201003249 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種含有聚丙烯系樹脂之相位差薄膜及 使用該相位差薄膜的橢圓偏光板,特別是於含有聚丙烯系 樹脂之相位差薄膜使特定的底塗層層合之附黏著劑層之相 位差薄膜,以及使用其之橢圓偏光板、液晶顯示裝置。 【先前技術】 近年,液晶顯示裝置有效地利用低消耗電力、低電壓 動作、質輕、薄型等特徵,在作爲手機、個人數位秘書( PDA )、電腦用監視器、電視等資訊用顯示器上急速地普 及。伴隨液晶技術的發展,藉由各種模式的液晶顯示器之 提案,逐漸解決所謂響應速度、對比、窄視角之液晶顯示 器的問題點。但是,與陰極射線管(CRT )比較,視角小 依舊被指摘,而進行各種擴大視角之嘗試。 作爲擴大視角的方法之一,例如使用符合液晶模式的 相位差薄膜。作爲相位差薄膜的例,例如各種塑膠的延伸 薄膜等所成的雙折射性薄膜、具有圓盤型液晶、向列型液 晶固定配向的液晶層之薄膜、薄膜基材上形成有上述液晶 層者等。 作爲形成雙折射性薄膜之塑膠的具體例’例如聚碳酸 酯、聚苯乙烯、聚甲基丙烯酸甲酯、聚烯烴、聚醯胺等。 作爲聚烯烴系樹脂的相位差薄膜,脂環式聚烯烴或被 稱爲冰片烯系樹脂之非晶性環狀聚烯烴系樹脂因耐熱性及 -5- 201003249 耐濕性較佳,透明度佳以及相位差値比較容易調整等 ,被廣泛使用。 例如於特開平1 1 -1 4 9 0 1 5號公報(專利文獻1 ) 露製作由環狀聚烯烴所成的λ/2延伸薄膜、λ/4延伸 之例。而且,於特開2007-2866 1 5號公報(專利文獻 ,揭露聚烯烴系樹脂應用於相位差薄膜。但是,非極 聚烯烴系樹脂因常與黏著劑層的接著力不足而被要求 〇 另一方面,於特開2004-2·776 1 7號公報(專利文 ),記載以不飽和聚羧酸或不飽和聚羧酸的衍生物以 甲基)丙烯酸或(甲基)丙烯酸的衍生物改性之聚烯 脂應用於聚丙烯系樹脂等的保護或裝飾爲目的之黏結 成物。 專利文獻1 :特開平1 1 - 1 4 9 0 1 5號公報 專利文獻2:特開2007-286615號公報 專利文獻3:特開2004-277617號公報 【發明內容】 發明所欲解決之課題 由聚丙烯系樹脂所成的相位差薄膜,與環狀聚烯 樹脂比較時’因與黏著劑層的接著性差,與偏光板及 差薄膜等光學薄膜貼合之光學構件從液晶胞剝離時, 黏著劑層的一部份殘留之不良情況。於本發明,爲了 如此的問題點,以提供由聚丙烯系樹脂所成的相位差 原因 ,揭 薄膜 2 ) 性的 改善 獻3 及( 烴樹 劑組 烴系 相位 產生 解決 薄膜 -6- 201003249 與黏著劑層之密合性提高之附黏著劑層之相位差薄膜爲目 的。而且,本發明之其他目的係提供使用該附黏著劑層之 相位差薄膜之橢圓偏光板。再者,本發明的目的係提供使 用前述橢圓偏光板之液晶顯示裝置。 解決課題之手段 本發明之附黏著劑層之相位差薄膜,其係依序由含有 聚丙烯系樹脂之相位差薄膜、底塗層及黏著劑層所形成, 該底塗層係含有以不飽和聚羧酸或不飽和聚羧酸的衍生物 ,及(甲基)丙烯酸或(甲基)丙烯酸的衍生物改性,且 重量平均分子量爲15,000〜150,000之改性聚烯烴樹脂。 前述含有聚丙烯系樹脂之相位差薄膜係由含有1〇重 量%以下的乙烯單元之丙烯與乙烯的共聚物所構成較理想 。而且,前述附黏著劑層之相位差薄膜的前述相位差薄膜 爲1M波長板較理想。 本發明係關於含有偏光板及層合於該偏光板所成的前 述附黏著劑層之相位差薄膜之橢圓偏光板。該橢圓偏光板 ,可於附黏著劑層之相位差薄膜與橢圓偏光板之間含有 1/2波長板。而且,本發明的其他態樣爲前述橢圓偏光板 層合於液晶胞的至少一側所成之液晶顯示裝置。 發明的效果 使用含有聚丙烯系樹脂的相位差薄膜之複合偏光板, 因含有聚丙烯系樹脂的相位差薄膜與黏著劑層的密合性低 -7- 201003249 ,貼合於液晶胞的玻璃基板,重新貼合時,黏著 部份會殘留於玻璃基板上,而使用根據本發明的 含有聚丙烯樹脂之相位差薄膜、底塗層樹脂及黏 附黏著劑層之相位差薄膜的橢圓偏光板,因改良 烯樹脂之相位差薄膜與黏著劑層的密合性,具有 的一部份不殘留於玻璃基板上之效果。 【實施方式】 以下,參照圖面,說明本發明的實施態樣。 示本發明的附黏著劑層之相位差薄膜的剖面示意 明的附黏著劑層之相位差薄膜1 〇係於含有聚丙 之相位差薄膜2 0之一側的面,依序形成底塗層: 劑層40。然後,使偏光板貼合於與黏著劑層40 相位差薄膜。 [相位差薄膜] 於本發明,通常使含有聚丙烯系樹脂之樹脂 爲相位差薄膜。因含有聚丙烯系樹脂之相位差薄 性,相位差値的發現率極高,藉由延伸可簡單地 相位差値。因此,以薄的膜厚,可得具有所期望 値之相位差薄膜。 而且,聚丙烯系樹脂因其波長40 Onm之面 射率與最小折射率之差(雙折射)An4G()以及波 之面內最大折射率與最小折射率之差(雙折射) 劑層的一 依序形成 著劑層之 含有聚丙 黏著劑層 圖1係表 圖。本發 烯系樹脂 (〇及黏著 相反側的 延伸而成 膜爲結晶 得到大的 的相位差 內最大折 長 5 0 0 nm A η 5 ο 〇 的 -8- 201003249 比(Δη^οο/Δι^οο)未達1.05,分別由聚丙儲系樹脂構成之 1 /2波長板與1 /4波長板組合的情況,可成爲優異的廣波 段1/4波長板。於本說明書,以上述An4QGMn5G()値,定義 爲相位差的波長色散。該相位差的波長色散亦只稱爲「波 長色散」。 再者,聚丙烯系樹脂因其光彈性係數約爲2x1 0_13cm2 /dyne左右的小,1/2波長板與1/4波長板貼合時,或與直 線偏光板貼合時,可抑制貼合不均。而且,亦可抑制耐熱 測試時的白化。再者,因聚丙烯系樹脂可高倍率延伸,可 製作橫延伸之完全一軸性相位差薄膜,可同時達成薄膜化 與寬幅化,利用效率佳。 如此從聚丙烯系樹脂製膜之原料薄膜藉由延伸,而使 相位差顯現。於該情況,相位差薄膜的膜厚可爲25 μηι以 下。其膜厚爲2 0 μηι以下更理想。相位差薄膜的膜厚超過 25μιη時’薄膜化的優點不易有效發揮。而且,其膜厚太 小時’相位差薄膜容易產生皺褶,捲取、貼合時的操作性 有惡化的傾向。所以,其膜厚爲5 μηι以上較理想,又 8 μ m以上更理想。 相位差薄膜的面內相位延遲軸方向的折射率爲nx、 面內相位超前軸方向(在面內與相位延遲軸垂直之方向) 的折射率爲ny、厚度方向的折射率爲Nz,又厚度爲d時 ,面內的相位差値(R〇 )、厚度方向的相位差値(Rth ) 以及N z係數分別由下式(〗)、(〗〗)及(! ! ϊ )定義。 201003249[Technical Field] The present invention relates to a retardation film containing a polypropylene resin and an elliptically polarizing plate using the retardation film, particularly to a retardation film containing a polypropylene resin. A retardation film having an adhesive layer laminated with a specific undercoat layer, and an elliptically polarizing plate or a liquid crystal display device using the same. [Prior Art] In recent years, liquid crystal display devices have been rapidly utilizing features such as low power consumption, low voltage operation, light weight, and thinness, and have been rapidly used as information displays for mobile phones, personal digital secretaries (PDAs), computer monitors, and televisions. Popularity. With the development of liquid crystal technology, the problems of so-called response speed, contrast, and narrow viewing angle liquid crystal displays have been gradually solved by proposals of liquid crystal displays of various modes. However, compared with a cathode ray tube (CRT), the angle of view is still small, and various attempts to expand the viewing angle are performed. As one of methods for expanding the viewing angle, for example, a retardation film conforming to the liquid crystal mode is used. Examples of the retardation film include a birefringent film formed of a stretched film of various plastics, a film having a liquid crystal layer in which a discotic liquid crystal and a nematic liquid crystal are fixedly aligned, and a liquid crystal layer formed on the film substrate. Wait. Specific examples of the plastic which forms the birefringent film are, for example, polycarbonate, polystyrene, polymethyl methacrylate, polyolefin, polyamide or the like. As a retardation film of a polyolefin resin, an alicyclic polyolefin or an amorphous cyclic polyolefin resin called a norbornene resin is preferred because of heat resistance and heat resistance of -5 to 201003249, and transparency is good. The phase difference is relatively easy to adjust and is widely used. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Further, JP-A-2007-2866-15 (Patent Literature discloses that a polyolefin-based resin is applied to a retardation film. However, the non-polar polyolefin-based resin is required to be insufficient in adhesion to the adhesive layer. On the one hand, Japanese Patent Publication No. 2004-27767-1 (patent document) describes derivatives of methyl acrylate or (meth) acrylate as derivatives of unsaturated polycarboxylic acids or unsaturated polycarboxylic acids. The modified polyolefin is used for the purpose of protecting or decorating a polypropylene resin or the like. [Patent Document 1] JP-A-2007-286615 (Patent Document 3) JP-A-2004-277617 When the retardation film made of the polypropylene resin is inferior to the cyclic polyene resin, the optical member bonded to the optical film such as the polarizing plate or the poor film is peeled off from the liquid crystal cell due to poor adhesion to the adhesive layer. The defect of a part of the agent layer remains. In the present invention, in order to solve such a problem, the reason for the phase difference caused by the polypropylene resin is provided, and the improvement of the film 2) and the hydrocarbon-based hydrocarbon phase generation solution film -6-201003249 are It is an object of the phase difference film of the adhesive layer with improved adhesion of the adhesive layer. Further, another object of the present invention is to provide an elliptically polarizing plate using the phase difference film of the adhesive layer. A liquid crystal display device using the above elliptically polarizing plate is provided. The object of the present invention is a retardation film with an adhesive layer of the present invention, which is sequentially provided with a retardation film containing a polypropylene resin, an undercoat layer, and an adhesive. Formed by a layer comprising a derivative of an unsaturated polycarboxylic acid or an unsaturated polycarboxylic acid, and a derivative of (meth)acrylic acid or (meth)acrylic acid, and having a weight average molecular weight of 15,000 ~150,000 modified polyolefin resin. The phase difference film containing the polypropylene resin is a copolymer of propylene and ethylene containing 1% by weight or less of ethylene unit. Preferably, the phase difference film of the phase difference film with the adhesive layer is preferably a 1M wave plate. The present invention relates to a pressure-sensitive adhesive layer comprising the polarizing plate and the pressure-sensitive adhesive layer laminated on the polarizing plate. An elliptically polarizing plate of a retardation film. The elliptically polarizing plate may have a 1/2 wavelength plate between the phase difference film with the adhesive layer and the elliptically polarizing plate. Further, the other aspect of the invention is the elliptically polarizing plate layer. A liquid crystal display device formed by at least one side of a liquid crystal cell. The effect of the invention is to use a composite polarizing plate containing a retardation film of a polypropylene resin, and a phase difference film containing a polypropylene resin and an adhesive layer are adhered to each other. Low--7-201003249, a glass substrate bonded to a liquid crystal cell, the adhesive portion remains on the glass substrate when re-adhesive, and the phase difference film containing the polypropylene resin and the undercoat resin are used according to the present invention. And an elliptically polarizing plate which adheres to the retardation film of the adhesive layer, and a part of the phase difference film of the modified olefin resin and the adhesive layer does not remain in the glass. [Embodiment] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. A phase difference film 1 with an adhesive layer as schematically shown in a cross section of a phase difference film with an adhesive layer of the present invention is shown. The undercoat layer: the agent layer 40 is sequentially formed on the surface of one side of the phase difference film 20 containing the polypropylene. Then, the polarizing plate is bonded to the phase difference film with the adhesive layer 40. [Retardation film] In the present invention, the resin containing the polypropylene resin is usually a retardation film. Since the phase difference of the polypropylene resin is contained, the phase difference 値 is extremely high, and the phase difference 値 can be easily extended by stretching. With a thin film thickness, a phase difference film having a desired enthalpy can be obtained. Moreover, the difference between the surface area and the minimum refractive index (birefringence) An4G() of the polypropylene resin due to its wavelength of 40 Onm and the in-plane of the wave The difference between the maximum refractive index and the minimum refractive index (birefringence) of a layer of the agent layer containing the polyacrylic adhesive layer is shown in FIG. The present invention is a olefin-based resin (the 〇 and the opposite side of the adhesive film are formed by crystallization, and the maximum phase length within the phase difference is 50,000 nm A η 5 ο -8 - 201003249 ratio (Δη^οο/Δι^ Οο) In the case of a combination of a 1 / 2 wave plate and a 1 / 4 wave plate made of a polypropylene resin, it is an excellent wide-band 1⁄4 wavelength plate. In the present specification, the above An4QGMn5G() is used.値, defined as the wavelength dispersion of the phase difference. The wavelength dispersion of this phase difference is also called "wavelength dispersion". Furthermore, the polypropylene resin has a photoelastic coefficient of about 2x1 0_13cm2 /dyne, 1/2 When the wavelength plate is bonded to the quarter-wave plate or when it is bonded to the linear polarizing plate, uneven bonding can be suppressed, and whitening during heat resistance test can be suppressed. Furthermore, the polypropylene resin can be used at a high magnification. By stretching, it is possible to produce a full-axial phase difference film which is horizontally stretched, and it is possible to simultaneously achieve film formation and widening, and the use efficiency is good. Thus, the phase difference is revealed by stretching the raw material film of the polypropylene resin film. In this case, the film thickness of the retardation film can be 25 Ηι以下以下。 The film thickness is preferably 20 μηη or less. When the film thickness of the retardation film exceeds 25 μm, the advantage of thin film formation is not easy to be effectively exhibited. Moreover, the film thickness is too small, and the retardation film is liable to wrinkle, and the film is wound. The operability at the time of bonding tends to deteriorate. Therefore, the film thickness is preferably 5 μηι or more, and more preferably 8 μm or more. The retardation of the in-plane phase retardation axis direction of the retardation film is nx, in-plane. The phase lead axis direction (the direction perpendicular to the phase delay axis in the plane) is ny, the refractive index in the thickness direction is Nz, and the thickness is d, the in-plane phase difference 値(R〇), thickness direction The phase difference 値(Rth) and the N z coefficient are defined by the following equations (〖), (〗), and (!! ϊ).
