TWI429954B

TWI429954B - A retardation film and a polarizing plate using the same, and a liquid crystal panel

Info

Publication number: TWI429954B
Application number: TW097104693A
Authority: TW
Inventors: Ryo Tamura; Takuhiro Ushino
Original assignee: Jsr Corp
Priority date: 2007-02-05
Filing date: 2008-02-05
Publication date: 2014-03-11
Also published as: KR20090116778A; WO2008096694A1; JP2008191392A; CN101578539A; TW200844486A; CN101578539B

Description

相位差薄膜及使用其之偏光板以及液晶面板Phase difference film and polarizing plate using the same, and liquid crystal panel

本發明有關光學特性優異、即使薄膜其耐熱衝擊性(heat shock resistance)仍然優異的相位差薄膜及使用其之偏光板以及液晶面板。The present invention relates to a retardation film which is excellent in optical characteristics and which is excellent in heat shock resistance of a film, and a polarizing plate and a liquid crystal panel using the same.

環狀烯烴系開環(共)聚合物，係起因於主鏈構造的剛性(rigidity)而玻璃化溫度高，主鏈構造中存在有膨體的基之故，具有非晶性而光線透射係數(light transmission factor)高，且由於折射的各向異性小之故顯示低雙折射性(low double refraction)等的優點，因此作為一種耐熱性、透明性、光學特性方面優異的透明熱塑性聚合物而受矚目。此種環狀烯烴系開環(共)聚合物而言，可例舉：專利文獻1至6所記載者等。The cyclic olefin is a ring-opening (co)polymer which has a high glass transition temperature due to the rigidity of the main chain structure, and has a bulky group in the main chain structure, and has an amorphous property and a light transmission coefficient. (light transmission factor) is high, and exhibits advantages such as low double refraction due to small anisotropy of refraction, and thus is a transparent thermoplastic polymer excellent in heat resistance, transparency, and optical properties. By the attention. The cyclic olefin-based ring-opening (co)polymer may, for example, be described in Patent Documents 1 to 6.

近年來，開始研究如何利用上述特徵，而於多種光學領域中應用環狀烯烴系開環(共)聚合物。又，亦有在嘗試應用於薄膜(film)或片材(sheet)(以下，包括片材統稱為薄膜)，以改良在來的光學用薄膜的問題點。In recent years, research into how to utilize the above characteristics has been made, and a cyclic olefin-based ring-opening (co)polymer has been used in various optical fields. Further, there has been an attempt to apply to a film or a sheet (hereinafter, including a sheet collectively referred to as a film) to improve the problem of the optical film to be used.

亦即，在來作為光學用薄膜所使用之聚碳酸酯、聚酯或三乙醯基乙酸酯等的薄膜，係由於光學彈性常數(optical elastic modulus)大之故有因微小的應力變化而顯現或變化相位差之問題、或耐熱性或吸水變形(water-absorbing deformation)等問題之故，作為能解決此種問題，有一種將環狀烯烴系開環(共)聚合物所製成之薄膜作為光學用的各種薄膜使用之提案。此種用途而言，可例舉：相位差薄膜、偏光板的保護膜、液晶顯示元件用基板等。In other words, a film such as polycarbonate, polyester, or triethyl decyl acetate used as an optical film has a small optical stress due to a large optical elastic modulus. The problem of appearing or changing the phase difference, or the problem of heat resistance or water-induced deformation, as a solution to this problem There is a proposal that a film made of a cyclic olefin-based ring-opening (co)polymer is used as various films for optics. Such a use may, for example, be a retardation film, a protective film of a polarizing plate, or a substrate for a liquid crystal display element.

另一方面，近年來，對移動式電腦或行動電話等所用之LCD(液晶)，有進一步輕量化、薄型化之要求。隨之，對使用於LCD之相位差薄膜，亦需要更薄膜且具有高功能性者，因而由耐熱性及光學特性優異的環狀烯烴系聚合物所製成之薄膜，於是更受矚目。然而發現，僅推動薄膜化時，當裝備於偏光板上而實施耐久性試驗時會產生裂紋等，在耐久性方面有其缺點之情形，而形成問題之所在。On the other hand, in recent years, there has been a demand for further reduction in weight and thickness of an LCD (Liquid Crystal) used for a mobile computer or a mobile phone. In the case of a retardation film for use in an LCD, a thin film and a high functionality are required. Therefore, a film made of a cyclic olefin polymer excellent in heat resistance and optical properties is attracting attention. However, it has been found that when only the film formation is promoted, cracks and the like are generated when the durability test is performed on the polarizing plate, and there are disadvantages in terms of durability, which poses a problem.

專利文獻1：日本專利特開平1-132625號公報專利文獻2：日本專利特開平1-132626號公報專利文獻3：日本專利特開昭63-218726號公報專利文獻4：日本專利特開平2-133413號公報專利文獻5：日本專利特開昭61-120816號公報專利文獻6：日本專利特開昭61-115912號公報Patent Document 1: Japanese Patent Laid-Open No. Hei 1-132225 Patent Document 2: Japanese Patent Laid-Open No. Hei 1-132626 Patent Document 3: Japanese Patent Laid-Open Publication No. SHO 63-218726 Patent Document 4: Japanese Patent Laid-Open No. 2-133413 Patent Document 5: Japanese Patent Laid-Open No. 61-120816 Patent Document 6: Japanese Patent Laid-Open No. 61-115912

本發明，係以提供一種即使在薄膜下仍然耐熱性、耐久性優異的相位差薄膜、以及使用前述相位差薄膜所製得之偏光板及液晶面板作為課題者。The present invention provides a retardation film which is excellent in heat resistance and durability even under a film, and a polarizing plate and a liquid crystal panel which are obtained by using the retardation film as a subject.

本發明人等，著眼於相位差薄膜在屈服點(yield point)下的引張力(tensile force)，發現如調整引張力則即使在薄膜下仍能獲得耐久性優異的相位差薄膜之事實。The inventors of the present invention paid attention to the tensile force of the retardation film at the yield point, and found that the retardation film can be adjusted to obtain a retardation film excellent in durability even under the film.

本發明的相位差薄膜之特徵為：係屬於膜厚30μm以下的環狀烯烴系聚合物薄膜，且準照JIB K7127及K7161而使用啞鈴2號型試片(dumb bell No.2 test piece)並朝向薄膜面內的最大折射率方向與在面內垂直相交之方向實施引張試驗(tension test)時在屈服點下之引張力為8N(牛頓)以上。The retardation film of the present invention is characterized in that it is a cyclic olefin-based polymer film having a film thickness of 30 μm or less, and a dumb bell No. 2 test piece is used in accordance with JIB K7127 and K7161. The tensile force at the yield point when the maximum refractive index direction in the film surface is perpendicular to the in-plane perpendicular direction is 8 N (Newton) or more.

本發明之相位差薄膜，較佳為如將波長550nm下之薄膜面內的最大折射率設為nx、將在薄膜面內與nx垂直相交方向的折射率設為ny、將薄膜厚度方向的折射率設為nz、將薄膜厚度設為d[nm]時，則薄膜面內的相位差R0 (550)[nm]=(nx-ny)×d為60nm以上300nm以下、且薄膜厚度方向的相位差Rth (550)[nm]={(nx+ny)/2-nz}×d為30nm以上300nm以下。The retardation film of the present invention preferably has a maximum refractive index in the plane of the film at a wavelength of 550 nm of nx, a refractive index in the direction perpendicular to the nx in the plane of the film, and a refractive index in the thickness direction of the film. When the ratio is nz and the film thickness is d [nm], the phase difference R0 (550) [nm] = (nx - ny) × d in the film plane is 60 nm or more and 300 nm or less, and the phase in the film thickness direction is obtained. The difference Rth (550) [nm] = {(nx + ny) / 2 - nz} × d is 30 nm or more and 300 nm or less.

在本發明之相位差薄膜之環狀烯烴系聚合物，較佳為具有可以下述式(1)表示之結構單元之聚合物。The cyclic olefin polymer of the retardation film of the present invention is preferably a polymer having a structural unit represented by the following formula (1).

(式(1)中，X為獨立可以式：-CH=CH-表示之基或式：-CH₂ CH₂ -表示之基，R¹ 至R⁶ 分別獨立表示氫原子；鹵素原子；可具有含有氧、氮、硫或矽之結合基之取代或非取代的碳原子數1至10的烴基；或極性基)。 (In the formula (1), X is independently a formula: -CH=CH- represents a group or a formula: -CH ₂ CH ₂ - represents a group, and R ¹ to R ⁶ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; or a polar group) containing a bond of oxygen, nitrogen, sulfur or hydrazine.

本發明之偏光板之特徵為：於起偏極鏡(polarizer)的至少單面上，層合有本發明之相位差薄膜。The polarizing plate of the present invention is characterized in that the retardation film of the present invention is laminated on at least one side of a polarizer.

本發明之偏光板，可於起偏極鏡的至少單面上，介由偏光板保護膜而層合有本發明之相位差薄膜。In the polarizing plate of the present invention, the retardation film of the present invention can be laminated on at least one side of the polarizing mirror through a polarizing plate protective film.

本發明之液晶面板之特徵為：係於液晶顯示元件的至少單面上，層合有本發明之偏光板而成者。The liquid crystal panel of the present invention is characterized in that it is formed by laminating a polarizing plate of the present invention on at least one surface of a liquid crystal display element.

如採用本發明，則即使為膜厚30μm以下的薄膜，仍能製得耐熱性、耐久性優異，光學特性亦優異之相位差薄膜。According to the present invention, even when the film has a film thickness of 30 μm or less, a retardation film excellent in heat resistance and durability and excellent in optical characteristics can be obtained.

本發明之相位差薄膜，即使為薄膜，仍然光學特性及耐熱衝擊性(耐久性)優異之故，很適合使用於光學全部用途，並很適合作為偏光板、液晶面板的材料使用。本發明之偏光板及液晶面板，可將所構成之相位差薄膜作成薄膜者，為輕量且耐久性優異。The retardation film of the present invention is excellent in optical properties and thermal shock resistance (durability) even if it is a film, and is suitable for use in optical all. It is suitable for use as a material for polarizing plates and liquid crystal panels. In the polarizing plate and the liquid crystal panel of the present invention, the retardation film formed can be formed into a film, which is lightweight and excellent in durability.

[發明之最佳實施形態][Best Embodiment of the Invention]

以下，就本發明加以具體說明。Hereinafter, the present invention will be specifically described.

環狀烯烴系聚合物構成本發明之相位差薄膜之環狀烯烴系聚合物，較佳為具有可以上述式(1)表示之結構單元(1)在此，本說明書中，聚合物表示單獨聚合物及共聚物。Cyclic olefin polymer The cyclic olefin polymer constituting the retardation film of the present invention preferably has a structural unit (1) represented by the above formula (1). In the present specification, the polymer means a single polymer and a copolymer.

此種結構單元(1)，可藉由開環聚合而從可以下述式(1m)表示之環狀烯烴系單體(1m)所衍生。Such a structural unit (1) can be derived from a cyclic olefin monomer (1m) represented by the following formula (1m) by ring-opening polymerization.

(式(1m)中，R¹ 至R⁶ ，係如前述(1)所定義者)。 (In the formula (1m), R ¹ to R ⁶ are as defined in the above (1)).

式(1)或(1m)中，極性基而言，可例舉：羥基、碳原子數1至10的烷氧基、羰氧基、烷氧羰基、芳氧羰基、氰基、醯胺基、醯亞胺基、三有機甲矽烷氧基、三有機甲矽烷基、胺基、醯基、烷氧甲矽烷基、磺醯基、以及羧基。更具體方式，就上述烷氧基而言，可例舉：甲氧基、乙氧基等；羰氧基而言，可例舉：乙醯氧基、丙醯氧基等的烷基羰氧基、以及苯醯氧基等的芳基羰氧基；烷氧羰基而言，可例舉：甲氧羰基、乙氧羰基等；芳氧羰基而言，可例舉：苯氧羰基、萘氧羰基、茀氧基羰基、聯苯氧基羰基等；三有機甲矽烷氧基而言，可例舉：三甲基甲矽烷氧基、三乙基矽烷氧基等；三有機甲矽烷基而言，可例舉：三甲基甲矽烷基、三乙基甲矽烷基等；胺基而言，可例舉：一級胺基；烷氧基甲矽烷基而言，可例舉：三甲氧基甲矽烷基、三乙氧基甲矽烷基。In the formula (1) or (1m), the polar group may, for example, be a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a decylamino group. , quinone imine, triorganomethaneoxy, three Mesitylene, amino, mercapto, alkoxymethyl, sulfonyl, and carboxyl. More specifically, the alkoxy group may, for example, be a methoxy group or an ethoxy group; and the carbonyloxy group may, for example, be an alkylcarbonyloxy group such as an ethoxycarbonyl group or a propyloxy group. And an arylcarbonyloxy group such as a benzoquinoneoxy group; the alkoxycarbonyl group may, for example, be a methoxycarbonyl group or an ethoxycarbonyl group; and the aryloxycarbonyl group may, for example, be a phenoxycarbonyl group or a naphthyloxy group. a carbonyl group, a decyloxycarbonyl group, a biphenyloxycarbonyl group or the like; and a triorganomyloxy group, a trimethylmethane alkoxy group, a triethyl decyloxy group, etc.; And may be exemplified by trimethylmethanealkyl, triethylcarbylalkyl, etc.; and the amine group may, for example, be a primary amino group; and the alkoxymethyl sulfonyl group may, for example, be a trimethoxy group. Mercaptoalkyl, triethoxycarbamyl.

