76 [Ϊ3618.09 No. 096Π9940] on January 4th of the following year. A liquid crystal display device comprising the planar thermoplastic resin molded article for optical use according to the first aspect of the invention.

2226-7326B-PF] 772226-7326B-PF] 77