Ro = (nx-ny)xd (I)Ro = (nx-ny)xd (I)
Rth-[(nx + ny)/2-Nz] xd (II)Rth-[(nx + ny)/2-Nz] xd (II)
Nz = (nx-Nz)/(nx-ny) (III) 而且,由這些式(I ) 、( II )及(III ) ,Nz係數與 面內的相位差値(R ο )以及厚度方向的相位差値(Rth ) 的關係可由下述式(IV)表示。 (IV) N z = Rth/Ro + 0.5 於本發明,相位差薄膜之面內的相位差値(Ro )爲 70〜160nm的範圍更理想。而且,Nz係數爲0.9〜1.6的 範圍,特別是0.95〜1.05的範圍更理想。相位差薄膜之 面內的相位差値(Ro )與Nz係數,符合相位差薄膜適用 的液晶顯示裝置所要求的特性,從上述範圍適當選擇即可 。此處,若Nz係數大約爲1,於上述式(III )中,係指 ny與Nz大約相等,如此的相位差薄膜成爲大致上完全一 軸性。 [聚丙烯系樹脂] 於本發明,構成相位差薄膜之聚丙烯系樹脂,係使用 習知的聚合用觸媒,藉由單獨聚合丙烯的方法、使丙烯與 其他共聚合性共聚單體共聚合的方法而可製造。作爲習知 的聚合用觸媒,例如下述。 -10- 201003249 (1 )由以鎂、鈦及鹵素爲必須成份之固體觸媒 所成之Ti-Mg系觸媒;(2 )於以鎂、鈦及鹵素爲必 份之固體觸媒成份中組合有機鋁化合物以及依需要之 供給性化合物等第三成份之觸媒系;或(3 )金屬芳 (metallocene)系觸媒等。 此等觸媒系中,用於相位差薄膜的聚丙烯系樹脂 造’ 一般使用以鎂、鈦及鹵素爲必須成份之固體觸媒 中,組合有機鋁化合物以及電子供給性化合物。 更具體地,作爲有機鋁化合物,較理想爲例如三 銘、二異丁基錦、三乙基銘與氯化二乙基銘氯化物的 物、四乙基二鋁氧烷等,作爲電子供給性化合物,較 爲例如環己基乙基二甲氧基甲矽烷、第3 丁基丙基二 基甲矽烷、第3 丁基乙基二甲氧基甲矽烷、二環戊基 氧基甲矽烷等。 另一方面,作爲以鎂、鈦及鹵素爲必須成份之固 媒成份,例如特開昭 6 1 -2 1 8 606號公報、特開昭 2879〇4號公報、特開平7-216017號公報等記載之觸 ,此外作爲金屬芳香類(metallocene)系觸媒,例如 專利第2587251號公報、專利第2627669號公報、專 2668732號公報等記載之觸媒系。 聚丙烯系樹脂係例如藉由使用如己烷、庚烷、辛 壬烷、環己烷、甲基環己烷、苯、甲苯、二甲苯的碳 合物爲代表之不活性溶劑的溶液聚合法、使用液狀單 爲溶劑之塊狀聚合法、氣態的單體原樣聚合之氣相聚 成份 須成 電子 香類 之製 成份 乙基 混合 理想 甲氧 二甲 體觸 61 - 媒系 曰本 利第 烷、 氫化 體作 合法 -11 - 201003249 等而可製造。藉由此等方法之聚合,可以批次式進行,也 可以連續式進行。 聚丙烯系樹脂的立體規則性,可爲等規、間規、無規 中的任一種。於本發明’從耐熱性的點,使用間規或等規 的聚丙烯系樹脂較理想。 本發明所使用的聚丙烯系樹脂,除以丙烯的單獨聚合 物構成外,以丙烯爲主體,少量的可與其共聚合之共聚單 體,例如以2 0重量%以下’較理想爲1 0重量%以下的比 例共聚合。於共聚物的情況,共聚單體的量爲1重量%以 上較理想。 與丙烯共聚合之共聚單體’例如乙烯、碳原子數4〜 2 〇之α -烯烴。作爲該情況之α -燔烴,具體地例如下述。 亦即,1-丁烯、2 -甲基-卜丙烯(以上爲C4) ; 1-戊 烯、2 -甲基-1-丁烯、3 -甲基-卜丁烯(以上爲c5) ; 1-己 烯、2-乙基-1-丁烯、2,3-二甲基-1-丁烯、2-甲基-1-戊烯 、3-甲基-1-戊烯、4-甲基·卜戊烯、3,3-二甲基_;!•丁烯( 以上爲C6) ; 1-庚烯、2·甲基-1_己烯、2,3 -二甲基-卜戊 烯、2-乙基-1-戊烯、2-甲基-3-乙基-1· 丁烯(以上爲c7) ;1-辛烯、5-甲基-卜庚烯、2_乙基-1-己烯、3,3-二甲基-1-己烯、2-甲基-3-乙基-1·戊烯、2,3,4-三甲基-1-戊烯、2-丙基-1-戊烯、2,3-二乙基-丨_丁儲(以上爲<:8) ; 1-壬烯 (C9) ; 1-癸烯(C1Q);卜十一燃(Cu);丨·十二烯(Nz = (nx-Nz) / (nx-ny) (III) Moreover, from these formulas (I), (II) and (III), the Nz coefficient and the in-plane phase difference 値(R ο ) and the thickness direction The relationship of the phase difference 値(Rth ) can be expressed by the following formula (IV). (IV) N z = Rth / Ro + 0.5 In the present invention, the phase difference 値(Ro ) in the plane of the retardation film is preferably in the range of 70 to 160 nm. Further, the Nz coefficient is in the range of 0.9 to 1.6, and particularly preferably in the range of 0.95 to 1.05. The phase difference 値(Ro) and the Nz coefficient in the in-plane of the retardation film are in accordance with the characteristics required for the liquid crystal display device to which the retardation film is applied, and may be appropriately selected from the above range. Here, if the Nz coefficient is about 1, in the above formula (III), the fingers ny and Nz are approximately equal, and such a retardation film is substantially completely monoaxial. [Polypropylene-based resin] In the present invention, a polypropylene-based resin constituting a retardation film is copolymerized with propylene and another copolymerizable comonomer by a method of separately polymerizing propylene using a conventional polymerization catalyst. The method can be manufactured. As a conventional catalyst for polymerization, for example, the following. -10- 201003249 (1) Ti-Mg-based catalyst made of solid catalyst containing magnesium, titanium and halogen as essential components; (2) in solid catalyst component containing magnesium, titanium and halogen as essential components a catalyst system in which a third component such as an organoaluminum compound and a supply compound is required; or (3) a metallocene catalyst or the like. Among these catalyst systems, a polypropylene resin used for a retardation film is generally used in a solid catalyst containing magnesium, titanium and halogen as essential components, and an organoaluminum compound and an electron-donating compound are combined. More specifically, as the organoaluminum compound, it is preferable to use, for example, triammine, diisobutyl bromine, triethyl succinium and diethyl chloride chloride, tetraethyldialuminoxane, etc. as an electron supply. Compounds, for example, cyclohexylethyldimethoxymethane, butyl butyl dimethyl decane, butyl butyl dimethoxy methoxy decane, dicyclopentyloxy decane, etc. . On the other hand, as a solid-state component containing magnesium, titanium, and a halogen as an essential component, for example, JP-A-61-1-2868, JP-A-H2879-A-4, JP-A-7-216017, etc. In addition, as a metallocene-based catalyst, a catalyst system described in, for example, Japanese Patent No. 2,587,251, Japanese Patent No. 2,627,669, and No. 2,668,332. The polypropylene resin is a solution polymerization method represented by, for example, an inactive solvent represented by a carbon compound such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene or xylene. The liquid phase polymerization method using a liquid single solvent, the gas phase monomer polymerization, the gas phase polymerization component must be made into an electronic fragrance, the ethyl group is mixed with the ideal methoxy dimethyl body contact 61 - the medium ipidine, Hydride can be manufactured as law -11 - 201003249. The polymerization by this method can be carried out batchwise or continuously. The stereoregularity of the polypropylene resin may be any of isotactic, syndiotactic, and random. In the present invention, it is preferred to use a syndiotactic or isotactic polypropylene resin from the viewpoint of heat resistance. The polypropylene-based resin used in the present invention is composed of propylene alone, and a small amount of a comonomer copolymerizable therewith, for example, 20% by weight or less, more preferably 10% by weight. The ratio below % is copolymerized. In the case of a copolymer, the amount of the comonomer is preferably 1% by weight or more. The comonomer copolymerized with propylene, for example, ethylene, an α-olefin having 4 to 2 carbon atoms. The α-anthracene hydrocarbon in this case is specifically, for example, the following. That is, 1-butene, 2-methyl-propyl propylene (above C4); 1-pentene, 2-methyl-1-butene, 3-methyl-butene (above c5); 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4- Methyl·p-pentene, 3,3-dimethyl-;;•butene (above C6); 1-heptene, 2·methyl-1—hexene, 2,3-dimethyl-b Pentene, 2-ethyl-1-pentene, 2-methyl-3-ethyl-1.butene (above c7); 1-octene, 5-methyl-bheptene, 2_B 1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1.pentene, 2,3,4-trimethyl-1-pentene, 2-propyl-1-pentene, 2,3-diethyl-fluorene-butadiene (above <:8); 1-decene (C9); 1-decene (C1Q); Combustion (Cu); 丨·dodecene (
Ci2) ; 1-十三嫌(Cl3) ’ 1-十四嫌(C!4) ; 1-十五稀(Ci2); 1-Thirteen suspects (Cl3) ’ 1-fourteen suspects (C!4); 1-fifteen rare (
Cl5 ) ; 1-十六烯(Cl6 );卜十七烯(C17 );丨_十八烯( -12 - 201003249Cl5); 1-hexadecene (Cl6); hexadecene (C17); 丨_octadecene (-12 - 201003249
Cl8) ,1-十九稀(Ci9)等。 α-烯烴中較理想者爲碳原子數4〜12之α-烯烴,具體 地例如1-丁烯、2-甲基-1-丙烯;1-戊烯、2·甲基-1-丁烯 、3-甲基-1-丁烯;1-己烯、2-乙基-1· 丁烯、2,3-二甲基-1-丁烯、2-甲基-1-戊烯、3-甲基-卜戊烯、4-甲基-1-戊烯 、3,3 -二甲基-1-丁烯;1-庚烯、2 -甲基-1-己烯、2,3 -二甲 基-1-戊烯、2-乙基-1-戊烯、2·甲基-3-乙基-1-丁烯;1-辛 烯、5-甲基-1-庚烯、2-乙基-1-己烯、3,3-二甲基-1-己烯 、2-甲基-3-乙基-1-戊烯、2J,4-三甲基-1-戊烯、2-丙基-1-戊烯、2,3 -二乙基-1-丁烯;;!-壬烯;1-癸烯;1-十一烯 ;1-十二烯等。從共聚合性的觀點’以1-丁烯、1-戊烯、 1-己烯及1-辛烯較理想,特別是1-丁烯及1-己烯更理想 〇 共聚物可爲無規共聚物,也可爲嵌段共聚物。作爲較 理想的共聚物,例如丙烯/乙烯共聚物、丙烯/1-丁烯共聚 物。於丙烯/乙烯共聚物、丙烯/1-丁烯共聚物,乙烯單元 的含量、1-丁烯單元的含量例如可藉由「高分子分析手冊 」( 1995年、紀伊國屋書店發行)第616頁記載之紅外 線(IR )光譜測定方法而求得。 從提高作爲相位差薄膜的透明度、加工性的觀點’以 丙烯爲主體,與任意不飽和烴的無規共聚物較理想’其中 以與乙烯的無規共聚物較理想。於共聚物的情況’丙燃以 外的不飽和烴類爲其共聚物的1〜1〇重量%程度爲有利’ 更理想爲共聚物的3〜7重量%。丙烯以外的不飽和烴類 -13- 201003249 的單元爲1重量%以上,提高加工性、透明性之效果有顯 現的傾向。另一方面,若超過共聚物的10重量%,樹脂 的熔點降低,耐熱性有變差的傾向。而且,於2種以上的 共聚單體與丙烯成爲共聚物之情況,該共聚物所含的全部 來自共聚單體之單元的合計含量爲前述範圍較理想。 於本發明,根據JI s K 7 2 1 0,以溫度2 3 0 °C、負載 2 1 . 1 8N測定之相位差薄膜所使用的聚丙烯系樹脂的熔融 指數(MFR)爲0.1〜2〇〇g/l〇分,特別是0.5〜50g/10分 的範圍較理想。藉由使用MFR爲該範圍之聚丙烯系樹脂 ,對擠出機沒有大負擔,可得均勻的薄膜狀物。 該聚丙烯系樹脂,在不妨礙本發明效果的範圍下,也 可配合習知的添加物。作爲添加物,例如抗氧化劑、紫外 線吸收劑、帶電防止劑、潤滑劑、造核劑、防霧劑、防結 塊劑等。抗氧化劑係例如酚系抗氧化劑、磷系抗氧化劑、 硫系抗氧化劑、受阻胺系光安定劑等,而且也可使用具有 1分子中例如合倂具有酚系的抗氧化機構與磷系的抗氧化 機構之單元之複合型抗氧化劑。作爲紫外線吸收劑,例如 2 -羥基二苯甲酮系、羥基苯基苯並***系之紫外線吸收劑 、苯甲酸酯系紫外線遮斷劑等。帶電防止劑可爲聚合物型 、寡聚物型、單體型中的任一種。作爲潤滑劑,例如芥酸 醯胺、油酸醯胺之高級脂肪酸醯胺、如硬脂酸的高級脂肪 酸及其鹽等。作爲造核劑,例如山梨醇系造核劑、有機磷 酸鹽系造核劑、如聚乙烯基環己烷之高分子系造核劑等。 作爲防結塊劑,只要是球狀或近似其形狀的微粒子,可使 -14 - 201003249 用無機系、有機系。此等添加劑,可倂用複數種。 [聚丙烯系樹脂的原料薄膜] 聚丙烯系樹脂可以任意方法製膜,成爲原料薄膜。該 原料薄膜係透明且實質上無面內相位差者。例如藉由從熔 融樹脂之擠出成形法;溶解於有機溶劑之樹脂流延澆鑄於 平板上、除去溶劑而製膜之溶劑澆鑄法等,可得實質上無 面內相位差之聚丙烯系樹脂的原料薄膜。 作爲製造原料薄膜的方法之例,以藉由擠出成形之製 膜法詳細說明。聚丙烯系樹脂係在擠出機中藉由螺桿的旋 轉而熔融混練,從T型模頭擠出薄膜狀。擠出的熔融狀薄 片之溫度,通常爲180〜300 °c程度。此時的熔融狀薄片之 溫度比1 8 0 °c低時,延展性不足,所得的原料薄膜之厚度 變得不均勻,可能變成具有相位差不均之原料薄膜。此外 ,該溫度超過300r時,容易引起樹脂的劣化、分解,薄 片中產生氣泡、含有碳化物。 擠出機可爲單軸擠出機,亦可爲2軸擠出機。例如於 單軸擠出機的情況,可使用螺桿的長度L與直徑D的比 L/D爲24〜3 6的程度,樹脂供應部之螺紋的空間體積與 樹脂計量部之螺紋的空間體積之比(前者/後者)的壓縮 比爲1 ·5〜4的程度,具有全螺紋(full flight)型、阻隔 (barrier )型、美達克(Madoc )型混練部份之螺桿。從 抑制聚丙烯系樹脂的劣化、分解,均勻地熔融混練的觀點 ,使用L/D爲28〜36、壓縮比爲2.5〜3.5之阻隔( -15- 201003249 barrier )型螺桿較理想。而且,爲了儘可能地抑制聚丙烯 系樹脂的劣化、分解,擠出機內爲氮氣環境或真空較理想 。再者,爲了除去因丙烯系樹脂的劣化、分解所產生之揮 發氣體,於擠出機的前端,設置Ιηιηιφ以上5ιηπιφ以下的 孔口,提高擠出機前端部份的樹脂壓力較理想。所謂藉由 孔口提高擠出機前端部份的樹脂壓力,係指提高在前端的 背壓,藉此可提高擠出的安定性。所使用的孔口的直徑, 更理想爲2 m m φ以上4 m m φ以下。 擠出所使用的T型模頭,樹脂的流道表面無微小的階 差、傷痕者較理想,且使其唇部鍍敷或塗佈與熔融的聚丙 烯系樹脂之摩擦係數小的材料,又唇部前端硏磨成 0.3 m m φ以下之尖銳邊緣形狀者較理想。作爲摩擦係數小 的材料,例如碳化鎢系、氟系的特殊鍍敷等。藉由使用如 此的T型模頭,可抑制眼屎的產生,同時因可抑制模頭線 ,可得外觀均勻性佳之原料薄膜。該T型模頭,歧管爲衣 架形狀,且滿足以下的條件(1 )或(2 )較理想,又滿足 條件(3 )或(4 )更理想。 T型模頭的唇部寬度未達1500mm: T型模頭的厚度 方向之長度> 180mm…(1) T型模頭的唇部寬度爲1 5 0 0 m m以上:T型模頭的厚 度方向之長度>220mm…(2) T型模頭的唇部寬度未達1 50 0mm: T型模頭的厚度 方向之長度>250mm…(3) T型模頭的唇部寬度爲1 5 00mm以上:T型模頭的厚 -16- 201003249 度方向之長度> 280mm ... (4) 藉由使用滿足如此條件之T型模頭,可調整在τ型 模頭內部的熔融狀聚丙烯系樹脂的流動,且在唇部份亦可 抑制厚度不均地擠出,可得厚度精度更佳、相位差更均句 的原料薄膜。 從抑制聚丙烯系樹脂的擠出變動之觀點,擠出機與τ 型模頭間,介由連接器,安裝齒輪泵較理想。而且’爲了 除去聚丙烯系樹脂中的異物,安裝葉盤式過濾器(leaf disc filter)較理想。 金屬製冷卻輥(亦稱爲冷卻輥或澆鑄輥)與壓接於該 金屬製冷卻輥的圓周方向旋轉的含有彈性體的接觸輥之間 ,挾壓從T型模頭擠出之熔融狀薄片,使其冷卻固化,可 得所期望的原料薄膜。此時,接觸輥可爲橡膠等彈性體成 爲其表面者,也可爲彈性體輥的表面以金屬套筒所成的外 筒包覆者。於使用彈性體輥的表面以金屬套筒所成的外筒 包覆之接觸輥的情況’通常於金屬製冷卻輥與接觸輥之間 ,直接夾住聚丙烯系樹脂的熔融狀薄片,使其冷卻。另一 方面,於使用表面爲彈性體之接觸輥的情況,聚丙烯系樹 脂的熔融狀薄片與接觸輥之間’可存在熱塑性樹脂的二軸 延伸薄膜而挾壓。 聚丙烯系樹脂的熔融狀薄片’如上述以冷卻輥與接觸 輥夾住而使其冷卻固化’先使冷卻輥與接觸輕的表面溫度 降低,必須使熔融狀薄片急速冷卻。例如調整冷卻輥與接 觸輥的表面溫度爲0°C以上30°C以下的範圍較理想。這些 -17- 201003249 的表面溫度超過3 0 °C時,因熔融狀薄片的冷卻固化耗時, 聚丙烯系樹脂中的結晶成份成長,使所得的原料薄膜的透 明性劣化。冷卻輥與接觸輥的表面溫度,較理想爲3 0 °C以 下,未達2 5 °C更理想。另一方面,冷卻輥與接觸輥的表面 溫度低於〇°C時,金屬製冷卻輥表面結露,附著水滴,原 料薄膜的外觀有惡化的傾向。 所使用的金屬製冷卻輥,因其表面狀態轉寫至含有聚 丙烯系樹脂之原料薄膜的表面,於該表面具有凹凸的情況 ,可能降低所得的含有聚丙烯系樹脂之原料薄膜的厚度精 度。因此,金屬製冷卻輥的表面儘可能地爲鏡面狀態較理 想。具體地,金屬製冷卻輥的表面粗糙度,以最大高度的 標準數列表示,0.3S以下較理想,又0.1S〜0.2S更理想 〇 形成與金屬製冷卻輥夾持部份的接觸輥之彈性體的表 面硬度,以JIS K63 0 1規定的彈簧式硬度測試(A形)所 測得之値,爲65〜80較理想,又70〜80更理想。藉由使 用如此的表面硬度之橡膠輥,容易維持均勻的施加於熔融 狀薄片之線壓,且金屬製冷卻輥與接觸輥之間,不會製造 熔融狀薄片的囤積(bank)(樹脂積存),容易成形爲薄 膜狀。 挾壓熔融狀薄片時的壓力(線壓),由相對金屬製冷 卻輥壓住接觸輥的壓力決定。線壓爲 50N/Cm以上 3 00N/cm以下較理想,又l〇〇N/cm以上2 5 0N/cm以下更 理想。藉由線壓爲前述範圍,不形成囤積,一邊維持一定 -18- 201003249 的線壓,一邊可容易地製造含有聚丙烯系樹脂的原 〇 在金屬製冷卻輥與接觸輥之間,同時挾壓聚丙 脂的熔融狀薄片與熱塑性樹脂的二軸延伸薄膜的情 成該二軸延伸薄膜之熱塑性樹脂,只要是不與聚丙 脂堅固地熱熔合之樹脂,具體地例如聚酯、聚醯胺 乙烯、聚乙烯醇、乙烯-乙烯醇共聚物、聚丙烯腈 等之中,因濕度、熱等尺寸變化少之聚酯最理想。 