鹵素原子而言，可例舉：氟原子、氯原子以及溴原子。The halogen atom may, for example, be a fluorine atom, a chlorine atom or a bromine atom.

碳原子數1至10的烴基而言，可例舉：甲基、乙基、丙基等的烷基；環戊基、環己基等的環烷基；乙烯基、烯丙基、丙烯基等的鏈烯基等。The hydrocarbon group having 1 to 10 carbon atoms may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a vinyl group, an allyl group or a propenyl group; Alkenyl and the like.

又，取代或非取代的烴基，可直接結合於環結構上、或介由結合基(linkage)而結合。結合基而言，可例舉：碳原子數1至10的2元烴基(例如，可以-(CH₂ )_m -(式中，m為1至10的整數)表示之伸烷基)；含有氧、氮、硫或矽之結合基(例如、羰基(-CO-)、氧羰基(-O(CO)-)、磺酸基(-SO₂ -)、醚鍵(-O-)、硫醚鍵(-S-)、亞胺基(-NH)-、醯胺鍵(-NHCO-，-CONH-)、矽氧烷鍵(-OSi(R₂ )-(式中，R為甲基、乙基等的烷基)等，亦可為含有複數個結合基。Further, the substituted or unsubstituted hydrocarbon group may be bonded directly to the ring structure or bonded via a linkage. The binding group may, for example, be a 2-membered hydrocarbon group having 1 to 10 carbon atoms (for example, an alkyl group represented by -(CH ₂ ) _m - (wherein, m is an integer of 1 to 10); a bond of oxygen, nitrogen, sulfur or ruthenium (for example, carbonyl (-CO-), oxycarbonyl (-O(CO)-), sulfonic acid (-SO ₂ -), ether linkage (-O-), sulfur Ether bond (-S-), imine (-NH)-, guanamine bond (-NHCO-, -CONH-), decane bond (-OSi(R ₂ )-(wherein R is methyl An alkyl group such as an ethyl group or the like may contain a plurality of binding groups.

再者，此等基的例示，關於後述之式(2)(2A-m)以及(2B-m)亦同樣。In addition, the examples of these bases are also the same for the following formulas (2) (2A-m) and (2B-m).

此種環狀烯烴系單體(1m)而言，具體上，可例舉：三環[4.3.0.1^2,5 ]癸-3-烯、7-甲基-三環[4.3.0.1^2,5 ]癸-3-烯、8-甲基-三環[4.3.0.1^2,5 ]癸-3-烯、7-乙基-三環[4.3.0.1^2,5 ]癸-3-烯、7-異丙基-三環[4.3.0.1^2,5 ]癸-3-烯、7-環己基-三環[4.3.0.1^2,5 ]癸-3-烯、7-苯基-三環[4.3.0.1^2,5 ]癸-3-烯、7,7-二甲基-三環[4.3.0.1^2,5 ]癸-3-烯、7,8-二甲基-三環[4.3.0.1^2,5 ]癸-3-烯、7-甲基-8-乙基-三環[4.3.0.1^2,5 ]癸-3-烯、7-甲氧羰基-三環[4.3.0.1^2,5 ]癸-3-烯、8-甲氧羰基-三環[4.3.0.1^2,5 ]癸-3-烯、7-苯氧羰基-三環[4.3.0.1^2,5 ]癸-3-烯、7-甲基-7-甲氧羰基-三環[4.3.0.1^2,5 ]癸-3-烯、8-甲基-8-甲氧羰基-三環[4.3.0.1^2,5 ]癸-3-烯、7-氟代-三環[4.3.0.1^2,5 ]癸-3-烯、8-氟代-三環[4.3.0.1^2,5 ]癸-3-烯、7-氯代-三環[4.3.0.1^2,5 ]癸-3-烯、8-氯代-三環[4.3.0.1^2,5 ]癸-3-烯、7,7-二氟代-三環[4.3.0.1^2,5 ]癸-3-烯、 7,8-二氟代-三環[4.3.0.1^2,5 ]癸-3-烯、7,8-二氯代-三環[4.3.0.1^2,5 ]癸-3-烯等，惟不因此等例示而有所限定。Specific examples of such a cyclic olefin monomer (1m) include tricyclo [4.3.0.1 ^2,5 ]non-3-ene and 7-methyl-tricyclo[4.3.0.1 ^{2, 5} ] indole-3-ene, 8-methyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-ethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-isopropyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-cyclohexyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-phenyl-tricyclic [4.3.0.1 ^2,5 ] indol-3-ene, 7,7-dimethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,8-dimethyl-tricyclo[4.3 .0.1 ^2,5 ]non-3-ene, 7-methyl-8-ethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-methoxycarbonyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 8-methoxycarbonyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-phenoxycarbonyl-tricyclo[4.3.0.1 ^2,5 ]癸- 3-ene, 7-methyl-7-methoxycarbonyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 8-methyl-8-methoxycarbonyl-tricyclo[4.3.0.1 ^{2, 5} ] indole-3-ene, 7-fluoro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 8-fluoro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-Chloro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 8-chloro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,7-difluoro- Tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,8-difluoro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,8-Dichloro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, etc., but is not limited by the examples.

又，結構單元(1)，可藉由開環聚合及五員環的加氫，而從以下述式(1m')表示之環狀烯烴系單體(1m')所衍生。Further, the structural unit (1) can be derived from a cyclic olefin monomer (1m') represented by the following formula (1m') by ring-opening polymerization and hydrogenation of a five-membered ring.

(式(1m')中，R¹ 、R² 、R³ 以及R⁵ ，為如前述式(1)中之定義)。 (In the formula (1m'), R ¹ , R ² , R ³ and R ⁵ are as defined in the above formula (1)).

此種環狀烯烴系單體(1m')而言，具體上，可例舉：三環[4.3.0.1^2,5 ]癸-3,7-二烯(DCP)、7-甲基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、8-甲基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、9-甲基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7,8-甲基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-乙基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-環己基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、 7-苯基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-(4-聯苯基)-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-甲基羰基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-苯氧羰基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-甲基-7-甲氧羰基-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-氟代-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7,8-二氟代-三環[4.3.0.1^2,5 ]癸-3,7-二烯、7-氯代-三環[4.3.0.1^2,5 ]癸-3,7-二烯等，惟不因此等例示而有所限定。在本發明，此中特別好用者為三環[4.3.0.1^2,5 ]癸-3,7-二烯。Specific examples of such a cyclic olefin monomer (1m') include tricyclo [4.3.0.1 ^2,5 ] 癸-3,7-diene (DCP), and 7-methyl-three. Ring [4.3.0.1 ^2,5 ]癸-3,7-diene, 8-methyl-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 9-methyl-tricyclo[ 4.3.0.1 ^2,5 ]癸-3,7-diene, 7,8-methyl-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 7-ethyl-tricyclo[ 4.3.0.1 ^2,5 ]癸-3,7-diene, 7-cyclohexyl-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 7-phenyl-tricyclo[4.3. 0.1 ^2,5 ]癸-3,7-diene, 7-(4-biphenylyl)-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 7-methylcarbonyl-three Ring [4.3.0.1 ^2,5 ]癸-3,7-diene, 7-phenoxycarbonyl-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 7-methyl-7- Methoxycarbonyl-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 7-fluoro-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 7,8 -difluoro-tricyclo[4.3.0.1 ^2,5 ]indole-3,7-diene, 7-chloro-tricyclo[4.3.0.1 ^2,5 ]癸-3,7-diene, etc. It is not limited by the illustrations. In the present invention, particularly useful herein is tricyclo[4.3.0.1 ^2,5 ]癸-3,7-diene.

本發明中所用之環狀烯烴系聚合物，更佳為與結構單元(1)一起，具有其他的結構單元。其他的結構單元而言，較佳者可例舉：使具有降冰片烯(norbornen)骨架之環狀烯烴系單體開環共聚合後所衍生之結構單元，又可例舉：使環丁烯、環戊烯、環庚烯、環辛烯等的環烯烴系單體開環共聚合後所衍生之構造單元、使於聚丁二烯、苯乙烯-丁二烯共聚物、乙烯-非共軛二烯共聚物、聚降冰片烯等的主鏈上具有烯烴性不飽和鍵之不飽和烴系聚合物等共聚合後所衍生之結構單元。本發明中所用之環狀烯烴系聚合物，特佳為：僅具有使結構單元(1)、與環狀烯烴系單體開環共聚合後所衍生之結構單元之共聚物為宜。又，不含結構單元(1)，而使具有其他的降冰片烯骨架之環狀烯烴系單體開環聚合後所得之聚合物，亦可作為本發明中所用之環狀烯烴系聚合物使用。The cyclic olefin-based polymer used in the present invention preferably further has other structural units together with the structural unit (1). In other structural units, a structural unit derived by ring-opening copolymerization of a cyclic olefin monomer having a norbornen skeleton may be mentioned, and a cyclobutene is also exemplified. a structural unit derived from ring-opening copolymerization of a cycloolefin monomer such as cyclopentene, cycloheptene or cyclooctene, or a polybutadiene, a styrene-butadiene copolymer, or an ethylene-non-co- A structural unit derived from copolymerization of an unsaturated hydrocarbon-based polymer having an olefinic unsaturated bond in a main chain such as a conjugated diene copolymer or polynorbornene. The cyclic olefin polymer used in the present invention is particularly preferably a copolymer having only a structural unit derived from ring-opening copolymerization of the structural unit (1) and a cyclic olefin monomer. Further, the polymer obtained by ring-opening polymerization of a cyclic olefin monomer having another norbornene skeleton may be used as the cyclic olefin polymer used in the present invention, without the structural unit (1). .

本發明中所用之環狀烯烴系聚合物，更佳為可以前述式(1)表示之結構單元(1)一起，具有可以下述式(2)表示，式(2)中的R⁷ 至R¹⁰ 的至少1個為極性基、且其他R⁷ 至R¹⁰ 的至少1個為碳原子數1至10的烴基之結構單元(2A)及/或可以下述式(2)表示，而R⁷ 至R¹⁰ 均非極性值之結構單元(2B)為宜。再者，本發明中所用之環狀烯烴系聚合物，特佳為具有結構單元(1)、與結構單元(2A)與結構單元(2B)。The cyclic olefin polymer used in the present invention is preferably a structural unit (1) represented by the above formula (1), and may have the following formula (2): R ⁷ to R in the formula (2) hydrocarbon structural units of at least one polar group, and the other R ¹⁰ is at least 1 to ⁷ carbon atoms R ¹⁰ represents 1 to 10 (2A) and / or may be of the following formula (2), and R ⁷ It is preferred that the structural unit (2B) having a non-polar value to R ¹⁰ is suitable. Further, the cyclic olefin polymer used in the present invention particularly preferably has a structural unit (1), a structural unit (2A) and a structural unit (2B).

(式(2)中，X為獨立以式：-CH=CH-表示之基或式：-CH₂ CH₂ -表示之基，R⁷ 至R¹⁰ 為分別獨立表示氫原子；鹵素原子；可具有含有氧、氮、硫或矽之結合基之取代或非取代的碳原子數1至10的烴基；或極性基)。 (In the formula (2), X is a group represented by the formula: -CH=CH- or a formula: -CH ₂ CH ₂ -, and R ⁷ to R ¹⁰ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; or a polar group) having a bond group containing oxygen, nitrogen, sulfur or hydrazine.

結構單元(2A)，係可以下述式(2m)表示，可從式(2m)中的R⁷ 至R¹⁰ 的至少1個為極性基、且其他的R⁷ 至R¹⁰ 的至少1個為碳原子數1至10的烴基之環狀烯烴系單體(2A-m)藉由開環共聚合所衍生，結構單元( 2B)則可以下述式(2m)表示，可從R⁷ 至R¹⁰ 均非極性基之結構單元(2B-m)藉由開環共聚合所衍生者。The structural unit (2A) may be represented by the following formula (2m), and at least one of R ⁷ to R ¹⁰ in the formula (2m) may be a polar group, and at least one of the other R ⁷ to R ¹⁰ may be The cyclic olefin monomer (2A-m) having a hydrocarbon group having 1 to 10 carbon atoms is derived by ring-opening copolymerization, and the structural unit (2B) can be represented by the following formula (2m), which can be from R ⁷ to R The structural unit (2B-m) of each of ¹⁰ non-polar groups is derived by ring-opening copolymerization.

(式(2m)中，R⁷ 至R⁹ ，為如前述式(2)中之定義)。 (In the formula (2m), R ⁷ to R ⁹ are as defined in the above formula (2)).

此種環狀烯烴系單體(2A-m)而言，具體上，可例舉：5-甲基-5-甲氧羰基-雙環[2.2.1]庚-2-烯、5-甲基-5-苯氧羰基-雙環[2.2.1]庚-2-烯、5-甲基-6-甲氧羰基-雙環[2.2.1]庚-2-烯、5-甲基-6-苯氧羰基-雙環[2.2.1]庚-2-烯、8-甲基-8-甲氧羰基-四環[4.4.0.1^2,5 .1^7,10 ]-3-十二烯、8-甲基-8-乙氧羰基-四環[4.4.0.1^2,5 .1^7,10 ]-3-十二烯、8-甲基-8-正丙氧羰基-四環[4.4.0.1^2,5 .1^7,10 ]十二-3-烯、8-甲基-8-異丙氧羰基-四環[4.4.0.1^2,5 .1^7,10 ]十二-3-烯、8-甲基-8-正丁氧羰基-四環[4.4.0.1^2,5 .1^7,10 ]十二-3-烯、8-甲基-8-苯氧羰基-四環[4.4.0.1^2,5 .1^7,10 ]十二-3-烯、等，惟不因此等例示而有所限定。Specific examples of such a cyclic olefin monomer (2A-m) include 5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene and 5-methyl group. -5-phenoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-6-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-6-benzene Oxycarbonyl-bicyclo[2.2.1]hept-2-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 8- Methyl-8-ethoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 8-methyl-8-n-propoxycarbonyl-tetracyclo[4.4.0.1 ^{2 ,5} .1 ^7,10 ]dodec-3-ene, 8-methyl-8-isopropyloxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8 -methyl-8-n-butoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyl-8-phenoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^12-3 -ene, etc., but is not limited by the examples.

在此，結構單元(2A)及環狀烯烴系單體(2A-m)，較佳為其極性基係可以下述式(3)表示之基。亦即，式(2)或(2m)中的R⁷ 至R¹⁰ 的至少1個，較佳為可以下述式(3)表示之基。Here, the structural unit (2A) and the cyclic olefin monomer (2A-m) are preferably a group represented by the following formula (3). In other words, at least one of R ⁷ to R ¹⁰ in the formula (2) or (2m) is preferably a group represented by the following formula (3).

-(CH₂ )_p COOR'………(3) (式(3)中，p為0或1至5的整數，R'為碳數1至15的烴基)。-(CH ₂ ) _p COOR' (3) (In the formula (3), p is an integer of 0 or 1 to 5, and R' is a hydrocarbon group having 1 to 15 carbon atoms).

上述式(3)中，由於p值愈小者、或R'的碳數愈小者，所得之共聚物的玻璃化溫度增高而耐熱性將獲提升之故很合適。亦即，p值通常為0或1至5的整數，惟較佳為0或1，而R'通常為碳數1至15的烴基，惟較佳為碳數1至3的烷基為宜。In the above formula (3), the smaller the p value or the smaller the carbon number of R', the higher the glass transition temperature of the obtained copolymer, and the heat resistance is improved. That is, the p value is usually an integer of 0 or 1 to 5, preferably 0 or 1, and R' is usually a hydrocarbon group having 1 to 15 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms is suitable. .

再者，如於上述式(2)中，具有於經結合上述一般式(3)所表示之極性基之碳原子上再結合有烷基之結構單元(2A)時，則由於共聚物的耐熱性與吸水(濕)性間之平衡優異之故很合適。該烷基的碳數，較佳為1至5、更佳為1至2、特佳為1。Further, in the above formula (2), when the structural unit (2A) having an alkyl group bonded to the carbon atom represented by the above general formula (3) is further bonded, the heat resistance of the copolymer is It is suitable for the balance between sex and water absorption (wet). The carbon number of the alkyl group is preferably from 1 to 5, more preferably from 1 to 2, particularly preferably 1.

又，環狀烯烴系單體(2B-m)而言，具體上可例舉：雙環[2.2.1]庚-2-烯、四環[4.4.0.1^2,5 .1^7,10 ]十二-3-烯、六環[6.6.1.1^3.6 .1^10.13 .0^2.7 .0^9.14 ]庚-4-烯、5-乙基-雙環[2.2.1]庚-2-烯、5-甲基-雙環[2.2.1]庚-2-烯等，惟並不因此等例示而有所限定。此等之中，雙環[2.2.1]庚-2-烯特別好用。Further, the cyclic olefin monomer (2B-m) may specifically be bicyclo[2.2.1]hept-2-ene or tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]10 Di-3-ene, hexacyclo[6.6.1.1 ^3.6 .1 ^10.13 .0 ^2.7 .0 ^9.14 ]hept-4-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-methyl -bicyclo[2.2.1]hept-2-ene, etc., but is not limited by the examples. Among these, bicyclo [2.2.1] hept-2-ene is particularly useful.

本發明中所用之環狀烯烴系聚合物，在全結構單元中按較佳為5莫耳%以上、更佳為5至50莫耳%、特佳為10至40莫耳%的量之方式含有結構單元(1)為宜。又，本發明中所用之環狀烯烴系聚合物的玻璃化溫度(Tg)，可視結構單元(1)的含量而適當加以調節。The cyclic olefin-based polymer used in the present invention is preferably in an amount of 5 mol% or more, more preferably 5 to 50 mol%, particularly preferably 10 to 40 mol%, based on the total structural unit. It is preferred to contain the structural unit (1). Moreover, the glass transition temperature (Tg) of the cyclic olefin polymer used in the present invention can be appropriately adjusted depending on the content of the structural unit (1).

本發明中所用之環狀烯烴系聚合物，如具有結構單元(1)與結構單元(2A)、與結構單元(2B)時，則其含有比例係在全結構單元100莫耳%中，較佳為結構單元(1)5至50莫耳%、結構單元(2A)30至90莫耳%、結構單元(2B)1至30莫耳%、更佳為結構單元(1)10至40莫耳%、結構單元(2A)40至80莫耳%、結構單元(2B)1至20莫耳%。在此，結構單元(1)、(2A)、(2B)的合計係100莫耳%為宜。When the cyclic olefin-based polymer used in the present invention has the structural unit (1), the structural unit (2A), and the structural unit (2B), the content ratio thereof is 100% of the total structural unit. Preferably, the structural unit (1) is 5 to 50 mol%, the structural unit (2A) is 30 to 90 mol%, the structural unit (2B) is 1 to 30 mol%, and more preferably the structural unit (1) is 10 to 40 m. Ear %, structural unit (2A) 40 to 80 mol%, structural unit (2B) 1 to 20 mol%. Here, the total of the structural units (1), (2A), and (2B) is preferably 100% by mole.

有關本發明之環狀烯烴系聚合物，更佳為係一種將前述單體(1m)或(1m')、與前述單體(2A-m)及/或僅前述單體(2B-m)作為單體使用而進行開環共聚合後加氫所得之聚合物。The cyclic olefin polymer of the present invention is more preferably one of the above monomers (1m) or (1m'), the above monomers (2A-m) and/or only the aforementioned monomers (2B-m). The polymer obtained by hydrogenation after ring-opening copolymerization as a monomer is used.

當進行此種單體的共聚合時，可留意所用之各單體的反應性而適當選擇聚合條件後實施。當進行共聚合時，較佳為聚合系中的單體組成比在聚合初期及後期不宜大幅度變化，如單體濃度會經時性變化時，則較佳為在儘早階段中停止聚合，或聚合系內連續性或間歇性供給進行聚合中濃度所減少之單體，以保持單體組成比為一定。如此方式在控制單體組成比中進行共聚合時，則可製得能形成透明性優異的光學薄膜之共聚物。When carrying out the copolymerization of such monomers, attention can be paid to the monomers used. The reaction conditions are appropriately selected after the polymerization conditions are selected. When the copolymerization is carried out, it is preferred that the monomer composition ratio in the polymerization system is not drastically changed in the initial stage and the later stage of the polymerization. If the monomer concentration changes over time, it is preferred to stop the polymerization in the early stage, or The monomer having a reduced concentration in the polymerization is continuously or intermittently supplied in the polymerization system to keep the monomer composition ratio constant. When the copolymerization is carried out in the controlled monomer composition ratio in this manner, a copolymer capable of forming an optical film excellent in transparency can be obtained.

由於僅使各環狀烯烴系單體開環共聚合之開環共聚物，係於其分子內具有烯烴性不飽和鍵而具有耐熱著色等的問題之故，此種烯烴性不飽和鍵較佳為實施加氫步驟，惟此種加氫反應亦可適用周知之方法。例如，適用日本專利特開昭63-218726號公報、日本專利特開平1-132626號公報、日本專利特開平1-240517號公報、日本專利特開平2-10221號公報等中所記載之觸媒或溶劑以及溫度條件等，即可實施開環聚合反應及加氫反應。Since the ring-opening copolymer in which only the cyclic olefin monomer is ring-opened and copolymerized is a problem in that it has an olefinic unsaturated bond in its molecule and has heat-resistant coloring or the like, such an olefinic unsaturated bond is preferred. In order to carry out the hydrogenation step, only such a hydrogenation reaction can be applied to a known method. For example, the catalyst described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The ring-opening polymerization reaction and the hydrogenation reaction can be carried out by using a solvent or a temperature condition.

烯烴性不飽和鍵的加氫率而言，通常為80莫耳%以上、較佳為90莫耳%以上、更佳為95莫耳%以上為宜。在此，本發明中之加氫反應係指，如上所述，對分子內的烯烴性不飽和鍵所實施者，而如本發明中所用之環狀烯烴系聚合物具有芳香族時，有時此種芳香族基可於折射係數等光學特性或耐熱性方面有利方式發揮作用之故，不一定需要實施加氫作業。The hydrogenation rate of the olefinic unsaturated bond is usually 80 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more. Here, the hydrogenation reaction in the present invention means that, as described above, the olefinic unsaturated bond in the molecule is carried out, and when the cyclic olefin polymer used in the present invention has an aromatic group, sometimes Such an aromatic group can function in an advantageous manner in terms of optical characteristics such as refractive index or heat resistance, and it is not always necessary to carry out a hydrogenation operation.

本發明中所用之環狀烯烴系聚合物的分子量而言，利用凝膠滲透色譜法(GPC)所測定之聚苯乙烯換算的數平均分子量(Mn)在通常為8,000至1,000,000、較佳為10,000至500,000、更佳為10,000至100,000，又，聚苯乙烯換算的重量平均分子量(Mw)在通常為10,000至3,000,000、較佳為20,000至1,000,000、更佳為30,000至500,000的範圍為宜。如分子量過小時，則所得薄膜可能會成為強度低者。另一方面，如分子量過大時，則溶液黏度過高亦可能本發明之共聚物的生產性或加工性會惡化。The molecular weight of the cyclic olefin polymer used in the present invention is a polystyrene-converted number measured by gel permeation chromatography (GPC). The average molecular weight (Mn) is usually from 8,000 to 1,000,000, preferably from 10,000 to 500,000, more preferably from 10,000 to 100,000, and further, the polystyrene-equivalent weight average molecular weight (Mw) is usually from 10,000 to 3,000,000, preferably 20,000. A range of from 1,000,000, more preferably from 30,000 to 500,000 is preferred. If the molecular weight is too small, the resulting film may become low in strength. On the other hand, if the molecular weight is too large, the viscosity of the solution is too high, and the productivity or workability of the copolymer of the present invention may be deteriorated.

又，本發明中所用之環狀烯烴系聚合物的分子量分佈(Mw/Mn)，通常為1.5至10、較佳為2至8、更佳為2.5至5為宜。Further, the molecular weight distribution (Mw/Mn) of the cyclic olefin-based polymer used in the present invention is usually from 1.5 to 10, preferably from 2 to 8, more preferably from 2.5 to 5.

本發明中所用之環狀烯烴系聚合物，在23℃下之飽和吸水率，通常為0.01至1重量%、較佳為0.05至0.7重量%、更佳為0.1至0.5重量%為宜。如本發明中所用之環狀烯烴系聚合物的飽和吸水率在上述範圍內，則由於所得薄膜的各種光學特性、透明性、相位差以及相位差的均勻性、或尺寸精確度，即使在高溫多濕的條件下仍能穩定維持之同時，與其他材料的密合性‧黏接性優異之故，使用中不致於發生剝離時，又，由於與抗氧化劑等的添加劑的相溶性亦良好之故，添加劑的種類及添加量的選擇自由度會增大。The cyclic olefin polymer used in the present invention preferably has a saturated water absorption at 23 ° C of 0.01 to 1% by weight, preferably 0.05 to 0.7% by weight, more preferably 0.1 to 0.5% by weight. When the saturated water absorption of the cyclic olefin-based polymer used in the present invention is within the above range, the optical properties, transparency, phase difference, and phase difference uniformity or dimensional accuracy of the obtained film are high even at high temperatures. It can be stably maintained under conditions of excessive humidity, and has good adhesion to other materials. ‧Excellent adhesion, it does not cause peeling during use, and compatibility with additives such as antioxidants is also good. Therefore, the degree of freedom in the selection of the type and amount of the additive increases.

如該飽和吸水率在0.01重量%以下時，則所得薄膜將成為與其他材料的密合性或黏接性低者，以致使用中容易發生剝離，又可能抗氧化劑等的添加劑的添加量受限制。另一方面，如該飽和吸水率在1重量%以上時，則因吸水而容易發生光學特性的變化或尺寸變化。When the saturated water absorption is 0.01% by weight or less, the obtained film will have poor adhesion or adhesion to other materials, so that peeling tends to occur during use, and the amount of additives such as antioxidants may be limited. . On the other hand, if the saturated water absorption rate is 1% by weight or more, it is absorbed by water. It is prone to changes in optical characteristics or dimensional changes.

在此，飽和吸水率，係指準照ASTM D570，在23℃的水中浸漬1星期後測定所增加之重量所求得之值。Here, the saturated water absorption rate refers to a value obtained by measuring the increased weight after immersing in water at 23 ° C for one week in accordance with ASTM D570.