之二軸延伸薄膜的厚度,通常爲5〜50μιη程度’ 爲 10 〜30μιη。 於該方法,從Τ型模頭至以金屬製冷卻輥與接 壓的距離(空氣隙;air gap )爲2 00mm以下較理 1 60 mm以下更理想。從T型模頭擠出之熔融狀薄 唇部至金屬製冷卻輥之間被延伸,容易產生配向。 隙短如上述,可得配向較小的原料薄膜。空氣隙的 係由所使用的金屬製冷卻輥之直徑與接觸輥之直徑 所使用的唇部的前端形狀決定,通常爲5 0mm以上 以該方法製造含有聚丙烯系樹脂的原料薄膜時 速度,依據熔融狀薄片冷卻固化所需的時間而決定 用的金屬製冷卻輥的直徑變大時,因熔融狀薄片與 輥接觸之距離變長,可更高速進行製造。具體地’ 6 0 0 m m φ的金屬製冷卻輥之情況,加工速度最大 2 0 m /分的程度。 被挾壓於金屬製冷卻輥與接觸輥之間的熔融肜 料薄膜 烯系樹 況,構 烯系樹 、聚氯 等。此 該情況 較理想 觸輥挾 想,又 片,從 使空氣 下限値 ,以及 〇 的加工 。所使 該冷卻 於使用 爲 5〜 薄片, -19- 201003249 藉由與金屬性的冷卻輥接觸而冷卻固化。然後,依據需要 切斷端部後,以捲取機捲取,成爲原料薄膜。此時,直到 使用原料薄膜爲止之間,爲了保護其表面,可在其單面或 兩面與其他熱塑性樹脂所成的表面保護薄膜貼合的狀態下 捲取。於聚丙烯系樹脂的熔融狀薄膜與熱塑性樹脂所成的 二軸延伸薄膜一起挾壓於金屬製冷卻輥與接觸輥之間的情 況,該二軸延伸薄膜可成爲一側的表面保護薄膜。 [相位差薄膜的製造方法] 於本發明,相位差薄膜可藉由橫延伸前述的含有聚丙 烯系樹脂的原料薄膜而製造。此處,所謂橫延伸,係指從 金屬製冷卻輥捲取之長原料薄膜,使其在寬度方向(橫方 向)延伸。 橫延伸通常具備以下的步驟。 (A)使原料薄膜在聚丙烯系樹脂的熔點附近之預熱 溫度進行預熱之預熱步驟; (B )預熱的原料薄膜在比前述預熱溫度低之延伸溫 度,進行橫方向上的延伸之延伸步驟;以及 (C)橫方向延伸的原料薄膜進行熱固定之熱固定步 驟。 作爲代表的橫延伸的方法,例如拉幅法。拉幅法係將 被夾頭固定薄膜寬度方向的兩端之原料薄膜,在烤箱中擴 展夾頭間隔而延伸之方法。拉幅法所使用的延伸機(拉幅 延伸機),通常於進行預熱步驟的區域、進行延伸步驟的 -20- 201003249 區域及進行熱固定步驟的區域’具備可獨立調節各溫度之 機構。藉由使用如此的拉幅延伸機進行橫延伸’可得軸精 度佳且具有均勻的相位差之相位差薄膜。 橫延伸的預熱步驟’係原料薄膜進行寬度方向延伸的 步驟前所設置的步驟’延伸原料薄膜時’加熱原料薄膜至 充分的溫度之步驟。在預熱步驟之預熱溫度’係指烤箱的 進行預熱步驟之區域的環境溫度’採用被延伸的含有聚丙 烯系樹脂的原料薄膜之熔點附近的溫度。被延伸的原料薄 膜之預熱步驟的滯留時間,以3 0〜1 20秒較理想。在該預 熱步驟之滞留時間未達3 0秒時’在延伸步驟延伸原料薄 膜時,應力分散,對作爲相位差薄膜之軸精度、相位差的 均勻性恐會有不利的影響,且該滯留時間超過1 20秒時, 受到需要以上的熱,原料薄膜部份熔解,有下引(向下垂 )的可能性。在預熱步驟之滯留時間爲3 0〜60秒更理想 〇 橫延伸的延伸步驟,係原料薄膜在寬度方向進行延伸 的步驟。該延伸步驟之延伸溫度,通常爲比預熱溫度低之 溫度。該延伸步驟之延伸溫度,係指烤箱進行延伸步驟的 區域之環境溫度。藉由將預熱的原料薄膜在比預熱步驟低 的溫度下延伸,原料薄膜可均勻地延伸,結果可得光軸及 相位差的均勻性佳之相位差薄膜。延伸溫度比預熱步驟之 預熱溫度低5〜20°C較理想,7〜1 5 °C更理想。此時的延伸 倍率係在發現光軸的方向(成爲延遲相位軸的方向)上3 〜1 0倍程度的範圍,符合需要的相位差値,適當選擇即 -21 - 201003249 可,較理想爲3〜6倍的範圍。藉由此時的延伸倍率爲3 倍以上’可使前述Nz係數爲0.9〜1.1的範圍。另一方面 ,延伸倍率變得太大時,因可能損害相位差値的均句性, 止於10倍程度較理想。 橫延伸的熱固定步驟,係延伸步驟結束時保持薄膜寬 度的狀態下,使該原料薄膜通過烤箱內的既定溫度之區域 的步驟。爲了有效地提高原料薄膜的相位差、光軸等光學 特性的安定性’熱固定的溫度爲從比延伸步驟之延伸溫度 低5 °C的溫度至比延伸溫度高3 0 t:的溫度之範圍內較理想 〇 橫延伸的步驟可再具備熱緩和步驟。該熱緩和步驟, 於拉幅法’通常在延伸步驟與熱固定步驟之間進行,熱緩 和的區域’通常爲從其他區域獨立,設置可設定溫度者。 具體地’熱緩和步驟係於延伸步驟延伸原料薄膜至既定的 寬度後’爲了除去無益的彎曲,使夾頭的間隔只縮小數% ,通常使其比延伸結束時的間隔窄0 · 5〜7 %的程度。 [使用作爲波長板時的光學特性] 於本發明,相位差薄膜使用作爲1 /4波長板的情況, 其面內相位差値(R〇)爲70〜160nm的範圍較理想,又 8 0〜1 5 Onm的範圍更理想。1 /4波長板係具有分別將直線 偏光入射的光變換成以圓偏光爲主之橢圓偏光,或圓偏光 爲主之橢圓偏光入射的光變換成直線偏光而射出之功能。 另一方面,於本發明’相位差薄膜使用作爲1 /2波長板的 -22- 201003249 情況,其面內相位差値(Ro)爲24〇〜400nm的範圍較理 想,又260〜330nm的範圍更理想。1/2波長板係具有旋 轉直線偏光的方向之功能。 [底塗劑] 作爲變成改性聚烯烴樹脂的原料之聚烯烴樹脂,係以 丙烯爲主體,α-烯烴與其共聚合之丙烯-α-烯烴共聚物, 可選自嵌段共聚物及無規共聚物中任一種。作爲α_烯烴成 分,例如乙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛 烯' 4-甲基-1-戊烯等。丙烯成分的含量爲50〜9〇莫耳% 最適合’ 50莫耳%以下時,相位差薄膜對表皮層之附著 性差,另外90莫耳%以上時,相位差薄膜的柔軟性有不 足的傾向。 而且,改性聚烯烴樹脂的改性單體之不飽和聚羧酸或 不飽和聚羧酸的衍生物,以及(甲基)丙烯酸或(甲基) 丙烯酸的衍生物之接枝量分別爲0.1〜20重量%、0.1〜 3 〇重量%較理想。比該範圍少的接枝量時,對溶劑的溶 解性有降低的傾向。而且,比該範圍多的接枝量時,對聚 烯烴的密合性有降低的傾向。 作爲不飽和聚羧酸或不飽和聚羧酸的衍生物,例如順 丁烯二酸、反丁烯二酸、四氫酞酸、亞甲基丁二酸、甲基 順丁烯二酸、2-丁烯酸、鳥頭酸(aconitic acid)、酞酸 、苯偏三酸、冰片烯二羧酸等不飽和聚羧酸或這些的衍生 物(例如酸酐、酸鹵化物、醯胺、醯亞胺、酯等)。此等 -23- 201003249 之中,使用亞甲基丁二酸酐、順丁烯二酸酐’接枝量爲 0.1〜20重量%,從相位差薄膜對表皮層之附著力等的觀 點較理想。又此等改性單體,可單獨使用或使用複數種。 作爲(甲基)丙烯酸或(甲基)丙烯酸的衍生物’例 如(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯 酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸環己酯 、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸異冰片酯、 (甲基)丙烯酸苯甲酯、(甲基)丙烯酸縮水甘油酯、( 甲基)丙烯酸辛酯、(甲基)丙烯酸月桂酯、(甲基)丙 烯酸十三酯、(甲基)丙烯酸硬脂酯、丙烯醯胺等。又, 此等改性單體可單獨使用或使用複數種,從所得的改性聚 烯烴樹脂的各包覆膜物性,於改性聚烯烴樹脂中,(甲基 )丙烯酸或其衍生物中選自(甲基)丙烯酸辛酯、(甲基 )丙烯酸月桂酯、(甲基)丙烯酸十三酯、(甲基)丙烯 酸硬脂酯的至少1種之接枝量爲0.1〜30重量%較理想。 比該範圍少的接枝量時,改性聚烯烴樹脂的溶劑溶解性、 相位差薄膜對表皮層的附著力降低。而且,相反地太多時 ’反應性高之該改性單體形成超高分子量體,溶劑溶解性 變差’對聚烯烴骨架未改性之同元聚合物、共聚物的生成 量有增加的傾向。 而且,本發明使用的改性聚烯烴樹脂中,依據用途、 目的’在不損害本發明的特性之範圍,可倂用上述改性單 體以外的單體。作爲可能使用的單體,係如苯乙烯、環己 基乙烯基醚、二環戊二烯等可共聚合之不飽和單體。又, -24- 201003249 期望此等單體的使用量不超過改性單體的接枝量之合計。 使用上述改性單體得到改性聚烯烴樹脂之方法,可以 習知的方法進行。例如將聚烯烴樹脂於甲苯等溶劑中加熱 溶解,添加改性單體之溶液法;使用班巴立攪拌器( Bambari mixer)、捏揉機、擠出機等,熔融的聚烯烴樹 脂與改性單體一起添加之熔融法等。改性單體的添加法’ 可逐次添加,亦可一次添加。 作爲反應所使用的自由基引發劑,例如過氧化苯甲醯 、過氧化二-第3 丁基、氫過氧化第3 丁基、過氧化二異 丙苯、過氧化苯甲酸第3 丁酯、過氧化甲基乙基酮、氫過 氧化異丙苯之有機過氧化物、2,2’-偶氮雙異丁腈、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)等偶氮腈類。 於底塗劑使用的改性聚烯烴樹脂,作爲起始原料之聚 烯烴樹脂的分子量無特別限制。但是,改性聚烯烴樹脂的 重量平均分子量爲 15,000〜150,000較理想,更理想爲 30, 〇〇〇〜120,000,更加理想爲 30,000〜100,000。若改性 聚烯烴樹脂的重量平均分子量小於15,000,相位差薄膜對 表皮層的附著力、凝聚力差,大於1 5 0,000時,因黏度增 加’操作性、對溶劑的溶解性有降低的傾向。 本發明所使用的底塗劑,可將上述改性聚烯烴樹脂溶 解於有機溶劑使用。作爲可使用的有機溶劑,例如甲苯、 二甲苯等芳香族系溶劑、環己烷、甲基環己烷、乙基環己 烷、庚烷、壬烷、癸烷等脂肪族系溶劑、乙酸乙酯、乙酸 丁酯等酯系溶劑、丙酮、甲基乙基酮、甲基丁基酮等酮系 -25- 201003249 溶劑、甲醇、乙醇、丙醇、丁醇等醇系溶劑或此等的混合 溶劑。而且,該改性聚烯烴樹脂溶液的固體成分濃度爲 1 0〜5 0重量%較理想。 而且’作爲底塗液的消泡劑,將醇混合於改性聚烯烴 樹脂較理想。作爲醇,例如乙醇、1 _丙醇、2 -丙醇、1 - 丁 醇等。作爲上述改性聚烯烴樹脂,例如作爲市售的樹脂之 曰本製紙製 “Auroren 350T,,、“Auroren S-5106MX”、 “Auroren S-5189T”、三井化學的“UNISTOLE P401”、 “UNISTOLE P801”(皆爲商品名)等。 而且’作爲上述底塗劑塗佈於相位差薄膜之方法,無 特別限制,例如可採用旋轉塗佈法、棒塗法、滾輪塗佈法 、淋幕法及狹縫式塗佈、擠出式塗佈等鑄模式塗佈法等。 塗佈溶液後’組合藉由加熱器加熱、吹熱風等的方法除去 溶劑(乾燥)之步驟等,適當地乾燥溶劑而除去。 再者’底塗層30塗佈於含有聚丙烯系樹脂之相位差 薄膜2 0時,進行電暈處理較理想。藉此,可提高底塗層 3 〇與含有聚丙烯系樹脂之相位差薄膜2 0之密合性。 [黏著劑層] 作爲黏著劑層40,可由丙烯酸系聚合物、聚矽氧系 聚合物、聚酯、聚胺酯、聚醚等爲基質聚合物者所構成。 其中,選擇如丙烯酸系黏著劑之光學透明性佳、保持適度 的潤濕性、凝聚力、與基材的接合性佳,又具有耐候性、 耐熱性等,加熱、加濕的條件下不產生漂浮、剝離等剝離 -26- 201003249 問題者使用較理想。 於丙烯酸系黏著劑,將具有甲基、乙基、丁基等碳數 20以下的烷基之丙烯酸的烷酯,與含有(甲基)丙烯酸 、(甲基)丙烯酸羥基乙酯等所成的官能基之丙烯酸系單 體配合成爲玻璃轉移溫度較理想爲2 5 °C以下,更理想爲 〇°C以下之重量平均分子量爲10萬以上之丙烯酸系共聚物 可有用地作爲基質聚合物。 黏著劑層40係藉由塗佈以上述基質聚合物爲主體之 黏著劑溶液、進行乾燥之方法而可形成外,使用施以離型 處理之薄膜的離型處理面上形成黏著劑層者(附有黏著劑 層之薄膜),藉由將其以黏著劑層側與底塗層30的表面 貼合之方法亦可形成。 而且’於本發明,可使用含有光擴散劑之黏著劑作爲 黏著劑層。此處,所使用的光擴散劑,只要是與構成黏著 劑層之基質聚合物之折射率相異之微粒子即可,可使用由 無機化合物所成的微粒子、由有機化合物(聚合物)所成 的微粒子。含有上述丙烯酸系基質聚合物,構成黏著劑層 40之基質聚合物,因大多顯示1.4左右的折射率,其配合 的光擴散劑,可由折射率爲1〜2程度者適當選擇即可。 構成黏著劑層之基質聚合物與光擴散劑之折射率差,通常 爲0.01以上,且從圖像顯示裝置的亮度與辨識性的觀點 ’ 0.01以上0.5以下較適合。使用作爲光擴散劑的微粒子 ,球形者、近似單分散者較理想,例如適合使用平均粒徑 爲2〜6μιη程度範圍之微粒子。 -27- 201003249 作爲由無機化合物所成的微粒子,例如氧化鋁 率1.76)、氧化矽(折射率1.4 5)等。 而且,作爲由有機化合物所成的微粒子,例如 胺粒子(折射率1 · 57 )、聚甲基丙烯酸甲酯粒子( 1.49 )、甲基丙烯酸甲酯/苯乙烯共聚物樹脂粒子 率1.50〜1.59)、聚碳酸酯粒子(折射率1.55)、 粒子(折射率1.53)、聚苯乙烯粒子(折射率1.6 氯乙烯(折射率1.46)、矽氧樹脂粒子(折射率 等。 光擴散劑的配合量,係考慮所配合之光擴散性 劑層需要之霧度値、應用其之圖像顯示裝置的亮度 當地決定,一般對構成黏著劑層40之基質聚合物 量份而言,爲3〜30重量份的程度。 而且,光擴散劑所配合之光擴散性的黏著劑層 保其橢圓偏光板所應用之圖像顯示裝置的亮度,同 產生顯示圖像之滲透、遲鈍之觀點,其霧度爲20 範圍者較理想。霧度係依JIS K 7 1 0 5規定之(擴 率/全光線透過率)χ100(%)表示的値。 黏著劑層的厚度係依據其接著力等而決定,通 〜40μπι的範圍。爲了作爲本發明的目的之薄型橢 板,在無損加工性、耐久性等的特性之範圍下,期 地塗。因此,黏著劑層的厚度爲3〜25μηι者,從 好的加工性’顯示高耐久性,且保持圖像顯示裝置 觀看時、從側面觀看時的亮度,不易產生顯示圖像 (折射 三聚氰 折射率 (折射 聚乙烯 )、聚 1.46 ) 的黏著 等而適 100重 ,從確 時不易 〜80% 散透過 常爲1 圓偏光 望薄薄 保持良 從正面 之滲透 -28- 201003249 、遲鈍之觀點較適合。 [橢圓偏光板] 1/4波長板可藉由在既定軸角度與直線偏光板層合, 或與1/2波長板一起在既定軸角度與直線偏光板層合,可 成爲橢圓偏光板。圖2(A)、圖2(B)係關於本發明之 橢圓偏光板之一態樣,顯示層構成之剖面圖及說明軸角度 關係用之圖。 參照圖2(A),本發明的一態樣,含有由前述含有 聚丙烯系樹脂之相位差薄膜所成之1/4波長板的附黏著劑 層之相位差薄膜10藉由與直線偏光板50層合,可成爲橢 圓偏光板5 2。於該情況,參照圖2 ( B ),以直線偏光板 50的吸收軸22爲基準,逆時針旋轉的方向爲正,至1/4 波長板的面內延遲相位軸12之角度Θ爲40〜50度,較理 想爲配置成約4 5度,大致上可作爲圓偏光板的功能。或 者,以直線偏光板5 0的吸收軸22爲基準,逆時針旋轉的 方向爲正,至1/4波長板的面內延遲相位軸12之角度Θ爲 130〜140度,較理想爲配置成約135度,依然大致上可 作爲圓偏光板的功能。以下,表示角度時,與此處的說明 相同,相對基準軸,以逆時針旋轉的方向爲正。 而且,參照圖3(A),本發明的另一態樣,分別將 含有由前述含有聚丙烯系樹脂之相位差薄膜所成之1/4波 長板的附黏著劑層之相位差薄膜1 〇與1 /2波長板25層合 ,再於該1/2波長板25側藉由與直線偏光板50層合,可 -29 - 201003249 成爲橢圓偏光板5 5。於該情況,參照圖3 ( B ),以直線 偏光板50的吸收軸22爲基準,至1/2波長板25的面內 延遲相位軸17之角度Φ爲1〇〜20度,較理想爲約15度, 從1/2波長板25的面內延遲相位軸17至1/4波長板的面 內延遲相位軸12之角度φ爲55〜65度,較理想爲配置成 約6 0度,大致上可作爲圓偏光板的功能。或者,以直線 偏光板50的吸收軸22爲基準,至1/2波長板25的面內 延遲相位軸17之角度Φ爲100〜110度,較理想爲約105 度,從1/2波長板25的面內延遲相位軸17至1/4波長板 的面內延遲相位軸1 2之角度φ爲5 5〜6 5度,較理想爲配 置成約6 0度,大致上可作爲圓偏光板的功能。後者的關 係(由直線偏光板的吸收軸至1 /2波長板2 5的面內延遲 相位軸的角度爲100〜110度),係相當於圖3(B)之直 線偏光板的吸收軸2 2以「直線偏光板的透過軸」代替的 狀態。於直線偏光板’吸收軸與透過軸具有在面內垂直的 關係。 特別是如圖3 ( A )所示’含有1 / 4波長板之附有黏 著劑層之相位差薄膜與1/2波長板25層合者’在可見 光區域的寬廣的波長範圍,亦即在寬範圍下作爲1 /4波長 板之功能’其1 /2波長板2 5側層合直線偏光板5 0之橢圓 偏光板5 5,在寬範圍下’可將直線偏光轉換成圓偏光或 將圓偏光轉換爲直線偏光。再者,以如此的構成’可降低 反射防止效果之角度依賴性。 直線偏光板5 0係賦予吸收具有某方向的振動面之直 -30- 201003249 線偏光’透過具有與其垂直的振動面之直線偏光的功能之 光學元件’可使用該領域一般所使用者。具體地,一般由 聚乙烯醇系樹脂所成的偏光薄膜之至少一側的面上形成透 明保護層之聚乙烯醇系直線偏光板。藉由使二色性色素吸 附配向於聚乙烯醇系樹脂的薄膜,如上述可賦予吸收具有 某方向的振動面之直線偏光,透過具有與其垂直的振動面 之直線偏光的功能。作爲二色性色素,可使用碘、二色性 有機染料。於聚乙烯醇系樹脂的薄膜,藉由施以一軸延伸 、以二色性色素之染色及染色後的硼酸處理,可得該偏光 薄膜。 偏光板5 0的透明保護層,例如傳統作爲偏光薄膜的 保護層之一般使用的三醋酸纖維素(TAC )、二醋酸纖維 素爲代表之醋酸纖維素系樹脂薄膜所構成,其他可由冰片 烯系樹脂爲代表之環狀聚烯烴系樹脂的薄膜、聚丙烯系樹 脂的薄膜、聚對苯二甲酸乙二酯樹脂的薄膜、聚(甲基) 丙烯酸甲酯的薄膜等構成。 而且,作爲上述所使用的1/2波長板,可使用上述含 有聚丙烯系樹脂之相位差薄膜,亦可使用其他習知的1/2 波長板,沒有特別限制。作爲其他習知的1 /2波長板,例 如含有環狀聚烯烴系樹脂的相位差薄膜、含有聚碳酸酯的 相位差薄膜等。 在橢圓偏光板的製作時,波長板(相位差薄膜)與直 線偏光板50的貼合,或1/4波長板與1/2波長板25貼合 ,例如可使用黏著劑層。作爲黏著劑層,特別適合使用透 -31 - 201003249 明性及耐久性佳之丙烯酸系聚合物爲主體者。黏著劑層的 厚度,通常爲5〜50μιη的範圍。 如以上構成的橢圓偏光板5 2、5 5,於其1 /4波長板的 面側,配置黏著劑層,可貼附於液晶胞。將該橢圓偏光板 5 2、5 5層合於液晶胞的至少一側而構成液晶顯示裝置。 亦可於液晶胞的兩面配置該橢圓偏光板,亦可於液晶胞的 單面配置該橢圓偏光板而於另一面配置其他的偏光板。貼 合於液晶胞時,使1 /4波長板側朝向液晶胞配置。 [液晶顯示裝置] 於圖4,係以液晶胞的兩面配置本發明的橢圓偏光板 作爲液晶顯示裝置之例,顯示各模型剖面圖。圖4係表示 圖2(A)所示的含有1/4波長板的附有黏著劑層之相位 差薄膜1 〇與直線偏光板5 0的層合物之橢圓偏光板5 2配 置於液晶胞60的兩側之例。亦即,於該例,在液晶胞60 的下側,介由黏著劑層40,由1 /4波長板/直線偏光板50 所成的橢圓偏光板5 2,使其1 /4波長板側朝向液晶胞6 0 而層合,在液晶胞6 0的上側’亦介由黏著劑層4 〇 ’由 1/4波長板/直線偏光板5〇所成的橢圓偏光板52’使其 1 /4波長板側朝向液晶胞6 0而層合。各橢圓偏光板5 2 ’ 使其直線偏光板5 0的吸收軸互相垂直而配置。該液晶顯 示裝置使用作爲透過型或半透過型的情況下,於一側的橢 圓偏光板5 2的外側(圖中爲下側)’配置背光7 0。 圖5係表示圖3(A)所示的含有1Μ波長板的附有 -32 - 201003249 黏著劑層之相位差薄膜1 0與1 /2波長板25與直線偏光板 50的層合物之橢圓偏光板55配置於液晶胞60的兩側之 例。亦即,於該例,在液晶胞60的下側,介由黏著劑層 40,由1/4波長板/1/2波長板25/直線偏光板50所成的橢 圓偏光板5 5,使其1 /4波長板側朝向液晶胞6 0而層合, 在液晶胞60的上側,亦介由黏著劑層40,由1/4波長板 /1/2波長板25/直線偏光板50所成的橢圓偏光板55,使 其1/4波長板側朝向液晶胞60而層合。各橢圓偏光板55 ,使其直線偏光板5 0的吸收軸互相垂直而配置。該液晶 顯示裝置使用作爲透過型或半透過型的情況下,依然於一 側的橢圓偏光板的外側(圖中爲下側),配置背光70。 實施例 以下,顯示實施例更具體地說明本發明,但本發明不 限於此等實施例。例中,表示含量之%,在沒有特別限制 下係重量基準。 [由聚丙烯系樹脂所成的相位差薄膜] 將含有約5%乙烯單元之丙烯/乙烯無規共聚物[住友 化學(股)製“住友Noburene W151”]進行製膜,得到厚 度40μιη的原料薄膜。該原料薄膜藉由進行橫向一軸延伸 ,得到一軸性的相位差薄膜。該相位差薄膜具有R0 = 9〇nm 、Rth = 45nm,厚度爲9μιη。又於含有聚丙稀系樹脂的相 位差薄膜之單面,貼合Toray薄膜加工(股)製的商@ $ -33- 201003249 「Toretec7332」作爲保護薄膜。 [底塗劑1 ] 作爲底塗劑’對順丁烯二酸酐.丙烯酸改性烯烴之曰 本製紙化學(股)製的商品名「Auroren S-5189T」100重 量份’添加甲苯4 5份’ 2 -丙醇1重量份,成爲塗佈用組 成物。Cl8), 1-nine (Ci9), etc. The α-olefin is preferably an α-olefin having 4 to 12 carbon atoms, specifically, for example, 1-butene or 2-methyl-1-propene; 1-pentene, 2·methyl-1-butene; , 3-methyl-1-butene; 1-hexene, 2-ethyl-1·butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3 -methyl-p-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene; 1-heptene, 2-methyl-1-hexene, 2,3 - Dimethyl-1-pentene, 2-ethyl-1-pentene, 2·methyl-3-ethyl-1-butene; 1-octene, 5-methyl-1-heptene, 2 -ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2J,4-trimethyl-1-pentene, 2-propyl-1-pentene, 2,3-diethyl-1-butene;!