本發明中所用之環狀烯烴系聚合物的玻璃化溫度(Tg)，通常為110至250℃、較佳為115至220℃、更佳為120至200℃。如Tg在110℃以上時，由於具有優異的耐熱性之故較合適。如Tg在110℃以下時，則由於熱變形溫度降低之故，可能在耐熱性上有問題，又可能產生所得薄膜因溫度所引起之光學特性的變化增大之問題。另一方面，如Tg在250℃以上時，則在進行延伸加工時加工溫度過高以致可能本發明之共聚物熱劣化。The glass transition temperature (Tg) of the cyclic olefin-based polymer used in the present invention is usually from 110 to 250 ° C, preferably from 115 to 220 ° C, more preferably from 120 to 200 ° C. When the Tg is 110 ° C or more, it is suitable because of its excellent heat resistance. When the Tg is 110 ° C or less, there is a problem in heat resistance due to a decrease in the heat distortion temperature, and there is a possibility that the change in optical characteristics due to temperature of the obtained film increases. On the other hand, if the Tg is at least 250 ° C, the processing temperature is too high during the elongation processing so that the copolymer of the present invention may be thermally deteriorated.

＜添加劑＞本發明中所用之環狀烯烴系聚合物中，在不影響本發明的效果之範圍內，為耐熱劣化性或耐光性的改良而可添加周知的抗氧化劑或紫外線吸收劑等的添加使用。例如，將選自下述苯酚系化合物、硫醇系化合物、硫化物系化合物、二硫化物化合物、磷系化合物所成群之至少1種化合物，對本發明中所用之聚合物100重量份添加0.01至10重量份，則可提升耐熱劣化性。<additive> In the cyclic olefin polymer to be used in the present invention, a known antioxidant or an ultraviolet absorber may be added and used in order to improve the heat deterioration resistance or the light resistance within a range that does not impair the effects of the present invention. For example, at least one compound selected from the group consisting of a phenol-based compound, a thiol-based compound, a sulfide-based compound, a disulfide compound, and a phosphorus-based compound is added to 0.01 part by weight of the polymer used in the present invention. When it is 10 parts by weight, the heat deterioration resistance can be improved.

又，本發明中所用之環狀烯烴系聚合物中，亦可按照作為目的之光學薄膜的特性，而添加其他添加劑。例如，以能製得所著色之薄膜為目的，亦可添加染料、顏料等的著色劑、以能提升所得薄膜的平滑性為特徵，亦可添加調平劑(leveling agent)調平劑而言，可例舉：含氟系非離子表面活性劑、特殊丙烯酸聚合物系調平劑、聚矽氧系調平劑等。Further, in the cyclic olefin polymer used in the present invention, other additives may be added in accordance with the characteristics of the intended optical film. For example, for the purpose of producing a colored film, a coloring agent such as a dye or a pigment may be added, and the smoothness of the obtained film may be improved, and a tone may be added. The leveling agent leveling agent may, for example, be a fluorine-containing nonionic surfactant, a special acrylic polymer-based leveling agent, or a polyfluorene-based leveling agent.

再者，本發明中，如對環狀烯烴系聚合物添加有添加劑時，此種添加劑可在溶解於溶劑之前添加，或可在溶解於溶劑之階段或經溶解後過濾之前添加，亦可在過濾後製膜前添加。Further, in the present invention, when an additive is added to the cyclic olefin-based polymer, the additive may be added before being dissolved in the solvent, or may be added before the solvent is dissolved or after being dissolved, or may be added After filtration, it is added before film formation.

薄膜之成型環狀烯烴系聚合物薄膜之成型方法而言，可例舉：溶液流涎法(溶劑流鑄法)或熔融擠出法等。Film forming The molding method of the cyclic olefin-based polymer film may, for example, be a solution flow method (solvent casting method) or a melt extrusion method.

溶液流涎法，係需將時將環狀烯烴系聚合物溶液過濾後，塗佈於載體(carrier)上，使其乾燥以去除溶劑之方法。The solution flow method is a method in which a cyclic olefin-based polymer solution is filtered, applied to a carrier, and dried to remove a solvent.

所用之載體而言，可例舉：由金屬圓筒(drum)、鋼帶(steel belt)、聚對苯二甲酸乙二醇酯(PET)或聚萘二甲酸乙二醇酯(PEN)等所成之聚酯薄膜、聚四氟乙烯製皮帶等。如作為載體而使用聚酯薄膜時，亦可使用經表面處理之薄膜。在此，表面處理之方法而言，可例舉：一般所實施之親水法處理方法、例如將丙烯酸系聚合物或含磺酸鹽之聚合物進行塗佈或層合(laminate)以形成由此等聚合物所成之層之方法、或利用電暈放電(corona discharge)處理等以提升薄膜表面的親水性之方法等。The carrier to be used may, for example, be a metal drum, a steel belt, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). A polyester film, a Teflon belt, or the like. When a polyester film is used as the carrier, a surface-treated film can also be used. Here, as the method of the surface treatment, a hydrophilic treatment method generally performed, for example, coating or laminating an acrylic polymer or a sulfonate-containing polymer, may be exemplified. A method of forming a layer formed by a polymer, or a method of improving the hydrophilicity of a surface of a film by a corona discharge treatment or the like.

於載體上塗佈作為薄膜形成液之溶液之方法而言，可利用：使用塑模(dies)或塗佈器(coater)之方法、噴漿(spray)法、刷子塗佈法、輥子塗佈(roll coating)法、旋轉塗佈(spin coating)法、浸漬(dip)法等。又如重複塗佈濾液，亦可控制所得薄膜之厚度。For coating a solution of a film forming solution on a carrier, Use: a method using a dies or a coater, a spray method, a brush coating method, a roll coating method, a spin coating method, and dipping ( Dip) law and so on. Alternatively, if the filtrate is repeatedly applied, the thickness of the resulting film can also be controlled.

經如上述方式所製膜之薄膜，通常經過乾燥之過程即成為薄膜。The film formed by the film as described above is usually a film after being dried.

本發明中，乾燥方法並不特別限定，例如可利用藉由多數的輥子而通過乾燥爐內之方法，惟在乾燥過程中如隨著溶劑之蒸發而發生氣泡，則由於會顯著降低所得薄膜的特性之故，為避免起見，較佳為將乾燥過程作成2段以上的複數過程，以控制各過程中之溫度或風量。In the present invention, the drying method is not particularly limited. For example, a method in which the inside of the furnace is dried by a plurality of rolls can be used, but bubbles are generated in the drying process such as evaporation of the solvent, since the resulting film is remarkably lowered. For the sake of avoidance, it is preferable to make the drying process a complex process of two or more stages to control the temperature or the amount of air in each process.

如此方式所得薄膜中之殘留溶劑量，通常為10重量%以下、較佳為5重量%以下、更佳為1重量%以下、特佳為0.5重量%以下。在此，如薄膜中的殘留溶劑量在10重量%以上時，當實際使用該薄膜時會因經時之尺寸變化增大之故不宜。又因殘留溶劑而玻璃化溫度降低、耐熱性亦會降低之故不宜。The amount of the residual solvent in the film obtained in this manner is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. Here, when the amount of the residual solvent in the film is 10% by weight or more, when the film is actually used, it is unfavorable because the dimensional change over time is increased. Further, since the residual temperature causes the glass transition temperature to decrease and the heat resistance to decrease, it is not preferable.

再者，為順利進行後述之延伸過程起見，有時需要將薄膜中的殘留溶劑量適當調節於上述範圍內。具體而言，為藉由延伸定向處理而使薄膜穩定均勻顯現相位差起見，有時將薄膜中的殘留溶劑量作成通常10至0.1重量%、較佳為5至0.1重量%、更佳為1至0.1重量%。如使微量的溶劑殘留於薄膜中，有時延伸定向處理能容易進行、或相位差的控制能容易進行。Further, in order to smoothly carry out the stretching process described later, it is sometimes necessary to appropriately adjust the amount of residual solvent in the film within the above range. Specifically, the amount of residual solvent in the film is usually 10 to 0.1% by weight, preferably 5 to 0.1% by weight, more preferably in order to stabilize the film uniformly and exhibit phase difference by the stretching treatment. 1 to 0.1% by weight. If a small amount of solvent remains in the film, the stretching and orientation treatment can be easily performed, or the control of the phase difference can be easily performed.

藉由熔融擠出法而製得環狀烯烴系聚合物之方法而言，並不特別限定，可適用周知的方法。可例舉：從經組裝於擠出機上之模頭擠出熔融狀態的環狀烯烴系聚合物，並將該聚合物壓貼於鏡面輥(mirror-plane roll)表面，然後，冷卻後剝離，使其片材化之方法。The method for producing a cyclic olefin polymer by a melt extrusion method is not particularly limited, and a known method can be applied. For example, a molten olefin-based polymer is extruded from a die assembled on an extruder, and the polymer is pressed against a surface of a mirror-plane roll, and then peeled off after cooling. , the method of making it sheet.

進行環狀烯烴系聚合物之熔融之方法而言，較佳為利用擠出機以熔融聚合物之方法，較佳為使用齒輪泵(gear pump)以定量供給該熔融聚合物，並利用金屬過濾器將此熔融聚合物過濾以去除不純物後，在使用模頭(die)成型為薄膜形狀之下擠出之方法。In the method of melting the cyclic olefin-based polymer, it is preferred to use a melter to melt the polymer, preferably a gear pump to quantitatively supply the molten polymer, and to filter with the metal. After the molten polymer is filtered to remove impurities, it is formed by extrusion using a die to form a film under the shape of a film.

冷卻經從模頭所擠出之薄膜並使其片材化之方法而言，可例舉：夾輥(nip roll)方式、施加靜電之方式、空氣刮刀(air knife)方式、壓延機(calender)方式、片面皮帶方式、雙面皮帶方式、三輥(three-rolls)方式等，惟為欲製造光學失真(optical strain)少的片材時，很適合採用：片面皮帶式、尤其稱為套筒(sleeve)方式之片材製造裝置、施加靜電之方式等。可例舉：於模頭的排出口下方配置有鏡面輥及金屬皮帶，並按與該鏡面輥並行排列之方式配置有剝離輥之薄膜製造裝置。上述金屬皮帶，係藉由按與其內面相接觸之方式所設置之2個支撐輥(supporting roller)而施加張力之狀態所支撐者。從排出口所排出之聚合物，則通過上述鏡面輥與金屬皮帶之間而被夾壓，經轉寫(transeript)於鏡面輥並冷卻後，藉由剝離輥而被剝離而使其薄膜化。又，在所排出之薄膜兩端的位置，從經按模頭的排出口下方的鏡面輥相對向之方式所配置之帶電電極，將薄膜貼合於鏡面輥側，藉以在不致於發生光學失真之下將薄膜表面作成良好之方法亦為很適合的方法。The method of cooling and extruding the film extruded from the die may be exemplified by a nip roll method, a method of applying static electricity, an air knife method, and a calender (calender) ), one-sided belt method, double-sided belt method, three-rolls method, etc., but it is suitable for the production of sheets with less optical strain: one-sided belt type, especially called sleeve A sheet manufacturing apparatus of a sleeve type, a method of applying static electricity, and the like. A film manufacturing apparatus in which a mirror roll and a metal belt are disposed under the discharge port of the die, and a peeling roll is disposed in parallel with the mirror roll is exemplified. The metal belt is supported by a state in which tension is applied by two supporting rollers provided in contact with the inner surface thereof. The polymer discharged from the discharge port is sandwiched between the mirror roll and the metal belt, and is transferred to a mirror roll and cooled, and then peeled off by a peeling roll to be thinned. Also, at the ends of the discharged film The film is attached to the mirror roll side from the opposite side of the mirror roll under the discharge port of the die, so that the film surface can be made a good method without causing optical distortion. A very suitable method.

擠出機而言，可採用單軸、雙軸、衛星式、共捏合機(cokneader)等任一種，惟較佳為採用單軸擠出機。又，擠出機的螺桿(screw)形狀而言，可例舉：排氣(vent)型、副刮板(sub flight)型、前端杜爾梅奇(Dulmage)型、全刮板(full flight)型者，壓縮比大者，小者、壓縮部長度較長的緩慢壓縮、長度較短的快速壓縮型等，惟因氧氣的混入及擠壓部內部之受剪發燒，而容易於聚合物中產生凝膠。由於此種凝膠會成為薄膜中的稱為魚眼(fish eye)之點狀缺陷或泛黃(yellowing)的原因之故，較佳為能抑制氧氣的溶解、並能抑制受剪發燒之刮板形狀‧壓縮型者，較佳之壓縮比為1.5至4.5、特佳為1.8至3.6使用為聚合物的計量之齒輪泵，係可使用內部潤滑式、外部潤滑式之任一種，惟其中較佳為外部潤滑方式。For the extruder, a single shaft, a double shaft, a satellite type, a cokneader or the like may be employed, but a single shaft extruder is preferably used. Further, the shape of the screw of the extruder may be vent type, sub flight type, front end Dulmage type, full flight (full flight) Type, the compression ratio is larger, the smaller one, the compression part is longer, the slow compression, the shorter length, the quick compression type, etc., but the polymer is easy to be polymerized due to the mixing of oxygen and the sheared fever inside the extrusion part. A gel is produced in the middle. Since such a gel may cause a point-like defect or yellowing of a fish eye in a film, it is preferable to suppress the dissolution of oxygen and suppress the scraping of the cut hair. For the shape of the plate and the compression type, the preferred compression ratio is 1.5 to 4.5, and particularly preferably 1.8 to 3.6. The gear pump used for the measurement of the polymer can be either an internal lubrication type or an external lubrication type, but preferably. For external lubrication.