-pinene; 1-decene; 1-undecene; 1-dodecene, and the like. From the viewpoint of copolymerization, it is preferred that 1-butene, 1-pentene, 1-hexene and 1-octene, especially 1-butene and 1-hexene, be a random copolymer. The copolymer may also be a block copolymer. As a preferred copolymer, for example, a propylene/ethylene copolymer, a propylene/1-butene copolymer. The propylene/ethylene copolymer, the propylene/1-butene copolymer, the content of the ethylene unit, and the content of the 1-butene unit can be described, for example, on page 616 of the "Handbook of Polymer Analysis" (published by Kiyoshiya Shoten, 1995). It is obtained by an infrared (IR) spectrometry method. From the viewpoint of improving the transparency and workability of the retardation film, propylene is mainly used as a random copolymer of any unsaturated hydrocarbon, and it is preferable to use a random copolymer with ethylene. In the case of the copolymer, the unsaturated hydrocarbon other than the propylene oxide is advantageously 1 to 1% by weight of the copolymer, and more preferably 3 to 7% by weight of the copolymer. The unit of the unsaturated hydrocarbons other than propylene, -13 - 201003249, is 1% by weight or more, and the effect of improving workability and transparency tends to be remarkable. On the other hand, when it exceeds 10% by weight of the copolymer, the melting point of the resin is lowered, and the heat resistance tends to be deteriorated. Further, when two or more kinds of comonomers and propylene are copolymerized, the total content of all the units derived from the comonomer contained in the copolymer is preferably in the above range. In the present invention, according to JI s K 7 2 1 0, the temperature is 2 30 ° C, and the load is 2 1 . The polypropylene resin used in the phase difference film measured by 1 8N has a melt index (MFR) of 0. 1~2〇〇g/l points, especially 0. The range of 5 to 50 g/10 minutes is ideal. By using a polypropylene-based resin having an MFR of this range, there is no large burden on the extruder, and a uniform film-like material can be obtained. The polypropylene-based resin may be blended with a conventional additive in a range that does not impair the effects of the present invention. As the additive, for example, an antioxidant, an ultraviolet absorber, a charge preventing agent, a lubricant, a nucleating agent, an antifogging agent, an antiblocking agent and the like. The antioxidant is, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hindered amine-based light stabilizer, or the like, and an anti-oxidation mechanism having a phenol type in one molecule, and a phosphorus-based anti-oxidation system can also be used. A composite antioxidant in the unit of an oxidizing mechanism. Examples of the ultraviolet absorber include a 2-hydroxybenzophenone-based, hydroxyphenylbenzotriazole-based ultraviolet absorber, and a benzoate-based ultraviolet-blocking agent. The charge preventing agent may be any of a polymer type, an oligomer type, and a monomer type. As the lubricant, for example, oleic acid decylamine, oleic acid decylamine, a higher fatty acid decylamine, a higher fatty acid such as stearic acid, and a salt thereof. Examples of the nucleating agent include a sorbitol-based nucleating agent, an organic phosphate-based nucleating agent, and a polymer-based nucleating agent such as polyvinylcyclohexane. As the anti-caking agent, as long as it is a spherical or nearly fine particle, the inorganic or organic system can be used for -14 - 201003249. These additives can be used in a plurality of types. [Material Film of Polypropylene Resin] The polypropylene resin can be formed into a film by any method. The raw material film is transparent and substantially free of in-plane retardation. For example, a polypropylene resin which is substantially free of in-plane retardation can be obtained by an extrusion molding method from a molten resin, a resin casting method in which a resin dissolved in an organic solvent is cast on a flat plate, and a solvent is removed to form a film. Raw material film. As an example of a method of producing a raw material film, a film forming method by extrusion molding will be described in detail. The polypropylene resin was melt-kneaded by rotation of a screw in an extruder, and extruded into a film shape from a T-die. The temperature of the extruded molten sheet is usually about 180 to 300 °C. When the temperature of the molten flakes at this time is lower than 180 ° C, the ductility is insufficient, and the thickness of the obtained raw material film becomes uneven, which may become a raw material film having a phase difference. Further, when the temperature exceeds 300 Torr, deterioration and decomposition of the resin are likely to occur, and bubbles and carbides are formed in the sheet. The extruder can be a single-shaft extruder or a 2-axis extruder. For example, in the case of a single-axis extruder, the ratio L/D of the length L to the diameter D of the screw can be used to the extent of 24 to 36, the space volume of the thread of the resin supply portion and the space volume of the thread of the resin metering portion. The screw having a compression ratio of the former (the latter/the latter) of 1·5 to 4, a full flight type, a barrier type, and a Madoc type kneading portion. From the viewpoint of suppressing deterioration and decomposition of the polypropylene resin and uniformly melting and kneading, L/D is 28 to 36 and the compression ratio is 2. 5~3. 5 barrier ( -15- 201003249 barrier ) type screw is ideal. Further, in order to suppress the deterioration and decomposition of the polypropylene resin as much as possible, the inside of the extruder is preferably a nitrogen atmosphere or a vacuum. In addition, in order to remove the volatile gas generated by the deterioration and decomposition of the propylene resin, an orifice of 5% or less and 5 ηηπι or less is provided at the tip end of the extruder, and the resin pressure at the tip end portion of the extruder is preferably increased. Increasing the resin pressure at the front end portion of the extruder by the orifice means increasing the back pressure at the front end, thereby improving the stability of the extrusion. The diameter of the orifice to be used is more preferably 2 m m φ or more and 4 m m φ or less. For the T-die used for extrusion, it is preferable that the surface of the flow path of the resin has no slight step and scratches, and the material whose lip is plated or coated with a molten polypropylene resin has a small coefficient of friction. The front end of the lip is honed to 0. Sharp edge shapes below 3 m m φ are preferred. As a material having a small friction coefficient, for example, tungsten carbide-based or fluorine-based special plating. By using such a T-die, the generation of the eyelids can be suppressed, and at the same time, the raw material film having good uniformity of appearance can be obtained because the die line can be suppressed. In the T-die, the manifold is in the shape of a garment, and it is preferable that the following conditions (1) or (2) are satisfied, and the condition (3) or (4) is satisfied. The lip width of the T-die is less than 1500mm: the length of the T-die in the thickness direction> 180mm...(1) The lip width of the T-die is 1 500 mm or more: the thickness of the T-die Length of direction>220mm...(2) The width of the lip of the T-die is less than 1 50 0mm: the length of the T-die in the thickness direction>250mm...(3) The lip width of the T-die is 1 5 00mm or more: T-die thickness -16-03203249 length of direction > 280mm. . . (4) By using a T-die that satisfies such conditions, the flow of the molten polypropylene resin inside the τ-type die can be adjusted, and the uneven thickness can be suppressed in the lip portion, and it is obtained. Raw material film with better thickness accuracy and more phase difference. From the viewpoint of suppressing the extrusion variation of the polypropylene resin, it is preferable to install a gear pump between the extruder and the τ-type die via a connector. Further, in order to remove foreign matter in the polypropylene resin, it is preferable to install a leaf disc filter. A metal cooling roll (also referred to as a cooling roll or a casting roll) and a contact roll containing an elastomer which is pressed in the circumferential direction of the metal cooling roll, and a molten sheet extruded from the T die The film is cooled and solidified to obtain a desired raw material film. At this time, the contact roller may be an elastic body such as rubber as a surface thereof, or may be an outer cylinder coated with a metal sleeve on the surface of the elastic roller. In the case where a contact roller coated with an outer cylinder made of a metal sleeve is used on the surface of the elastic roller, a molten sheet of a polypropylene resin is directly sandwiched between the metal cooling roller and the contact roller, so that the molten sheet is directly sandwiched between the metal cooling roller and the contact roller. cool down. On the other hand, in the case where a contact roll having an elastomer surface is used, a biaxially stretched film of a thermoplastic resin may be pressed between the molten sheet of the polypropylene resin and the contact roll. The molten sheet of the polypropylene resin is cooled and solidified by the cooling roll and the contact roll as described above. The temperature of the surface of the cooling roll and the light contact is lowered first, and the molten sheet must be rapidly cooled. For example, it is preferable to adjust the surface temperature of the cooling roll and the contact roll to a range of 0 ° C or more and 30 ° C or less. When the surface temperature of these -17-201003249 exceeds 30 °C, the cooling and solidification of the molten sheet takes time, the crystal component in the polypropylene resin grows, and the transparency of the obtained raw material film is deteriorated. The surface temperature of the chill roll and the contact roll is preferably 30 ° C or less, preferably less than 25 ° C. On the other hand, when the surface temperature of the cooling roll and the contact roll is lower than 〇 ° C, the surface of the metal cooling roll is dew condensation, and water droplets adhere thereto, and the appearance of the raw material film tends to deteriorate. The metal cooling roll to be used is transferred to the surface of the raw material film containing the polypropylene resin, and has irregularities on the surface, which may lower the thickness accuracy of the obtained raw material film containing the polypropylene resin. Therefore, it is preferable that the surface of the metal cooling roll is as mirror-like as possible. Specifically, the surface roughness of the metal chill roll is expressed by a standard series of maximum heights, 0. 3S or less is ideal, and 0. 1S~0. 