關於使用為異物的過濾之過濾器而言，可例舉：葉盤型(leaf disk type)、燭濾器型(candle filter type)、垂板型(leaf type)、篩孔(screen mesh)等。其中，為減少聚合物的滯留時間分佈之目的而言，最佳為葉盤型、表示過濾器的濾孔之公稱濾孔，為20μm以下、較佳為10μm以下、更佳為5μm以下、最佳為3μm以下。如公稱濾孔在20μm以上時，由於除難於去除可目視之異物之外，難於去除凝膠之故，作為製作光學薄膜用的過濾器而言並不適宜。The filter used for filtering foreign matter may, for example, be a leaf disk type, a candle filter type, a leaf type, a screen mesh or the like. Among them, in order to reduce the distribution of the residence time of the polymer, the preferred pore size of the leaf disc type and the filter pores of the filter is 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less, or most. Good is 3μm or less. If the nominal filter hole is above 20 μm, it is difficult to remove the visible foreign matter. It is difficult to remove the gel, and it is not suitable as a filter for producing an optical film.

作為模頭而言，需要將模頭內部的聚合物流動作成均勻，如欲保持薄膜厚度的均勻性時，在模頭出口附近的模頭內部的壓力分佈，需要在寬幅方向為一定者。能符合此種條件者而言，可採用：歧管式模頭(manifold die)、魚尾形模頭(fish-tail die)、衣架式模頭(coat-hanger die)等，此等之中，較佳為衣架式模頭。又，為模頭的流量調整，較佳為彎曲模唇式(bending-lip type)。又，特佳為具有藉由利用熱螺栓方式(heat bolt type)之自動控制而實施厚薄調整之功能之模頭。由於為流量調整而組裝抑制桿(choke bar)、或組裝為厚度調整之模唇塊(lip block)的作法，可能在組裝部分產生段差、或在組裝部分的間隙等中混藏空氣之結果，成為泛黃(yellowing)發生之原因、或成為掛料線(die line)的原因之故不宜。模頭的排出口，較佳為施加有鎢碳化物等的超硬塗佈等的塗佈。又，模頭的材質而言，可例舉：SCM(鉻鉬鋼)系的鋼鐵、SUS(不鏽鋼)等的不鏽鋼材等，惟並不限定於此等。又，亦可使用：經於表面施加鉻、鎳、鈦等的電鍍者、採用PVD(Physical Vapor Deposition，物理汽相沈積)法等形成有TiN(氮化鈦)、TiAlN(氮化鋁鈦)、TiC(鈦碳化物)、CrN(氮化鉻)、DLC(鑽石狀碳)等的被膜者，經火焰噴射(flame spray)其他陶瓷者，經表面氮化處理者等。由於此等模頭係表面硬度高、與聚合物之間的摩擦小之故，從可防止所製得之透明聚合物片材中混入泛黃垃圾(yellow refuse)等之同時，可防止掛料線來看，很合適。As the die, it is necessary to operate the polymer flow inside the die to be uniform. If the film thickness uniformity is to be maintained, the pressure distribution inside the die near the exit of the die needs to be constant in the width direction. For those who can meet such conditions, a manifold die, a fish-tail die, a coat-hanger die, etc. can be used, among them, A hanger type die is preferred. Further, the flow rate adjustment of the die is preferably a bending-lip type. Further, it is particularly preferable to have a die which is capable of performing thickness adjustment by automatic control using a heat bolt type. Due to the assembly of a choke bar for flow adjustment or a lip block that is assembled into a thickness adjustment, there may be a result of a step difference in the assembly portion, or a mixture of air in the assembly portion, or the like. It is not appropriate to become the cause of yellowing or to become the cause of the die line. The discharge port of the die is preferably coated with a hard coating such as tungsten carbide. In addition, the material of the die is, for example, steel such as SCM (chromium molybdenum steel) or stainless steel such as SUS (stainless steel), but is not limited thereto. Further, it is also possible to use TiN (Titanium Nitride) or TiAlN (Titanium Nitride) by a plating method using chromium, nickel, titanium or the like on the surface and PVD (Physical Vapor Deposition). A film such as TiC (titanium carbide), CrN (chromium nitride), or DLC (diamond-like carbon) is subjected to flame spraying other ceramics, and is subjected to surface nitriding treatment. Due to the high surface hardness and polymerization of these die heads The friction between the materials is small, and it is possible to prevent the yellowing refuse from being mixed into the obtained transparent polymer sheet, and it is suitable to prevent the hanging line from being seen.

鏡面輥，較佳為內部具備有加熱手段及冷卻手段者，其表面粗糙度較佳為0.5μm以下、特佳為0.3μm以下。作成如此方式，即可更提升光學薄膜的透明性、特別是拉伸使用時，可更發揮效果。此時，鏡面輥而言，較佳為使用經於金屬輥上施加有電鍍者、特佳為使用施加有鉻電鍍、無電解鎳電鍍等者。The mirror roll preferably has a heating means and a cooling means inside, and has a surface roughness of preferably 0.5 μm or less, and particularly preferably 0.3 μm or less. In such a manner, the transparency of the optical film can be further improved, and particularly when it is stretched, the effect can be further exerted. In this case, it is preferable that the mirror roll is a person who applies electroplating to a metal roll, and particularly preferably uses chromium plating or electroless nickel plating.

鏡面輥的加熱方法，可作為很合適的方法而採用夾套(jacket)式油溫調方式、或介電(dieleatric)加熱方式等。輥子的加熱方法並不特定限定，惟較佳為輥子的溫度在薄膜製膜範圍而無溫度差者，所容許之輥子的寬幅方向的溫度差較佳為2℃以內、更佳為1℃以內。The heating method of the mirror roll can be a very suitable method using a jacket type oil temperature adjustment method or a dielectric (dieleatric heating method). The heating method of the roller is not particularly limited, but it is preferred that the temperature of the roller is in the film forming range without temperature difference, and the temperature difference in the width direction of the roller to be allowed is preferably within 2 ° C, more preferably 1 ° C. Within.

為單面皮帶式裝置、或套筒(sleave)式捲取裝置所使用之金屬皮帶而言，較佳為採用無接頭之環形皮帶(endless belt)。構成金屬皮帶之材料而言，可使用不鏽鋼、鎳等。又，支撐金屬皮帶之支撐輥，較佳為其表面經以聚矽氧橡膠或其他具有耐熱性之彈性物(elastomer)等被覆者。金屬皮帶的厚度，較佳為0.1至0.4mm、如在0.1mm以上時，由於彎曲(deflection)大而皮帶容易受損之故不宜。另一方面，如較0.4mm為厚時，由於加工時不能追隨薄膜而變形之故不宜。For a metal belt used in a single-sided belt type device or a sleave type winding device, a jointless endless belt is preferably used. As the material constituting the metal belt, stainless steel, nickel, or the like can be used. Further, the support roller for supporting the metal belt preferably has a surface covered with a polyoxyethylene rubber or other heat-resistant elastomer (elastomer) or the like. The thickness of the metal belt is preferably 0.1 to 0.4 mm, and if it is 0.1 mm or more, the belt is easily damaged due to the large deflection. On the other hand, if it is thicker than 0.4 mm, it is not suitable because it cannot be deformed following the film during processing.

利用上述裝置，例如作成下述方式即可製造薄膜。The film can be produced by the above apparatus, for example, in the following manner.

通常，於擠壓機中飼入環狀烯烴系聚合物之前，以預先去除該聚合物中所含之水分、氣體(氧氣等)、殘留溶劑等為目的，在該聚合物的Tg以下的適當溫度之下實施聚合物的乾燥。In general, before the cyclic olefin polymer is fed into the extruder, it is appropriate to remove the water, gas (oxygen, etc.) contained in the polymer, residual solvent, etc., below the Tg of the polymer. Drying of the polymer is carried out at a temperature.

為乾燥所用之乾燥機，較佳為使用惰氣循環式乾燥機、真空乾燥機。又，為抑制加料漏斗(hopper)內吸收水分或氧氣起見，藉由氮氣或氬氣等的惰性氣體密封加料漏斗、或使用能保持於減壓狀態之真空加料漏斗亦很合適的方法。For the dryer used for drying, it is preferred to use an inert gas circulation dryer or a vacuum dryer. Further, in order to suppress absorption of moisture or oxygen in the hopper, it is also suitable to seal the addition funnel by an inert gas such as nitrogen or argon or to use a vacuum addition funnel which can be maintained under reduced pressure.

擠出機汽缸，為防止在熔融擠出中聚合物被氧化而發生凝膠起見，較佳為藉由氮氣或氬氣等的惰性氣體而加以密封。The extruder cylinder is preferably sealed by an inert gas such as nitrogen or argon in order to prevent the gel from being oxidized during melt extrusion.

經由擠出機所熔融之環狀烯烴系聚合物，即被從模頭排出口朝向垂直方向之下方按片狀之方式擠出。模頭出口的溫度分佈，為減少聚合物的熔融黏度差起見，較佳為控制在±1℃以下。The cyclic olefin-based polymer melted through the extruder is extruded in a sheet form from the die discharge port toward the lower side in the vertical direction. The temperature distribution at the exit of the die is preferably controlled to be less than ±1 °C in order to reduce the difference in melt viscosity of the polymer.

然後，所擠出之聚合物即被鏡面輥與金屬皮帶夾壓，並被冷卻。並且經轉寫於鏡面輥表面之聚合物，被剝離用輥而從鏡面輥表面剝離後，即可製得片材狀之薄膜。The extruded polymer is then pinched by the mirror roll and the metal belt and cooled. Further, the polymer which has been transferred onto the surface of the mirror roll is peeled off from the surface of the mirror roll by a peeling roll, and a sheet-like film can be obtained.

＜薄膜延伸加工(film elongation processing)＞經上述方式所得之薄膜，如實施延伸加工(延伸定向處理(elongation orientation processing))，形成薄膜之本發明之共聚物的分子鏈則朝一定方向有規則性定向，而可作成具有對透射光賦與相位差之功能之光學薄膜(相位差薄膜)。<film elongation processing> The film obtained by the above method is subjected to elongation processing (elongation orientation processing), and the molecular chain of the copolymer of the present invention which forms the film is regularly oriented in a certain direction. Further, an optical film (phase difference film) having a function of imparting a phase difference to the transmitted light can be produced.

在此，「有規則性定向」，係指在未延伸的薄膜，薄膜中的高分子化合物(聚合物)的分子鏈不會朝特定方向而形成無規的狀態，相對地，高分子化合物的分子鏈朝薄膜的平面的單軸方向或雙軸方向或者厚度方向形成有規則性方式定向之狀態之意。高分子化合物的定向的規則性程度係各不相同者，可依延伸條件而加以控制。Here, "regular orientation" means that the molecular chain of the polymer compound (polymer) in the film does not form a random state in a specific direction in an unextended film, and relatively, a polymer compound The uniaxial direction or the biaxial direction or the thickness direction of the molecular chain toward the plane of the film is intended to be in a state of being oriented in a regular manner. The degree of regularity of the orientation of the polymer compound is different, and can be controlled according to the extension conditions.

延伸加工法而言，可具體例舉：單向延伸法或雙向延伸法。亦即，可採用：依拉幅機(tenter)法之橫單向延伸法、輥子間壓縮延伸法、利用圓周不相同的兩組輥子之縱單向延伸法、或者經組合橫單向與縱單向之雙向延伸法、依薄膜吹塑成型(inflation)法之延伸法等。The extension processing method may specifically be exemplified by a one-way extension method or a two-way extension method. That is, a transverse unidirectional stretching method according to a tenter method, a compression stretching method between rollers, a longitudinal unidirectional stretching method using two sets of rollers having different circumferences, or a combination of lateral unidirectional and longitudinal directions may be employed. One-way two-way extension method, extension method by film blow molding method, and the like.

如利用單向延伸法時，延伸速度通常為1至5,000%/分鐘、較佳為50至1,000%/分鐘、更佳為100至1,000%/分鐘、特佳為100至500%/分鐘。When the unidirectional stretching method is used, the stretching speed is usually from 1 to 5,000%/min, preferably from 50 to 1,000%/min, more preferably from 100 to 1,000%/min, particularly preferably from 100 to 500%/min.

雙向延伸法而言，可利用朝同時互相相交之兩方向實施延伸之方法或經單向延伸後朝與最初的延伸方向不相同的方向實施延伸之方法。於此等方法中，由於兩個延伸方向軸的相交角度，係按照所需要的特性所決定之故不特別加以限定，惟通常在120至60度的範圍。又，延伸速度可為在各延伸方向相同或不相同，通常為1至5,000%/分鐘、較佳為50至1,000%/分鐘、更佳為100至1,000%/分鐘、特佳為100至500%/分鐘。In the biaxial stretching method, a method of performing stretching in two directions simultaneously intersecting each other or a method of extending in a direction different from the initial extending direction after unidirectional stretching may be utilized. In these methods, the angle of intersection of the axes extending in the two directions is not particularly limited as determined by the required characteristics, but is usually in the range of 120 to 60 degrees. Further, the stretching speed may be the same or different in each extending direction, and is usually from 1 to 5,000%/min, preferably from 50 to 1,000%/min, more preferably from 100 to 1,000%/min, particularly preferably from 100 to 500. %/minute.

於延伸加工之加工溫度，並不特別加以限定，惟如將構成薄膜之環狀烯烴系聚合物的玻璃化溫度作為Tg時，通常為在Tg-5℃至Tg+20℃、較佳為Tg至Tg+10℃的範圍為宜。如將處理溫度作成上述範圍，則由於能抑制高的相位差及相位差不均的發生，又折射率橢圓體(indox ellipsoid)的控制會成為容易之故很合適。The processing temperature for the stretching process is not particularly limited. However, when the glass transition temperature of the cyclic olefin polymer constituting the film is Tg, it is usually from Tg - 5 ° C to Tg + 20 ° C, preferably Tg. A range of up to Tg + 10 ° C is preferred. When the treatment temperature is made into the above range, since it is possible to suppress the occurrence of high phase difference and phase difference unevenness, it is easy to control the refractive index ellipsoid (indox ellipsoid).

延伸倍率，係由於按照所需要的相位差等的特性所決定之故不特別加以限定，惟通常為1.01至10倍、較佳為1.03至5倍、更佳為1.03至3倍。The stretching ratio is not particularly limited as long as it is determined according to the characteristics of the required phase difference or the like, but is usually 1.01 to 10 times, preferably 1.03 to 5 times, more preferably 1.03 to 3 times.

經延伸之薄膜，可直接在室溫下冷卻，並在Tg-100℃至Tg程度的溫度氣氛下至少保持10秒鐘以上、較佳為30秒鐘至60分鐘、更佳為1分鐘至60分鐘後熱固(heat-setting)，然後，較佳為冷卻至室溫，則可製得透射光的相位差的經時變化少且穩定的相位差薄膜。The stretched film can be directly cooled at room temperature and maintained at a temperature of from about Tg-100 ° C to Tg for at least 10 seconds, preferably from 30 seconds to 60 minutes, more preferably from 1 minute to 60 minutes. After a minute, heat-setting, and preferably cooling to room temperature, a retardation film having a small change in phase of the transmitted light with a small change over time can be obtained.

經上述方式所得之本發明之相位差薄膜，係由於因延伸而分子經定向之故成為對透射光賦與相位差者，惟此種相位差，如藉由延伸倍率或延伸前的厚度等之調整即可控制。例如，延伸倍率而言，由於即使延伸前的厚度相同的薄膜，有延伸倍率愈大的薄膜對透射光的相位差的絕對值會愈大的傾向之故，藉由延伸倍率之改變即可製得能對透射光賦與所需要的相位差之薄膜。又，延伸前的薄膜厚度而言，由於即使延伸倍率相同，有延伸前的薄膜厚度愈厚對透射光所賦與之相位差的絕對值會愈大的傾向之故，藉由延伸前的薄膜厚度之改變即可製得能對透射光賦與所需要的相位差之光學薄膜。The retardation film of the present invention obtained in the above manner is a phase difference between the transmitted light due to the orientation of the molecules due to the extension, but the phase difference is, for example, by the stretching ratio or the thickness before stretching. Adjustments can be controlled. For example, in the case of the stretching ratio, even if the film having the same thickness before stretching has a tendency that the absolute value of the phase difference of the transmitted light is larger as the film having the larger stretching ratio, the elongation ratio can be changed. A film that imparts the desired phase difference to the transmitted light. Further, in the film thickness before stretching, even if the stretching ratio is the same, the thicker the film thickness before stretching, the greater the absolute value of the phase difference imparted by the transmitted light tends to be, and the film before stretching The change in thickness can be made to impart the required light The desired optical film of phase difference.

＜薄膜特性＞本發明之相位差薄膜，係準照JIS K717及K7161，使用啞鈴2號型試片，而朝與薄膜面的最大折射率方冋垂直相垂之方向進行引張試驗(tension test)時在屈服點之引張力(tensile fonce)為8N以上，較佳為10N以上者。具有在上述值時之屈服點下之引張力之薄膜，即使膜厚30μm以下的薄膜型薄膜，仍然耐熱衝擊性優異、並於耐久性試驗中不會發生裂紋。在此，上述之薄膜面內的最大折射率方向，通常係與延伸方向一致者。因而，例如，係經實施縱單向延伸之薄膜，則按薄膜寬幅方向施加張力之方式製作試片後實施引張試驗，如係經實施橫單向延伸之薄膜，則按薄膜長度方向施加張力之方式製作試片後實施引張試驗。<film properties> The retardation film of the present invention is a JIS K717 and K7161, and uses a dumbbell No. 2 test piece, and is subjected to a tensile test in a direction perpendicular to the maximum refractive index of the film surface. The tensile fonce is 8N or more, preferably 10N or more. The film having the tensile force at the yield point at the above value has excellent thermal shock resistance even in a film-type film having a film thickness of 30 μm or less, and does not cause cracking in the durability test. Here, the direction of the maximum refractive index in the surface of the film described above is generally the same as the direction of extension. Therefore, for example, a film which is longitudinally unidirectionally stretched is subjected to a tensile test in which a tensile test is applied in such a manner that a tensile force is applied in a wide direction of the film, and if a film which is transversely unidirectionally stretched is applied, tension is applied in the longitudinal direction of the film. The test was carried out after the test piece was produced.

又，本發明之相位差薄膜中，對透射光賦與相位差之值，如將光線波長550nm下之薄膜面內的最大折射率設為nx、將在薄膜面內對nx垂直相交之方向的折射率設為ny、將薄膜厚度方向的折射率設為nz、將薄厚度設為d[nm]時，則薄膜面內的相位差R0 (550)[nm]=(nx-ny)×d為60nm以上300nm以下、較佳為90nm以上270nm以下，且薄膜厚度方向的相位差Rth (550)[nm]={(nx+ny)/2-nz}×d為30nm以上300nm以下、較佳為45nm以上300nm以下為宜。該R0及Rth之值，係因用於液晶面板所用之液晶或面板的種類而有所異。Further, in the retardation film of the present invention, the value of the phase difference is given to the transmitted light, such as the maximum refractive index in the film plane at a light wavelength of 550 nm is nx, and the direction perpendicular to nx in the film plane is perpendicularly intersected. When the refractive index is ny, the refractive index in the film thickness direction is nz, and the thin thickness is d [nm], the phase difference R0 in the film plane (550) [nm] = (nx - ny) × d 60 nm or more and 300 nm or less, preferably 90 nm or more and 270 nm or less, and a phase difference Rth (550) [nm] = {(nx + ny) / 2 - nz} × d in the thickness direction of the film is preferably 30 nm or more and 300 nm or less. It is preferably 45 nm or more and 300 nm or less. The values of R0 and Rth are used for the liquid crystal panel. The type of LCD or panel varies.

又，經透射薄膜之光的相位差，較佳為其均勻性高者，具體而言，在光線波長550nm下之偏差通常為±20%以下、較佳為10%以下、更佳為±5%以下為宜。如相位差的偏差超過±20%的範圍時，則當使用為液晶顯示元件等時可能發生發花(floating)等，而產生顯示器本體的性能會降低之問題。同樣，光軸(optical axis)的偏差，通常為±2.0度以下、較佳為±1.0度以下、更佳為±0.5度以下為宜。Further, the phase difference of the light transmitted through the film is preferably such that the uniformity is high. Specifically, the deviation at a light beam wavelength of 550 nm is usually ±20% or less, preferably 10% or less, more preferably ±5. % below is appropriate. When the deviation of the phase difference exceeds the range of ±20%, when a liquid crystal display element or the like is used, floating or the like may occur, which may cause a problem that the performance of the display body is lowered. Similarly, the deviation of the optical axis is usually ±2.0 degrees or less, preferably ±1.0 degrees or less, more preferably ±0.5 degrees or less.

本發明之相位差薄膜的膜厚，為30μm以下、較佳為30至20μm、更佳為30至25μm。如將膜厚作成薄，則可大幅度因應相位差薄膜所使用之領域的製品上所要求的小型化、薄膜化。在此，如欲控制相位差的膜厚時，藉由延伸前的薄膜的膜厚之控制、或藉由延伸倍率之控制即可達成。但，如將膜厚作成過薄時，則由於薄膜的操作處理會發生困難，以致製造時的生產性會降低之故不宜。The film thickness of the retardation film of the present invention is 30 μm or less, preferably 30 to 20 μm, more preferably 30 to 25 μm. When the film thickness is made thin, it is possible to greatly reduce the size and thickness required for the products in the field used for the retardation film. Here, when the film thickness of the phase difference is to be controlled, it can be achieved by controlling the film thickness of the film before stretching or by controlling the stretching ratio. However, if the film thickness is made too thin, the handling of the film may be difficult, so that the productivity at the time of production may be lowered.

偏光板本發明之偏光板之特徵為：於由PVA(聚乙烯醇)系薄膜所成之起偏極鏡的至少一面上層合有本發明之相位差薄膜。相位差薄膜可直接層合於起偏極鏡上、亦可介由偏光板保護膜而層合。偏光板保護膜而言，三乙醯基纖維素(TAC)膜、或未經拉伸之環狀烯烴系聚合體薄膜等特別好用。於起偏極鏡或偏光板保護膜上層合本發明之相位差薄膜之方法而言，可例舉：使用以PVA聚合物為主體之由水溶液所成之水性黏接劑、含有極性基之黏接劑、光硬化性黏接劑等加以貼合，需要時將此加熱或曝光後壓貼之方法。Polarizer The polarizing plate of the present invention is characterized in that the retardation film of the present invention is laminated on at least one surface of a polarizing mirror made of a PVA (polyvinyl alcohol) film. The retardation film may be laminated directly on the polarizing mirror or laminated through the protective film of the polarizing plate. As the polarizing plate protective film, a triethylenesulfonyl cellulose (TAC) film or an unstretched cyclic olefin polymer film or the like is particularly preferably used. Laminating the phase difference of the present invention on a polarizing mirror or a polarizing plate protective film The method of the film may be carried out by using an aqueous adhesive agent made of an aqueous solution mainly composed of a PVA polymer, a binder containing a polar group, a photocurable adhesive, etc., and if necessary, This method of heating or post-exposure pressing.

液晶面板本發明之液晶面板，係於液晶經夾持於2片玻璃基板間所成之液晶顯示元件之至少一面上貼合本發明之偏光板，以使液晶顯示元件與偏光板黏接(層合)，即可製造。LCD panel In the liquid crystal panel of the present invention, the polarizing plate of the present invention is bonded to at least one surface of the liquid crystal display element formed by sandwiching the liquid crystal between the two glass substrates, so that the liquid crystal display element and the polarizing plate are bonded (laminated). , you can make it.

以下，依據實施例再具體說明本發明內容，惟本發明並不因此等實施例而有所限定。另外，下述中，除非特別註解，份或%係以重量為基準者。Hereinafter, the present invention will be specifically described based on the examples, but the present invention is not limited by the examples. In addition, in the following, unless otherwise noted, a part or % is based on weight.

再者，各種物性，係按如下方式所測定或評價者。Further, various physical properties were measured or evaluated as follows.

玻璃化溫度(Tg) 採用精工儀器(Seiko Instruments)公司製DSC6200，按升溫速度每分鐘20℃、在氮氣流下進行測定。Tg，係將微分示差掃描熱量的最大峰值溫度(A點)及較最大峰值溫度為-20℃的溫度(B點)，點繪於示差掃描熱量曲線上，作為以B點為起點之基線(base line)上的切線(tangent line)與以A點為起點之切線的交點所求得者。Glass transition temperature (Tg) DSC6200 manufactured by Seiko Instruments Co., Ltd. was used, and the measurement was carried out under a nitrogen flow at a heating rate of 20 ° C per minute. Tg, which is the maximum peak temperature of differential differential scanning heat (point A) and the temperature with maximum peak temperature of -20 °C (point B), plotted on the differential scanning heat curve as the baseline starting from point B ( The tangent line on the base line is obtained from the intersection of the tangent line starting from point A.

加氫率核磁共振光譜計(NMR)係採用布爾卡(Bruker)公司製AVANCE500，測定溶劑則使用d-(左旋)氯仿以測定¹ H-NMR(氫原子核磁共振)。從5.1至5.8ppm的伸乙烯基、3.7ppm的甲氧基、0.6至2.8ppm的脂肪族質子的積分值算出單體的組成後，算出加氫率。The hydrogenation rate nuclear magnetic resonance spectrometer (NMR) was an AVANCE500 manufactured by Bruker, Inc., and the solvent was measured using d-(left-handed) chloroform to determine ¹ H-NMR (hydrogen nuclear magnetic resonance). The composition of the monomer was calculated from the integral values of the vinyl group of 5.1 to 5.8 ppm, the methoxy group of 3.7 ppm, and the aliphatic proton of 0.6 to 2.8 ppm, and the hydrogenation rate was calculated.

重量平均分子量採用東曹(股)公司製HLC-8020凝膠滲透色譜法(GPC)使用四氫呋喃(THF)溶劑，測定聚苯乙烯換算的重量平均分子量(Mw)、分子量分佈(Mw/Mn)。Mn表示數平均分子量。Weight average molecular weight The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) in terms of polystyrene were measured using a HLC-8020 gel permeation chromatography (GPC) manufactured by Tosoh Corporation using a tetrahydrofuran (THF) solvent. Mn represents a number average molecular weight.

薄膜膜厚採用三豊(股)製的「Decimatic Indicator」以測定薄膜膜厚。Film thickness A "Decimatic Indicator" manufactured by Sanken Co., Ltd. was used to measure the film thickness.