2S is more preferable to form the surface hardness of the elastic body of the contact roller which is formed with the metal cooling roll holding portion, and is measured by a spring type hardness test (A shape) prescribed in JIS K63 0 1 to be 65 to 80. Ideal, 70~80 is more ideal. By using such a rubber roller having a surface hardness, it is easy to maintain a uniform line pressure applied to the molten sheet, and a bank of molten flakes is not produced between the metal cooling roll and the contact roll (resin accumulation) It is easy to form into a film. The pressure (line pressure) at the time of rolling the molten sheet is determined by the pressure of the contact roller being pressed against the metal. The line pressure is preferably 50 N/cm or more and 3 00 N/cm or less, and more preferably 1 0N/cm or more and 2500 N/cm or less. By the wire pressure being in the above range, the original pressure of the polypropylene resin can be easily produced between the metal cooling roll and the contact roll while maintaining the line pressure of -18-201003249 without forming the enthalpy. The thermoplastic resin of the biaxially stretched film of the molten foil of the polypropylene and the biaxially stretched film of the thermoplastic resin is a resin which is not thermally fused to the polypropylene, specifically, for example, polyester, polyamide, or poly Among vinyl alcohol, ethylene-vinyl alcohol copolymer, polyacrylonitrile, and the like, polyester having a small dimensional change such as humidity and heat is most preferable. The thickness of the two-axis stretching film is usually 5 to 50 μm, and the thickness is 10 to 30 μm. In this method, it is more preferable that the distance from the 模-type die to the metal chill roll and the pressure (air gap) is 200 mm or less and 1 60 mm or less. The molten thin lip extruded from the T-die is extended between the metal cooling rolls to easily form an alignment. The gap is as short as described above, and a raw material film having a small alignment can be obtained. The air gap is determined by the diameter of the metal cooling roller to be used and the shape of the tip end of the lip used for the diameter of the contact roller, and is usually 50 mm or more. The speed of the raw material film containing the polypropylene resin is produced by this method. When the diameter of the metal cooling roll to be used is determined by the time required for the molten sheet to cool and solidify, the distance between the molten sheet and the roll becomes long, and the production can be performed at a higher speed. Specifically, in the case of a metal cooling roll of '600 mm mφ, the processing speed is at most 20 m/min. A molten tantalum film which is pressed between a metal cooling roll and a contact roll, an olefinic tree, an olefinic tree, a polychlorine or the like. In this case, it is ideal to touch the roller, and the film is cut from the lower limit of the air and the processing of the crucible. This cooling is used as a 5~ sheet, -19-201003249 by cooling in contact with a metallic cooling roll. Then, the end portion is cut as necessary, and then taken up by a winder to form a raw material film. In this case, in order to protect the surface thereof until the raw material film is used, the surface protective film formed of another thermoplastic resin may be wound on one side or both sides thereof. When the molten film of the polypropylene resin is pressed between the metal cooling roll and the contact roll together with the biaxially stretched film made of the thermoplastic resin, the biaxially stretched film can be a surface protective film on one side. [Method for Producing Phase Difference Film] In the present invention, the retardation film can be produced by laterally stretching the above-mentioned raw material film containing a polypropylene resin. Here, the horizontal extension means a long raw material film which is taken up from a metal cooling roll and extends in the width direction (horizontal direction). Horizontal extension usually has the following steps. (A) a preheating step of preheating the raw material film at a preheating temperature near the melting point of the polypropylene resin; (B) preheating the raw material film at a temperature lower than the preheating temperature and performing the transverse direction And an extension step of extending; and (C) a heat-fixing step of thermally fixing the raw material film extending in the lateral direction. As a representative horizontal extension method, for example, a tenter method. The tentering method is a method in which the raw material film at both ends in the width direction of the film is fixed by a chuck, and the gap between the chucks is extended in the oven. The stretching machine (the tenter stretching machine) used in the tenter method generally has a mechanism for independently adjusting the temperature in the region where the preheating step is performed, the region where the stretching step is performed, and the region where the heat fixing step is performed. A retardation film having a good axis precision and a uniform phase difference can be obtained by performing lateral stretching using such a tenter stretching machine. The pre-heating step of the lateral stretching is a step which is provided before the step of extending the raw material film in the width direction. The step of heating the raw material film to a sufficient temperature when the raw material film is stretched. The preheating temperature in the preheating step is the ambient temperature in the region where the preheating step of the oven is performed. The temperature near the melting point of the stretched raw material film containing the polypropylene resin is used. The residence time of the preheating step of the stretched raw material film is preferably from 3 to 10 seconds. When the residence time of the preheating step is less than 30 seconds, when the raw material film is stretched in the stretching step, the stress is dispersed, which may adversely affect the axial precision and the phase difference of the retardation film, and the retention may be caused. When the time exceeds 1 20 seconds, the heat of the raw material is required to be partially melted, and there is a possibility that the raw material film is sag (downward). The residence time in the preheating step is preferably from 30 to 60 seconds. 延伸 The step of extending the transverse direction is a step of stretching the raw material film in the width direction. The extension temperature of the extension step is usually a temperature lower than the preheating temperature. The extension temperature of the extension step refers to the ambient temperature of the region in which the oven is subjected to the stretching step. By extending the preheated raw material film at a temperature lower than the preheating step, the raw material film can be uniformly extended, and as a result, a retardation film having excellent optical axis and phase difference uniformity can be obtained. The extension temperature is 5 to 20 ° C lower than the preheating temperature of the preheating step, and more preferably 7 to 15 ° C. The stretching ratio at this time is in the range of 3 to 10 times in the direction in which the optical axis is found (the direction in which the phase axis is delayed), and the phase difference 符合 is required, and the appropriate selection is 21 - 201003249, preferably 3 ~6 times the range. With the stretching ratio at this time being more than 3 times, the aforementioned Nz coefficient can be made 0. 9~1. The scope of 1. On the other hand, when the stretching ratio becomes too large, the uniformity of the phase difference 可能 may be impaired, and it is preferable to be 10 times. The horizontally extending heat-fixing step is a step of passing the raw material film through a predetermined temperature region in the oven while maintaining the film width at the end of the stretching step. In order to effectively improve the phase difference of the raw material film and the stability of the optical characteristics such as the optical axis, the temperature of the heat fixation is from a temperature lower by 5 ° C than the elongation temperature of the stretching step to a temperature higher than the extension temperature by 30 t: The step of ideally extending transversely can be further provided with a thermal mitigation step. The heat relaxation step, in which the tentering method is carried out, is usually carried out between the stretching step and the heat fixing step, and the region where the heat is moderated is generally independent of the other regions, and the settable temperature is set. Specifically, the 'heat relaxation step is after the extension step extends the raw material film to a predetermined width'. In order to remove the undesired bending, the interval of the chuck is reduced by only a few %, which is usually narrower than the interval at the end of the extension 0 · 5~7 %Degree. [Optical Characteristics When Using a Wavelength Plate] In the present invention, the retardation film is used as a 1/4 wavelength plate, and the in-plane phase difference 値(R〇) is preferably in the range of 70 to 160 nm, and is also 80 0~ The range of 1 5 Onm is more ideal. The 1/4 wavelength plate system has a function of converting light incident on a linearly polarized light into elliptically polarized light mainly composed of circularly polarized light, or light having an elliptically polarized light mainly composed of circularly polarized light, which is converted into linearly polarized light and emitted. On the other hand, in the case where the retardation film of the present invention is used as a 1/2 wave plate, -22-201003249, the in-plane phase difference 値(Ro) is preferably in the range of 24 〇 to 400 nm, and is in the range of 260 to 330 nm. More ideal. The 1/2 wavelength plate has the function of rotating the direction of linear polarization. [Substrate] The polyolefin resin which is a raw material of the modified polyolefin resin is a propylene-α-olefin copolymer mainly composed of propylene and a copolymer of α-olefin, and may be selected from block copolymers and random. Any of the copolymers. The α-olefin component is, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene 4-methyl-1-pentene or the like. The content of the propylene component is 50 to 9 〇 mol%. When the film is most suitable for '50 mol% or less, the adhesion of the retardation film to the skin layer is poor, and when it is 90 mol% or more, the flexibility of the retardation film tends to be insufficient. . Further, the graft amount of the unsaturated polycarboxylic acid or the unsaturated polycarboxylic acid derivative of the modified monomer of the modified polyolefin resin, and the derivative of (meth)acrylic acid or (meth)acrylic acid are respectively 0. . 1 to 20% by weight, 0. 1 to 3 〇% by weight is ideal. When the amount of grafting is less than this range, the solubility in a solvent tends to be lowered. Further, when the amount of grafting is larger than this range, the adhesion to the polyolefin tends to be lowered. As an unsaturated polycarboxylic acid or a derivative of an unsaturated polycarboxylic acid, such as maleic acid, fumaric acid, tetrahydrofurfuric acid, methylene succinic acid, methyl maleic acid, 2 - unsaturated polycarboxylic acids such as crotonic acid, aconitic acid, citric acid, trimellitic acid, borneol dicarboxylic acid or derivatives thereof (for example, acid anhydrides, acid halides, guanamines, guanidines) Amines, esters, etc.). In these -23- 201003249, the grafting amount of methylene succinic anhydride and maleic anhydride was 0. From 1 to 20% by weight, it is preferable from the viewpoint of adhesion of the retardation film to the skin layer and the like. Further, these modified monomers may be used singly or in plural. As a derivative of (meth)acrylic acid or (meth)acrylic acid, for example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, (a) Cyclohexyl acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, octyl (meth) acrylate And lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, acrylamide, and the like. Further, these modified monomers may be used singly or in plural, and selected from the properties of the coating film of the obtained modified polyolefin resin, (meth)acrylic acid or a derivative thereof in the modified polyolefin resin. The graft amount of at least one of octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate is 0. 1 to 30% by weight is preferred. When the amount of grafting is less than this range, the solvent solubility of the modified polyolefin resin and the adhesion of the retardation film to the skin layer are lowered. Further, when the amount is too large, the modified monomer having a high reactivity forms an ultrahigh molecular weight body, and the solvent solubility is deteriorated, and the amount of the unmodified polymer or copolymer of the polyolefin skeleton is increased. tendency. Further, in the modified polyolefin resin used in the present invention, a monomer other than the above-mentioned modified monomer can be used depending on the purpose and purpose of the present invention without impairing the characteristics of the present invention. As the monomer which may be used, a copolymerizable unsaturated monomer such as styrene, cyclohexyl vinyl ether or dicyclopentadiene is used. Further, -24-201003249 It is desirable that the amount of such monomers used does not exceed the total amount of grafting of the modified monomers. The method of obtaining a modified polyolefin resin by using the above modified monomer can be carried out by a conventional method. For example, a method of adding a modified monomer by heating and dissolving a polyolefin resin in a solvent such as toluene; using a Bambari mixer, a kneading machine, an extruder, etc., a molten polyolefin resin and a modified single The fusion method in which the body is added together. The addition method of the modified monomer ' may be added one by one or one time. As the radical initiator used in the reaction, for example, benzamidine peroxide, di-tert-butyl peroxide, d-butyl hydroperoxide, dicumyl peroxide, d-butyl peroxybenzoate, Methyl ethyl ketone peroxide, organic peroxide of cumene hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4 -Azo nitrile such as dimethyl valeronitrile. The molecular weight of the polyolefin resin used as the starting material for the modified polyolefin resin used in the primer is not particularly limited. However, the modified polyolefin resin preferably has a weight average molecular weight of from 15,000 to 150,000, more preferably from 30, 〇〇〇 1 to 120,000, still more preferably from 30,000 to 100,000. When the weight average molecular weight of the modified polyolefin resin is less than 15,000, the adhesion and cohesive force of the retardation film to the skin layer are inferior, and when it is more than 1,500, the viscosity is increased, and the solubility in the solvent tends to decrease. . The primer used in the present invention can be used by dissolving the above modified polyolefin resin in an organic solvent. Examples of the organic solvent that can be used include an aromatic solvent such as toluene or xylene, an aliphatic solvent such as cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, decane or decane, and ethyl acetate B. An ester solvent such as ester or butyl acetate; a ketone such as acetone, methyl ethyl ketone or methyl butyl ketone - 25-201003249 Solvent, alcohol solvent such as methanol, ethanol, propanol or butanol or a mixture thereof Solvent. Further, the modified polyolefin resin solution preferably has a solid content concentration of from 10 to 50% by weight. Further, as the antifoaming agent for the primer liquid, it is preferred to mix the alcohol with the modified polyolefin resin. As the alcohol, for example, ethanol, 1-propanol, 2-propanol, 1-butanol or the like can be mentioned. As the modified polyolefin resin, for example, "Auroren 350T,", "Auroren S-5106MX", "Auroren S-5189T", "UNISTOLE P401" and "UNISTOLE P801" of Mitsui Chemicals, which are commercially available resins. The method of applying the primer to the retardation film is not particularly limited, and for example, a spin coating method, a bar coating method, a roller coating method, a shower method, and the like can be employed. A casting mode coating method such as a slit coating or an extrusion coating method, etc. After the solution is applied, a step of removing the solvent (drying) by heating by a heater, blowing of hot air, or the like is carried out, and the solvent is appropriately dried. Further, when the undercoat layer 30 is applied to the retardation film 20 containing a polypropylene resin, corona treatment is preferably performed, whereby the phase of the undercoat layer 3 and the polypropylene-containing resin can be improved. Adhesive film 20. [Adhesive layer] The adhesive layer 40 may be composed of an acrylic polymer, a polyoxymethylene polymer, a polyester, a polyurethane, a polyether or the like as a matrix polymer. , choose such as acrylic The adhesive has good optical transparency, moderate wettability, cohesive force, good adhesion to the substrate, weather resistance, heat resistance, etc., and does not cause peeling or peeling under heating or humidification conditions. - 201003249 It is preferred that the problem is solved. For the acrylic adhesive, an alkyl ester of acrylic acid having an alkyl group having a carbon number of 20 or less such as a methyl group, an ethyl group or a butyl group, and (meth)acrylic acid or (meth) The acrylic monomer having a functional group formed by hydroxyethyl acrylate or the like is preferably an acrylic copolymer having a glass transition temperature of preferably 25 ° C or less, more preferably 〇 ° C or less and a weight average molecular weight of 100,000 or more. Useful as a matrix polymer. The adhesive layer 40 can be formed by applying an adhesive solution mainly composed of the above-mentioned matrix polymer, and drying it, and using a release treatment surface of the release-treated film. The layer on which the adhesive layer is formed (the film with the adhesive layer) can also be formed by bonding the adhesive layer side to the surface of the undercoat layer 30. Moreover, in the present invention, An adhesive containing a light diffusing agent is used as the adhesive layer. Here, the light diffusing agent to be used may be a fine particle having a refractive index different from that of the matrix polymer constituting the adhesive layer, and may be formed of an inorganic compound. The fine particles, the fine particles formed of the organic compound (polymer), and the matrix polymer which comprises the above acrylic matrix polymer and constitutes the adhesive layer 40, since most of them show 1. The refractive index of about 4, and the light diffusing agent to be blended may be appropriately selected from the range of the refractive index of 1 to 2. The refractive index difference between the matrix polymer constituting the adhesive layer and the light diffusing agent is usually 0. 01 or more, and from the viewpoint of brightness and visibility of the image display device ’ 0. 01 or more 0. 5 is more suitable. The use of fine particles as a light diffusing agent is preferably a spherical one or an almost monodisperse. For example, it is suitable to use fine particles having an average particle diameter of about 2 to 6 μm. -27- 201003249 As a fine particle formed by an inorganic compound, for example, an alumina ratio of 1. 76), yttrium oxide (refractive index 1. 4 5) Wait. Further, as fine particles composed of an organic compound, for example, amine particles (refractive index 1 · 57 ), polymethyl methacrylate particles (1) 49), methyl methacrylate / styrene copolymer resin particles rate 1. 50~1. 59), polycarbonate particles (refractive index 1. 55), particles (refractive index 1. 53), polystyrene particles (refractive index 1. 6 vinyl chloride (refractive index 1. 46), oxime resin particles (refractive index, etc.. The amount of the light diffusing agent is determined by considering the haze required for the light diffusing agent layer to be blended, and the brightness of the image display device to be used is determined locally. The amount of the matrix polymer of the adhesive layer 40 is about 3 to 30 parts by weight. Moreover, the light diffusing adhesive layer to which the light diffusing agent is blended maintains the brightness of the image display device to which the elliptically polarizing plate is applied. The viewpoint of the penetration and dullness of the display image is ideal, and the haze is preferably in the range of 20%. The haze is expressed in accordance with JIS K 7 1 0 5 (expansion rate / total light transmittance) χ 100 (%). The thickness of the adhesive layer is determined according to the adhesion force, etc., and is in the range of ~40 μm. For the purpose of the invention, the thin ellipsoid is coated in a range of properties such as non-destructive workability and durability. Therefore, the thickness of the adhesive layer is 3 to 25 μm, which is excellent in durability, exhibits high durability, and maintains brightness when viewed from the side while being viewed by the image display device, and is hard to produce a display image (refraction trimerization) Cyanide refraction (Refractive polyethylene), poly 1. 46) The adhesion is equal to 100 weights, and it is not easy to be true. ~80% scatter through. [Elliptical Polarizing Plate] The 1/4 wavelength plate can be laminated with a linear polarizing plate at a predetermined axial angle, or laminated with a linear polarizing plate at a predetermined axial angle together with a half-wavelength plate, and can be an elliptically polarizing plate. Fig. 2 (A) and Fig. 2 (B) are views showing a cross-sectional view of a display layer and a view for explaining the relationship of the axial angles with respect to one aspect of the ellipsic polarizing plate of the present invention. Referring to Fig. 2(A), in one aspect of the present invention, a phase difference film 10 comprising an adhesive layer comprising a quarter-wave plate made of the retardation film containing a polypropylene resin is used with a linear polarizing plate. 