相位差R0及Rth 採用王子計測機器(股)製的「KOBRA-21ADH」，在波長550nm下，測定薄膜面內的相位差R0及薄膜厚度方向的相位差Rth。Phase difference R0 and Rth "KOBRA-21ADH" manufactured by Oji Scientific Instruments Co., Ltd. was used to measure the phase difference R0 in the film plane and the phase difference Rth in the film thickness direction at a wavelength of 550 nm.

於屈服點之引張力按能朝薄膜面內的最大折射率方向與面內垂直相交之方向施加張力方式，製作啞鈴2號型試片。具體而言，經實施縱單向延伸之薄膜，係按能朝薄膜寬幅方向，經橫單向延伸之薄膜，則按能朝薄膜長度方向施加張力之方式，製作試片。就所製得之試片，採用引張試驗機((Instron Japan(股)公司製、萬能材料試驗機5564型)，準照JIS K7127及K7161，依引張速度5mm/分鐘的條件以進行引張試驗，求出於屈服點之引張力。在此，關於本實施例之薄膜，係就具有屈服點的情形加以記述者，惟因厚度或延伸條件之關係，有時不會顯示屈服點而直接裂斷。在此種情形，則將裂斷點(breaking point)之引張力。替代解讀為屈服點之引張力以實施試驗。Tension at the yield point According to the direction of the maximum refractive index in the plane of the film, perpendicular to the in-plane A tension type is applied in the direction to produce a dumbbell type 2 test piece. Specifically, the film which is longitudinally unidirectionally stretched is formed into a film which can extend in one direction in the width direction of the film, and a test piece can be produced in such a manner that tension can be applied in the longitudinal direction of the film. For the test piece prepared, a tensile tester (manufactured by Instron Japan Co., Ltd., Universal Material Testing Machine No. 5564), JIS K7127 and K7161, and a tensile test at a tensile speed of 5 mm/min were used. The tension of the yield point is obtained. Here, the film of the present embodiment is described as having a yield point, but the yield point may not be directly broken due to the thickness or the extension condition. In this case, the tension of the breaking point will be replaced by the tension of the yield point to carry out the test.

耐熱衝擊性(耐久性) 將10cm×10cm的相位差薄膜，使用黏接膜按較薄膜為大的尺寸貼合於厚度1mm的無失真玻璃(undistorted glass)以製造試樣，以目視觀察經在-40℃及85℃分別保持30分鐘之循環重複500循環後的試樣，並將無裂紋者作成良、有裂紋者作成不良之方式加以評價。Thermal shock resistance (durability) A phase difference film of 10 cm × 10 cm was bonded to an undistorted glass having a thickness of 1 mm by using an adhesive film to a large size to produce a sample, which was visually observed at -40 ° C and 85 ° C, respectively. The sample after 500 cycles was repeated for 30 minutes, and the case where the crack-free one was made into a good crack and the crack was made was evaluated.

＜合成例1＞<Synthesis Example 1>

將可以下述式表示之8-甲基-8-甲氧羰基四環[4.4.0.1^2,5 .1^7,10 ]-3-十二烯(DNM)71份、二環戊二烯(DCP)15份、以及雙環[2.2.1]庚-2-烯(NB)1份作為單體使用，與分子量調節劑的1-己烯18份、以及甲苯200份一起飼入於經氮氣置換之反應容器內，並加熱為100℃。8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (DNM) 71 parts, dicyclopentadiene DCP) 15 parts, and 2 parts of bicyclo [2.2.1] hept-2-ene (NB) were used as a monomer, and were fed with nitrogen-substituted 18 parts of 1-hexene and 200 parts of toluene with a molecular weight regulator. The reaction vessel was heated to 100 °C.

對此添加三乙基鋁0.005份、甲醇改性WCl₅₆ (無水甲醇：PhPOCl₂ :WCl₆ =103:630:427重量比)0.005份並反應1分鐘，接著，耗費5分鐘之下追加添加DCP10份及NB3份，再反應45分鐘後，製得DNM/DCP/NB=69.77/26.01/4.23(wt%)的共聚物。0.005 parts of triethylaluminum and 0.005 parts of methanol-modified WCl ₅₆ (anhydrous methanol: PhPOCl ₂ :WCl ₆ =103:630:427 weight ratio) were added thereto and reacted for 1 minute, and then additional DCP10 was added under 5 minutes. After the reaction was carried out for 45 minutes, a copolymer of DNM/DCP/NB = 69.77/26.01/4.23 (wt%) was obtained.

接著，將所製得之共聚物的溶液置入高壓鍋內，再添加甲苯200份。接著，作為反應調整劑而添加十八烷基-3-(3, 5-二第三丁基-4-羥苯基)丙烯酸酯1份及屬於加氫觸媒之RuHCl(CO)[P(C₆ H₅ )]₃ 0.006份，並加熱為155℃後，將氫氣引入反應器並將壓力作成10MPa。然後，維持壓力為10MPa之下，在165℃下進行反應3小時。反應完成後，添加甲苯100重量份、蒸餾水3重量份、乳酸0.72重量份、過氧化氫0.00214重量份，在60℃下加熱30分鐘。然後，添加甲醇200重量份，在60℃下加熱30分鐘，如將此冷卻至25℃時，則分離為2層。去除上澄液500重量份，再添加甲苯350重量份、水3重量份並在60℃下加熱30分鐘，然後添加甲醇240重量份，在60℃下加熱30分鐘，如冷卻至25℃時，則分離為2層。最後，去除上澄液500重量份後，將殘留之聚合物溶液，使用2.0μm、1.0μm、0.2μm的各種過濾片加以過濾。然後，將聚合物固體成分量濃縮至55%、按250℃、4托(torr)、滯留時間1小時的條件實施脫溶劑處理，通過10μm的聚合物過濾片，製得共聚物(1)。所得共聚物(1)，為重量平均分子量(Mw)=6.1×10⁴ 、分子量分佈(Mw/Mn)=3.8、固有黏度(η_inh )=0.52、玻璃化溫度(Tg)=131℃。又，加氫率為99.9%以上。Next, the solution of the obtained copolymer was placed in an autoclave, and 200 parts of toluene was further added. Next, as the reaction regulator, 1 part of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylate was added, and RuHCl(CO) [P() which is a hydrogenation catalyst. After C ₆ H ₅ )] ₃ 0.006 parts and heated to 155 ° C, hydrogen gas was introduced into the reactor and the pressure was made 10 MPa. Then, the pressure was maintained at 10 MPa, and the reaction was carried out at 165 ° C for 3 hours. After completion of the reaction, 100 parts by weight of toluene, 3 parts by weight of distilled water, 0.72 parts by weight of lactic acid, and 0.00214 parts by weight of hydrogen peroxide were added, and the mixture was heated at 60 ° C for 30 minutes. Then, 200 parts by weight of methanol was added, and the mixture was heated at 60 ° C for 30 minutes, and when it was cooled to 25 ° C, it was separated into two layers. 500 parts by weight of the supernatant liquid was removed, 350 parts by weight of toluene and 3 parts by weight of water were added and heated at 60 ° C for 30 minutes, and then 240 parts by weight of methanol was added thereto, and heated at 60 ° C for 30 minutes, for example, when cooled to 25 ° C. Then it is separated into 2 layers. Finally, after removing 500 parts by weight of the supernatant liquid, the residual polymer solution was filtered using various filter sheets of 2.0 μm, 1.0 μm, and 0.2 μm. Then, the amount of the polymer solid component was concentrated to 55%, and the solvent removal treatment was carried out under the conditions of 250 ° C, 4 torr, and a residence time of 1 hour, and the polymer (1) was passed through a 10 μm polymer filter. The obtained copolymer (1) had a weight average molecular weight (Mw) = 6.1 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.8, an intrinsic viscosity (η _inh ) = 0.52, and a glass transition temperature (Tg) = 131 °C. Further, the hydrogenation rate was 99.9% or more.

＜合成例2＞<Synthesis Example 2>

於經氮氣置換之反應容器中置入DNM225份、與雙環[2.2.1]庚-2-烯25份、作為分子量調節劑之1-己烯27份、與作為溶劑之甲苯750份，將此溶液加熱為60℃。接著，於反應容器內的溶液中，添加作為聚合觸媒之含有三甲基鋁1.5莫耳/公升之甲苯溶液0.62份、與含有經以第三丁醇及甲醇改性之六氯化鎢(第三丁醇：甲醇：鎢=0.35莫耳：0.3莫耳：1莫耳)之濃度0.05莫耳/公升的甲苯溶液3.7份，將此全系在80℃下加熱攪拌3小時以進行開環共聚合反應後，製得開環共聚物溶液。225 parts of DNM, 25 parts of bicyclo [2.2.1] hept-2-ene, 27 parts of 1-hexene as a molecular weight modifier, and 750 parts of toluene as a solvent were placed in a reaction vessel substituted with nitrogen. The solution was heated to 60 °C. Next, 0.62 parts of a toluene solution containing 1.5 Mole/L of trimethylaluminum as a polymerization catalyst was added to the solution in the reaction vessel, and tungsten hexachloride modified with a third butanol and methanol was added. Third butanol: methanol: tungsten = 0.35 mol: 0.3 mol: 1 mol) 6.5 parts of a 0.05 mol/liter toluene solution, and the whole system was heated and stirred at 80 ° C for 3 hours to open the ring. After the copolymerization reaction, a ring-opening copolymer solution was obtained.

於此聚合反應中之聚合轉化率為97%，經測定構成所得開環共聚物溶液之開環共聚物的30℃的氯仿中之固有黏度(η_inh )之結果，為0.51dl/克。The polymerization conversion ratio in the polymerization reaction was 97%, and the intrinsic viscosity (η _inh ) in the chloroform at 30 ° C of the ring-opening copolymer of the obtained ring-opening copolymer solution was measured and found to be 0.51 dl / g.

將如此方式製得之開環聚合物溶液4000部飼入高壓鍋中，於此開環聚合物溶液中添加RuHCl(CO)[P(C₆ H₅ )₃ ]₃ 0.48份、將氫氣在10MPa、反應溫度165℃的條件下加熱攪拌3小時以進行加氫反應後，製得共聚物(2)。所得共聚物(2)，為重量平均分子量(Mw)=6.2×10⁴ 、分子量分佈(Mw/Mn)=3.0、固有黏度(η_inh )=0.51、玻璃化溫度(Tg)=130℃。又，加氫率為99.9%以上。4000 parts of the ring-opening polymer solution prepared in this manner was fed into a pressure cooker, and 0.45% of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution, and hydrogen gas was 10 MPa. The copolymer (2) was obtained by heating and stirring for 3 hours under the conditions of a reaction temperature of 165 ° C to carry out a hydrogenation reaction. The obtained copolymer (2) had a weight average molecular weight (Mw) = 6.2 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.0, an intrinsic viscosity (η in _h ) = 0.51, and a glass transition temperature (Tg) = 130 °C. Further, the hydrogenation rate was 99.9% or more.

[實施例1][Example 1]

將共聚物(1)按濃度能成為30%之方式溶解於甲苯中。於此溶液中，作為抗氧化劑，對共聚物100份，添加異戊四醇基肆[3-(3,5-二第三丁基-4-羥苯基)丙酸酯]0.3份、使用日本精線(股)製的篩孔5μm的金屬纖維燒結過濾片，差壓能成為0.4MPa以內之方式控制溶液的流速之下將所得溶液加以過濾後，採用經設置於等級(class)1000的潔淨室(clean room)內之井上金屬工業製的「INVEX實驗室塗佈(labocoater)」，塗佈於藉由丙烯酸系表面處理劑而親水化(易黏接化)處理之厚度100μm的PET(對苯二甲酸乙二醇酯)薄膜(東麗(股)製的[裕美芙U94」)上。接著，對所得液層，在25℃下實施乾燥處理10分鐘，再在101℃ (Tg-30℃)下實施乾燥處理10分鐘，並使其從PET薄膜剝離後，形成厚度50μm的薄膜(1)。又，按與上述同樣方法，形成厚度35μm的薄膜(2)The copolymer (1) was dissolved in toluene so as to have a concentration of 30%. In this solution, as an antioxidant, 0.3 part of the copolymer was added, and 0.3 parts of pentaerythritol ruthenium [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was used. Japanese fine wire (strand) made of 5μm mesh metal fiber sintered filter, the differential pressure can be controlled within 0.4 MPa to control the flow rate of the solution, and the solution is set to 1000. INVEX laboratory coating (Labocoater) manufactured by Inoue Metal Co., Ltd. in a clean room, coated with PET (100 μm thick) treated with an acrylic surface treatment agent (hydrophilic) A film of ethylene terephthalate ([Yufufu U94" made by Toray Co., Ltd.). Next, the obtained liquid layer was subjected to a drying treatment at 25 ° C for 10 minutes, and then dried at 101 ° C (Tg - 30 ° C) for 10 minutes, and peeled off from the PET film to form a film having a thickness of 50 μm (1). ). Further, a film having a thickness of 35 μm was formed in the same manner as above (2)

使用所得薄膜(1)，在拉幅機內加熱為138℃ (Tg+7℃)，按延伸速度300%/分鐘朝縱方向進行不固定橫方向的寬幅之縱單向延伸2.8倍，製得厚度28μm的相位差薄膜。所得相位差薄膜在屈服點之引張力為9.4N。經評價該相位差薄膜之結果，薄膜面內的相位差(R0)為280nm、厚度方向的相位差(Rth)為140nm。耐熱衝擊性係良好者。將其結果表示於表1中。Using the obtained film (1), the film was heated to 138 ° C (Tg + 7 ° C) in a tenter, and the longitudinal direction of the width direction was 2.8 times in the longitudinal direction at an extension speed of 300% / minute. A phase with a thickness of 28 μm Poor film. The resulting retardation film had a tensile force at the yield point of 9.4 N. As a result of evaluation of the retardation film, the phase difference (R0) in the film plane was 280 nm, and the phase difference (Rth) in the thickness direction was 140 nm. The thermal shock resistance is good. The results are shown in Table 1.

[實施例2][Embodiment 2]

採用實施例1所得薄膜(2)，除將延伸條件改變為拉幅機內溫度136℃ (Tg+5℃)、延伸倍率1.4倍以外，其餘則按與實施例1同樣方式實施縱單向延伸，製得厚度29μm、在屈服點之引張力0.8N的相位差薄膜。將所得相位差薄膜的評價結果合併表示於表1中。The film (2) obtained in Example 1 was subjected to longitudinal unidirectional stretching in the same manner as in Example 1 except that the stretching conditions were changed to a tenter temperature of 136 ° C (Tg + 5 ° C) and a stretching ratio of 1.4 times. A retardation film having a thickness of 29 μm and a tensile tension of 0.8 N at the yield point was obtained. The evaluation results of the obtained retardation film are shown in Table 1.

[實施例3][Example 3]

採用實施例1所得薄膜(1)、在拉幅機內加熱為132℃ (Tg+1℃)，按延伸速度300%/分鐘朝橫方向進行經固定縱方向的寬幅之橫單向延伸1.8倍，製得厚度28μm、在屈服點之引張力10.8N的相位差薄膜。將所得相位差薄膜的評價結果，合併表示於表1中。The film (1) obtained in Example 1 was heated to 132 ° C (Tg + 1 ° C) in a tenter, and the transverse direction of the fixed longitudinal direction was extended in the transverse direction at an extension speed of 300% / minute. A retardation film having a thickness of 28 μm and a tensile force of 10.8 N at the yield point was obtained. The evaluation results of the obtained retardation film were collectively shown in Table 1.

[實施例4][Example 4]

將共聚物(1)，按濃度能成為30%之方式溶解於甲苯中。於此溶液中，作為抗氧化劑，對共聚物100份，添加異戊四醇基肆[3-(3,5-二第三丁基-4-羥苯基)丙酸酯]0.3份、使用日本精線(股)製的篩孔5μm的金屬纖維燒結過濾片，差壓能成為0.4MPa以內之方式控制溶液的流速之下將所得溶液加以過濾後，採用雙軸擠出機(東芝機械(股)製；TEM-48)，在藉由3段排氣孔(3-step vent)使甲苯脫氣之下，使用齒輪泵往下游進行擠出，將從擠條模頭(strand die)所流出之樹脂利用冷卻水槽加以冷卻之後送往股線切割機(strand cutter)裁斷為米粒狀後，製得造粒樹脂。The copolymer (1) was dissolved in toluene so as to have a concentration of 30%. In this solution, as an antioxidant, 0.3 part of the copolymer was added, and 0.3 parts of pentaerythritol ruthenium [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was used. Japanese fine wire (strand) made of 5μm mesh metal fiber sintered The filter, the differential pressure can be filtered within a flow rate of 0.4 MPa or less, and the resulting solution is filtered, and then a twin-screw extruder (Toshiba Machine Co., Ltd.; TEM-48) is used. The 3-step vent degases the toluene and uses a gear pump to extrude downstream. The resin flowing from the strand die is cooled by a cooling water tank and sent to the strand cutter. (strand cutter) After cutting into rice grains, a granulated resin was obtained.

將此造粒樹脂在氮氣氣氛之下在100℃下乾燥4小時後送往單軸擠壓機(65mmΦ)，在260℃熔融之下使用齒輪泵實施定量擠出，使用公稱篩孔作成10μmI之日本精線製的金屬纖維燒結過濾片進行熔融過濾，利用衣架式模頭(650mm寬幅)，將模頭出口的間隙作成0.5mm，在260℃下依排出量13公斤/小時，捲取速度8公尺/分鐘行膜狀之擠出。將所擠出之薄膜夾介於表面粗糙度在0.1S(表面粗糙度)的250mmΦ的鏡面輥、與0.3mm厚的金屬皮帶之間，將薄膜表面轉寫於光澤面上。然後，將經從鏡面輥剝取之薄膜壓貼於冷卻輥後剝離薄膜，並於單面貼合掩蔽膜(masking film)，使用捲取機加以捲取，以形成為厚度50μm的薄膜(3)。The granulated resin was dried at 100 ° C for 4 hours under a nitrogen atmosphere, sent to a uniaxial extruder (65 mm Φ), and subjected to quantitative extrusion using a gear pump under 260 ° C melting, using a nominal sieve opening to make a 10 μm I. Japan's fine wire metal fiber sintered filter was melt-filtered, using a coat hanger die (650 mm wide), the gap at the exit of the die was made 0.5 mm, and the discharge rate was 13 kg/hr at 260 ° C. Film extrusion at 8 meters per minute. The extruded film was interposed between a mirror roll having a surface roughness of 0.1 S (surface roughness) of 250 mmφ and a metal belt of 0.3 mm thick, and the surface of the film was transferred onto a glossy surface. Then, the film peeled off from the mirror roll was pressed against a cooling roll, and the film was peeled off, and a masking film was attached to one side, and taken up by a coiler to form a film having a thickness of 50 μm (3) ).

使用所得薄膜(3)，在拉幅機內加熱為139℃ (Tg+8℃)，按延伸速度300%/分鐘進行縱單向延伸2.8倍，製得厚度28μm、在屈服點之引張力9.5N的相位差薄膜。將所得相位差薄膜的評價結果，合併表示於第1表中。Using the obtained film (3), the film was heated to 139 ° C (Tg + 8 ° C) in a tenter, and the longitudinal direction was extended by 2.8 times at an elongation speed of 300% / minute to obtain a thickness of 28 μm and a tensile force at the yield point of 9.5. N phase difference film. The evaluation results of the obtained retardation film were collectively shown in the first table.

[實施例5][Example 5]

除採用共聚物(2)以外，其餘則按與實施例4同樣方式，藉由熔融擠出而形成厚度50μm的薄膜(4)。又，將排出量作成11公斤/小時、9公斤/小時以外，其餘則按與上述同樣方式，以分別形成厚度40μm的薄膜(5)、厚度35μm的薄膜(6)。A film (4) having a thickness of 50 μm was formed by melt extrusion in the same manner as in Example 4 except that the copolymer (2) was used. Further, the discharge amount was changed to 11 kg/hr and 9 kg/hr, and the film (6) having a thickness of 40 μm and a film (6) having a thickness of 35 μm were formed in the same manner as described above.

使用所得薄膜(4)，在拉幅機內加熱為139℃ (Tg+9℃)，按延伸速度300%/分鐘，進行縱單向延伸2.5倍，製得厚度30μm、在屈服點之引張力9.8N的相位差薄膜。將所得相位差薄膜的評價結果，合併表示於表1中。Using the obtained film (4), it was heated to 139 ° C (Tg + 9 ° C) in a tenter, and extended by a longitudinal unidirectional extension of 2.5 times at an elongation speed of 300% / minute to obtain a tensile force at a yield point of 30 μm. 9.8N retardation film. The evaluation results of the obtained retardation film were collectively shown in Table 1.

[比較例1][Comparative Example 1]

採用實施例5所得薄膜(5)，在拉幅機內加熱為135℃ (Tg+5℃)，按延伸速度300%/分鐘，進行縱單向延伸2.5倍，製得厚度25μm、在屈服點之引張力7.2N的相位差薄膜。所得相位差薄膜，係耐熱衝擊性劣差者。將評價結果，合併表示於表1中。The film (5) obtained in Example 5 was heated to 135 ° C (Tg + 5 ° C) in a tenter, and extended in a longitudinal direction by 2.5 times at an elongation speed of 300% / minute to obtain a thickness of 25 μm at the yield point. A phase difference film with a tensile force of 7.2N. The obtained retardation film is inferior to heat shock resistance. The evaluation results are collectively shown in Table 1.

[比較例2][Comparative Example 2]

採用實施例5所得薄膜(6)，在拉幅機內加熱為146℃ (Tg+13℃)，按延伸速度300%/分鐘，進行縱單向延伸1.8倍，製得厚度26μm、在屈服點之引張力7.8N的相位差薄膜。所得相位差薄膜，係耐熱衝擊性劣差者。將評價結果，合併表示於表1中。Using the film (6) obtained in Example 5, the film was heated to 146 ° C (Tg + 13 ° C) in a tenter, and the longitudinal direction was extended 1.8 times at an elongation speed of 300% / minute to obtain a thickness of 26 μm at the yield point. A phase difference film with a tension of 7.8N. The obtained retardation film is inferior to heat shock resistance. The evaluation results are collectively shown in Table 1.

[產業上之利用可能性][Industry use possibility]

本發明之相位差薄膜，即使為薄膜，仍然光學特性及耐熱衝擊性(耐久性)優異之故，很適合使用於光學全部用途，惟特別合適使用於需要輕量化及耐熱性之用途。本發明之相位差薄膜，及使用該薄膜之偏光板以及液晶面板，係除可於行動電話、數位資訊端末機、導航(navigation)、車載用液晶顯示器、移動式液晶顯示器、電子辭典用液晶顯示器等上很適合使用之外，尚可用於液晶監視器、調光器面板(dimmer panel)、OA(辦公室自動化)設備用顯示器、AV(聲視訊號)設備用顯示器等的各種液晶顯示器元件、或電致發光(electroluminescent)顯示元件等。The retardation film of the present invention is excellent in optical properties and thermal shock resistance (durability) even if it is a film, and is suitably used for all optical applications, but is particularly suitably used for applications requiring weight reduction and heat resistance. The retardation film of the present invention, and the polarizing plate and the liquid crystal panel using the same, can be used in mobile phones, digital information end machines, navigation, vehicle liquid crystal displays, mobile liquid crystal displays, and electronic dictionary liquid crystal displays. It is also suitable for use in various liquid crystal display elements such as liquid crystal monitors, dimmer panels, OA (office automation) equipment displays, AV (audiovisual signal) equipment displays, or An electroluminescent display element or the like.

Claims

一種相位差薄膜，其為膜厚30μm以下且具有可以下述式(1)表示之結構單元之聚合物的環狀烯烴系聚合物薄膜，且準照JIS K7127及K7161而使用亞鈴2號型試驗片並朝向薄膜面內的最大折射率方向與在面內垂直相交之方向實施引張試驗時，在屈服點下之引張力為8N以上 (式(1)中，X為獨立地以式：-CH=CH-表示之基或式：-CH₂ CH₂ -表示之基，R¹ 至R⁶ 分別獨立表示氫原子；鹵素原子；可具有含有氧、氮、硫或矽之結合基之取代或非取代的碳原子數1至10的烴基；或極性基)。A retardation film which is a cyclic olefin-based polymer film having a thickness of 30 μm or less and having a polymer of a structural unit represented by the following formula (1), and is used in the JIS K7127 and K7161. When the test piece is subjected to the tensile test in the direction of the maximum refractive index in the plane of the film and the direction perpendicularly intersecting in the plane, the tensile force at the yield point is 8 N or more. (In the formula (1), X is a group represented by the formula: -CH=CH- or a group represented by the formula: -CH ₂ CH ₂ -, and R ¹ to R ⁶ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; or a polar group) having a bond group containing oxygen, nitrogen, sulfur or hydrazine.

如申請專利範圍第1項之相位差薄膜，其中如將波長550nm下之薄膜面內的最大折射率設為nx、將在薄膜面內與nx垂直相交方向的折射率設為ny、將薄膜厚度方向的折射率設為nz、將薄膜厚度設為d[nm]時，則薄膜面內的相位差R0(550)[nm]=(nx-ny)×d為60nm以上300nm以下，且薄膜厚度方向的相位差Rth(550)[nm]-{(nx+ny)/2-nz}×d為30nm以上300nm以下。 The retardation film of claim 1, wherein the maximum refractive index in the plane of the film at a wavelength of 550 nm is nx, the refractive index in the direction perpendicular to the nx in the plane of the film is set to ny, and the film thickness is obtained. When the refractive index in the direction is nz and the thickness of the film is d [nm], the phase difference R0 (550) [nm] = (nx - ny) × d in the film plane is 60 nm or more and 300 nm or less, and the film thickness is The phase difference Rth (550) [nm] - {(nx + ny) / 2 - nz} × d in the direction is 30 nm or more and 300 nm or less.

一種偏光板，其特徵為：於起偏極鏡的至少單面上，層合有申請專利範圍第1項之相位差薄膜。 A polarizing plate characterized by being on at least one side of a polarizing mirror A phase difference film of the first application patent range is laminated.

如申請專利範圍第3項之偏光板，其中於起偏極鏡的至少單面上，介由偏光板保護膜而層合有申請專利範圍第1項之相位差薄膜。 The polarizing plate of claim 3, wherein the retardation film of claim 1 is laminated on at least one side of the polarizing mirror through a protective film of a polarizing plate.

一種液晶面板，其特徵為：係於液晶顯示元件的至少單面上，層合有申請專利範圍第3項或第4項之偏光板而成者。A liquid crystal panel characterized in that a polarizing plate of the third or fourth aspect of the patent application is laminated on at least one side of a liquid crystal display element.