50 layers can be used to form an elliptically polarizing plate 52. In this case, referring to FIG. 2(B), the direction of counterclockwise rotation is positive with respect to the absorption axis 22 of the linear polarizing plate 50, and the angle Θ of the in-plane retardation phase axis 12 of the 1/4 wavelength plate is 40~. 50 degrees, preferably configured to be about 45 degrees, can generally function as a circular polarizing plate. Alternatively, the direction of counterclockwise rotation is positive with respect to the absorption axis 22 of the linear polarizing plate 50, and the angle Θ of the in-plane retardation phase axis 12 of the quarter-wavelength plate is 130 to 140 degrees, and is preferably configured to be approximately 135 degrees, still roughly functions as a circular polarizer. Hereinafter, when the angle is expressed, as in the description herein, the direction rotated counterclockwise with respect to the reference axis is positive. Further, referring to Fig. 3(A), in another aspect of the present invention, a phase difference film 1 containing an adhesive layer of a quarter-wave plate made of the retardation film containing the polypropylene resin is used. The 1/2 wavelength plate 25 is laminated, and the 1/2 wavelength plate 25 is laminated on the side of the 1/2 wavelength plate 25 to form an elliptically polarizing plate 55 by -29 - 201003249. In this case, referring to FIG. 3(B), the angle Φ of the in-plane retardation phase axis 17 to the half-wavelength plate 25 is 1 〇 to 20 degrees with respect to the absorption axis 22 of the linearly polarizing plate 50, which is preferably The angle φ of the in-plane retardation phase axis 12 from the in-plane retardation phase axis 17 of the 1/2 wavelength plate 25 from the in-plane retardation of the half-wavelength plate 25 is 55 to 65 degrees, preferably about 60 degrees, preferably about 15 degrees. It can be used as a function of a circular polarizer. Alternatively, the angle Φ of the in-plane retardation phase axis 17 to the half-wavelength plate 25 is 100 to 110 degrees, preferably about 105 degrees, from the 1/2 wavelength plate, based on the absorption axis 22 of the linear polarizing plate 50. The in-plane retardation phase axis of 25 is an in-plane retardation of the phase axis 17 to the quarter-wave plate. The angle φ of the phase axis 1 2 is 5 5 to 6 5 degrees, and is preferably configured to be about 60 degrees, which is substantially as a circular polarizing plate. Features. The relationship of the latter (from the absorption axis of the linear polarizing plate to the in-plane retardation phase axis of the 1 / 2 wavelength plate 25 is 100 to 110 degrees), which is equivalent to the absorption axis 2 of the linear polarizing plate of FIG. 3(B) 2 is replaced by the "transmission axis of the linear polarizer". In the linear polarizing plate, the absorption axis and the transmission axis have a perpendicular relationship in the plane. In particular, as shown in Fig. 3 (A), the "phase difference film with an adhesive layer and a half-wave plate 25 laminated with a 1/4 wavelength plate" has a wide wavelength range in the visible light region, that is, Wide range of functions as a 1 / 4 wave plate '1 /2 wave plate 2 5 side laminated linear polarizer 50 0 ellipsoidal plate 5 5, in a wide range 'can convert linear polarized light into circular polarized light or will Circular polarization is converted to linear polarization. Further, with such a configuration, the angle dependency of the antireflection effect can be reduced. The linear polarizing plate 50 is provided to absorb a vibration surface having a certain direction. -30-201003249 Linear polarized light 'Optical element that transmits a linearly polarized light having a vibrating surface perpendicular thereto' can be used by a general user in the field. Specifically, a polyvinyl alcohol-based linear polarizing plate having a transparent protective layer is generally formed on at least one surface of a polarizing film made of a polyvinyl alcohol-based resin. By absorbing the dichroic dye to the film of the polyvinyl alcohol-based resin, it is possible to impart a linearly polarized light that absorbs a vibrating surface having a certain direction as described above, and transmits a linearly polarized light having a vibrating surface perpendicular thereto. As the dichroic dye, iodine or a dichroic organic dye can be used. The polarizing film can be obtained by subjecting a film of a polyvinyl alcohol-based resin to one-axis stretching, dyeing with a dichroic dye, and boric acid treatment after dyeing. The transparent protective layer of the polarizing plate 50 is composed of, for example, cellulose triacetate (TAC) and cellulose acetate resin film generally represented by cellulose diacetate, which are conventionally used as a protective layer of a polarizing film, and other may be a borneol-based film. The resin is a film of a cyclic polyolefin resin represented by a resin, a film of a polypropylene resin, a film of a polyethylene terephthalate resin, a film of poly(methyl) methacrylate, or the like. Further, as the above-mentioned 1/2 wavelength plate, the above-mentioned retardation film containing a polypropylene resin may be used, and other conventional 1/2 wavelength plates may be used, and it is not particularly limited. Other conventional 1/2-wavelength plates include, for example, a retardation film containing a cyclic polyolefin resin, a retardation film containing polycarbonate, and the like. In the production of the elliptically polarizing plate, the wavelength plate (phase difference film) is bonded to the linear polarizing plate 50, or the 1⁄4 wavelength plate is bonded to the 1⁄2 wavelength plate 25, and for example, an adhesive layer can be used. As the adhesive layer, it is particularly suitable to use an acrylic polymer which is excellent in clarity and durability. The thickness of the adhesive layer is usually in the range of 5 to 50 μm. The elliptically polarizing plates 5 2, 5 5 having the above configuration are provided with an adhesive layer on the surface side of the 1/4 wavelength plate, and can be attached to the liquid crystal cell. The elliptically polarizing plates 5 2, 5 5 are laminated on at least one side of the liquid crystal cell to constitute a liquid crystal display device. The elliptically polarizing plate may be disposed on both sides of the liquid crystal cell, or the elliptically polarizing plate may be disposed on one side of the liquid crystal cell and the other polarizing plate may be disposed on the other surface. When bonding to the liquid crystal cell, the 1/4 wavelength plate side is placed toward the liquid crystal cell. [Liquid Crystal Display Device] In Fig. 4, an elliptically polarizing plate of the present invention is disposed on both surfaces of a liquid crystal cell as an example of a liquid crystal display device, and a cross-sectional view of each model is displayed. 4 is an elliptically polarizing plate 52 showing a laminate of a retardation film 1 〇 and a linear polarizing plate 50 with an adhesive layer shown in FIG. 2(A), which is disposed on a liquid crystal cell. Examples of the sides of the 60. That is, in this example, on the lower side of the liquid crystal cell 60, the elliptically polarizing plate 52 made of the 1/4 wavelength plate/linear polarizing plate 50 via the adhesive layer 40 is made to have a 1/4 wavelength plate side. Laminated toward the liquid crystal cell 60, and the upper side of the liquid crystal cell 60 is also made of an elliptically polarizing plate 52' formed of a quarter-wave plate/linear polarizing plate 5 by an adhesive layer 4'. The 4 wavelength plate side is laminated toward the liquid crystal cell 60. Each of the elliptically polarizing plates 5 2 ' is disposed such that the absorption axes of the linear polarizing plates 50 are perpendicular to each other. When the liquid crystal display device is used as a transmissive or semi-transmissive type, the backlight 70 is disposed on the outer side (lower side in the figure) of the elliptical polarizing plate 52 on one side. Fig. 5 is a view showing the ellipse of the laminate of the retardation film 10 and the 1/2 wave plate 25 and the linear polarizing plate 50 with the -32 - 201003249 adhesive layer shown in Fig. 3 (A). The polarizing plate 55 is disposed on both sides of the liquid crystal cell 60. That is, in this example, on the lower side of the liquid crystal cell 60, the elliptically polarizing plate 5 5 made of the 1/4 wavelength plate / the 1/2 wavelength plate 25 / the linear polarizing plate 50 via the adhesive layer 40 is used. The 1/4 wavelength plate side is laminated toward the liquid crystal cell 60, and on the upper side of the liquid crystal cell 60, also via the adhesive layer 40, by the 1/4 wavelength plate / the 1/2 wavelength plate 25 / the linear polarizing plate 50 The elliptically polarizing plate 55 is formed such that the 1/4 wavelength plate side thereof is laminated toward the liquid crystal cell 60. Each of the elliptically polarizing plates 55 is disposed such that the absorption axes of the linear polarizing plates 50 are perpendicular to each other. When the liquid crystal display device is used as a transmissive or semi-transmissive type, the backlight 70 is disposed on the outer side (lower side in the figure) of the elliptically polarizing plate on one side. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the example, the % of the content is shown, and the weight basis is not particularly limited. [Retardation film made of polypropylene resin] A propylene/ethylene random copolymer containing about 5% of ethylene units [Sumitomo Noburene W151" manufactured by Sumitomo Chemical Co., Ltd. was formed into a film to obtain a material having a thickness of 40 μm. film. The raw material film is stretched in the transverse direction to obtain a one-axis retardation film. The retardation film had R0 = 9 〇 nm, Rth = 45 nm, and a thickness of 9 μm. On the one side of the phase difference film containing the polypropylene resin, the Toray film processing company (Toretec7332) was attached as a protective film. [Substrate 1] as a primer 'for maleic anhydride. In the case of the acrylic acid-modified olefin, 100 parts by weight of the product name "Auroren S-5189T" manufactured by Tosoh Corp. was added, and 1 part by weight of toluene (5 parts) of 2-propanol was added to obtain a coating composition.
Auroren S-5189T 的分子量爲 60000〜80000 。 實施例1 (a )相位差薄膜與底塗層的層合 由聚丙烯系樹脂所成的相位差薄膜之層合表面保護薄 膜之相反側,以累積照射量15_9kJ/m2施以電暈放電處理 。在電暈放電處理後5分鐘內,於該電暈處理面,使用邁 耶(Mayer)棒(# 6 )塗佈上述底塗劑塗佈用組成物,以 8 0 °C的烤箱乾燥3分鐘,於相位差薄膜上形成厚度0.8 μιη 的底塗層。 (b)橢圓偏光板的製作 使用碘吸附配向於聚乙烯醇之偏光薄膜的兩面上接合 由三醋酸纖維素所成的保護薄膜之偏光板[住友化學(股 )製SRW062],於其單面貼合聚胺酯丙烯酸酯系薄片狀黏 著劑[Lintec (股)販售的NS 3 00MP] ’製作附黏著劑之偏 光板。另一方面,從上述(a )製作的附底塗層之相位差 -34- 201003249 薄膜,剝離表面保護薄膜,於該面(聚丙烯系樹脂面), 以累積照射量15.9kJ/m2施以電暈放電處理,在電暈放電 處理後5分鐘內,於該電暈處理面,貼合上述製作的附黏 著劑之偏光板的黏著劑層。然後,於底塗層側,亦以累積 照射量1 5 · 9k J/m2施以電暈放電處理。在電暈放電處理後 5分鐘內,於該電暈處理面,貼合丙烯酸系薄片狀黏著劑 [Lintec (股)販售的P3132],得到附黏著劑層之橢圓偏 光板。 (c)橢圓偏光板的厚度測定 (b )所得的附黏著劑層之複合偏光板,使用(股) 尼康(Nikon )製的數位測長度器“MH-1 5M”,測定厚度。 結果表示於表1。 (d )固著力測試 剝離(a )所得的附底塗層之相位差薄膜的保護薄膜 ,於該面以累積照射量15.9 k J/m2的條件施以電暈放電處 理。而且,對2軸性的熱塑性飽和冰片烯樹脂[日本ΖΕΟΝ (股)製的ZB 05 5 1 24]以累積照射量15.9k J/m2的條件施 以電暈放電處理。在電暈放電處理後10分鐘內,於2軸 性的熱塑性飽和冰片烯樹脂的電暈處理面,使用邁耶( Mayer )棒(# 1)塗佈含有環氧化合物的活性能量線硬化 性樹脂組成物,該塗佈面與附底塗層之相位差薄膜的電暈 處理面貼合,在 FUSION公司製 UV照射裝置,以 -35- 201003249 500mW/1500mJ進行UV硬化。接著,於底塗層表面,以 累積照射量15_9kJ/m2施以電暈放電處理後’在電暈放電 處理後5分鐘內,於該電暈處理面貼合丙烯酸系黏著劑( Lintec (股)販售的P3132 ),製作附黏著劑之相位差薄 膜,製作接著性評價用薄膜。然後,在溫度23°C濕度60 % RH的環境下,放置1天。將該接著性評價用薄膜切斷 成寬度25mm、長度約200mm,使用前述日本系統集團( 股)製“密合力評價裝置”,評價長度方向上3點的密合力 。評價係使用硬度60度的苯乙烯橡膠,一邊以0.4MP a的 按壓力按壓,一邊從一定的方向摩擦20次’黏著劑層從 塗佈相位差層剝離之長度的3點平均作爲剝離距離而求得 。此外,測定係在溫度23 °C濕度60 % RH的環境下進行。 結果表示於表1。 (e )貼附玻璃板之剝離測試 將前述(d )所得的接著性評價用薄膜切斷成寬度 25mm、長度約200mm,該感壓式黏著劑層面貼合於鈉玻 璃後,在高壓釜中,壓力5kgf/cm2、溫度50°C下進行20 分鐘的加壓處理,在溫度23 °C濕度60% RH的環境下,放 置1天。而且,剝離係使用萬能拉伸測試機(AG_ 1、 SHIMAZU (股)製),在溫度23t濕度60% RH的環境下 ,以十字頭速度(剝離速度)200mm/分,90°剝離測試進 行評價。而且,測定係在溫度23 °C濕度60% RH的環境下 進行。 -36- 201003249 表1中,剝離性的記號由以下表示。 良好:玻璃板上沒有殘留黏著劑層,可剝離。 不良·玻璃板上殘留黏著劑層而剝離。 [底塗劑2] 烴之曰 40重 重量份 60000 作爲底塗劑’對順丁烯二酸酐·丙烯酸改性儲 本製紙化學(股)製的商品名「Auroren 250_MX 量份’添加甲苯30份’作爲消泡劑之2 -丙醇i〇 ,成爲塗佈用組成物。Auroren 250-MX的分子量爲 〜8 0 0 0 0 〇 實施例2 保護薄 電處理 使用邁 組成物 成厚度 (a)相位差薄膜與底塗層的層合 由聚丙燃系樹脂所成的相位差薄膜之層合表面 膜之相反側,以累積照射量15.9k J/m2施以電暈放 。在電暈放電處理後5分鐘內,於該電暈處理面, 耶(Mayer )棒(#14)塗佈上述底塗劑2塗佈用 ,以8(TC的烤箱乾燥5分鐘,於相位差薄膜上形 Ι.Ομιη的底塗層。 (b )橢圓偏光板的製作 與實施例1同樣地製作橢圓偏光板。 (C )橢圓偏光板的厚度測定 -37- 201003249 與實施例1同樣地進行測定。測定結果表示 (d )固著力測試 與實施例1同樣地進行測定。測定結果表示 (e )貼附玻璃板之剝離測試 與實施例1同樣地進行測定。測定結果表汙 [底塗劑3] 作爲底塗劑,對順丁烯二酸酐•丙烯酸改怊 本製紙化學(股)製的商品名「Auroren 3 5 0T」 份,添加作爲消泡劑之2-丙醇3重量份,成赁 成物。Auroren 350T的分子量爲60000〜80000 實施例3 (a )相位差薄膜與底塗層的層合 由聚丙烯系樹脂所成的相位差薄膜之層合_ 膜之相反側,以累積照射量15.9kJ/m2施以電J 。在電暈放電處理後5分鐘內,於該電暈處理面 耶(Mayer )棒(#3)塗佈上述底塗劑3塗佈用 以的烤箱乾燥3分鐘,於相位差薄膜上 0.8 μ m的底塗層》 (b )橢圓偏光板的製作 於表1。 於表1。 於表1。 烯烴之曰 1 〇 0重量 塗佈用組 面保護薄 放電處理 ,使用邁 組成物, 形成厚度 -38- 201003249 與實施例1同樣地製作橢圓偏光板。 (c)橢圓偏光板的厚度測定 與實施例1同樣地進行測定。測定結果表示於表i。 (d )固著力測試 與實施例1同樣地進行測定。測定結果表示於表1。 (e )貼附玻璃板之剝離測試 與實施例1同樣地進行測定。測定結果表示於表1。 [底塗劑4] 作爲底塗劑,對順丁烯二酸酐·丙烯酸改性烯烴之曰 本製紙化學(股)製的商品名「Auroren S-5 106-MX」100 重量份,添加作爲消泡劑之2-丙醇3重量份,成爲塗佈 用組成物。Auroren S-5106-MX的分子量爲60000〜8 0000 實施例4 (a)相位差薄膜與底塗層的層合 由聚丙烯系樹脂所成的相位差薄膜之層合表面保護薄 膜之相反側,以累積照射量15.9kJ/m2施以電暈放電處理 。在電暈放電處理後5分鐘內’於該電暈處理面’使用邁 耶(Mayer )棒(# 3 )塗佈上述底塗劑4塗佈用組成物’ -39- 201003249 以 80°C的烤箱乾燥3分鐘,於相位差薄膜上形成厚度 0.8μηι的底塗層。 (b )橢圓偏光板的製作 與實施例1同樣地製作橢圓偏光板。 (c )橢圓偏光板的厚度測定 與實施例1同樣地進行測定。測定結果表示於表1。 (d )固著力測試 與實施例1同樣地進行測定。測定結果表示於表1。 (e )貼附玻璃板之剝離測試 與實施例1同樣地進行測定。測定結果表示於表1。 比較例1 (a )無底塗層之相位差薄膜的製作 於聚丙烯所成的相位差薄膜,對表面以累積照射量 1 5.9k J/m2施以電暈放電處理。在電暈放電處理後5分鐘 內,於該電暈處理面,貼合丙烯酸黏著劑[L intec (股)販 售的 P3 1 32]。 (b )橢圓偏光板的製作 與實施例1同樣地製作橢圓偏光板。 -40- 201003249 (c )橢圓偏光板的厚度測定 與實施例1同樣地進行,測定橢圓偏光板的厚度。結 果表示於表1。 (d )固著力測試 與實施例1同樣地進行,評價固著力。結果表示於表 (e )貼附玻璃板之剝離測試 與實施例1同樣地進行,評價剝離性。 表 1 厚度 (μιη) 密合性 從端部&剝離量 (mm) 剝離性 實施例1 140.8 11.2 良好 實施例2 14 1.0 11.2 良好 實施例3 140.8 11.8 良好 實施例4 140.8 10.6 良好 實施例5 140.8 10.9 良好 比較例1 140.0 20.1 不良 此次揭露之實施態樣及實施例爲全部的點之例示,但 不受其限制。本發明的範圍並非上述的說明,而是以請求 範圍表示,其係包含與請求範圍相等的意義及範圍內全部 的變更。 -41 - 201003249 產業上的利用可能性 根據本發明’可提供提高含有聚丙烯系樹脂之相位差 薄膜與黏著劑層的密合性之附黏著劑層之相位差薄膜。 【圖式簡單說明】 圖1係表示本發明的附黏著劑層之相位差薄膜的剖面 示意圖。 圖2 ( A )係本發明的橢圓偏光板之一態樣的剖面示 胃圖;(B)係說明偏光板的軸角度用之示意圖。 圖3 ( A )係本發明的橢圓偏光板之一態樣的剖面示 意圖;(B)係說明偏光板的軸角度用之示意圖。 圖4係表示本發明的液晶顯示裝置之剖面示意圖。 圖5係表示本發明的液晶顯示裝置之剖面示意圖。 [主要元件符號說明】 1 〇 :附黏著劑層之相位差薄膜 1 2 :面內延遲相位軸 1 7 :面內延遲相位軸 2〇 :相位差薄膜 2 2 :吸收軸 2 5 : 1 / 2波長板 30 :底塗層 4〇 :黏著劑層 -42- 201003249 5 〇 :偏光板 52 :橢圓偏光板 5 5 :橢圓偏光板 6 0 :液晶胞 70 ··背光 -43The molecular weight of Auroren S-5189T is 60000~80000. Example 1 (a) Lamination of retardation film and undercoat layer The opposite side of the laminated surface protective film of a retardation film made of a polypropylene-based resin was subjected to corona discharge treatment with a cumulative irradiation amount of 15_9 kJ/m 2 . The primer coating composition was applied to the corona-treated surface within 5 minutes after the corona discharge treatment using a Mayer bar (#6), and dried in an oven at 80 ° C for 3 minutes. An undercoat layer having a thickness of 0.8 μη was formed on the retardation film. (b) Preparation of an elliptically polarizing plate A polarizing plate made of a protective film made of cellulose triacetate (Suitable Chemical Co., Ltd. SRW062) was bonded to both sides of a polarizing film of a polyvinyl alcohol by a iodine-adsorbed film. A polyurethane-based flaky adhesive is adhered [NS 3 00MP sold by Lintec]. A polarizing plate with an adhesive is prepared. On the other hand, from the film of the phase difference of -34 - 201003249 prepared by the above (a), the surface protective film was peeled off, and the surface (polypropylene-based resin surface) was applied at a cumulative irradiation amount of 15.9 kJ/m 2 . In the corona discharge treatment, the adhesive layer of the polarizing plate with an adhesive prepared above was bonded to the corona-treated surface within 5 minutes after the corona discharge treatment. Then, on the undercoat layer side, a corona discharge treatment was also applied at a cumulative irradiation amount of 1 5 · 9 k J/m 2 . Five minutes after the corona discharge treatment, an acrylic sheet-like adhesive [P3132 sold by Lintec Co., Ltd.] was bonded to the corona-treated surface to obtain an elliptically polarizing plate with an adhesive layer. (c) Measurement of Thickness of Elliptical Polarizing Plate (b) The obtained composite polarizing plate with an adhesive layer was measured for thickness using a digital length measuring device "MH-1 5M" manufactured by Nikon. The results are shown in Table 1. (d) Fixing force test The protective film of the phase difference film of the undercoat layer obtained by peeling off (a) was subjected to corona discharge treatment on the surface under the condition of a cumulative irradiation amount of 15.9 kJ/m2. Further, the biaxial thermoplastic saturated borneol resin [ZB 05 5 1 24 manufactured by Nippon Co., Ltd.] was subjected to a corona discharge treatment under the condition of a cumulative irradiation amount of 15.9 kJ/m2. Applying an active energy ray-curable resin containing an epoxy compound to a corona-treated surface of a biaxial thermoplastic saturated borneol resin within 10 minutes after the corona discharge treatment using a Mayer rod (#1) The composition was bonded to the corona-treated surface of the retardation film with the undercoat layer, and UV-cured at -35-201003249 500 mW/1500 mJ in a UV irradiation apparatus manufactured by FUSION Corporation. Next, after the corona discharge treatment was applied to the surface of the undercoat layer at a cumulative irradiation amount of 15_9 kJ/m 2 , the acrylic adhesive was adhered to the corona treatment surface within 5 minutes after the corona discharge treatment (Lintec) The commercially available P3132) was prepared by using a retardation film with an adhesive to prepare a film for adhesion evaluation. Then, it was allowed to stand for 1 day in an environment of a temperature of 23 ° C and a humidity of 60 % RH. The adhesiveness evaluation film was cut into a width of 25 mm and a length of about 200 mm, and the adhesion force at three points in the longitudinal direction was evaluated using the "adhesion force evaluation device" manufactured by Nippon System Group Co., Ltd. In the evaluation, the styrene rubber having a hardness of 60 degrees was used, and while rubbing with a pressing force of 0.4 MP a, rubbing 20 times in a certain direction, the average of the three points of the length of the adhesive layer peeled off from the coating retardation layer was taken as the peeling distance. Seek. Further, the measurement was carried out in an environment of a temperature of 23 ° C and a humidity of 60 % RH. The results are shown in Table 1. (e) Peel test for attaching a glass plate The film for adhesion evaluation obtained in the above (d) was cut into a width of 25 mm and a length of about 200 mm, and the pressure-sensitive adhesive layer was laminated on a soda glass in an autoclave. The pressure was 5 kgf/cm2, and the pressure was applied at a temperature of 50 ° C for 20 minutes, and allowed to stand for 1 day in an environment of a temperature of 23 ° C and a humidity of 60% RH. Further, the peeling system was evaluated by a universal tensile tester (AG_1, SHIMAZU (manufactured by the company)) at a crosshead speed (peeling speed) of 200 mm/min and a 90° peeling test in an environment of a temperature of 23 t and a humidity of 60% RH. . Further, the measurement was carried out in an environment of a temperature of 23 ° C and a humidity of 60% RH. -36- 201003249 In Table 1, the symbol of the peelability is indicated by the following. Good: no adhesive layer remains on the glass plate and can be peeled off. Defective. The adhesive layer remains on the glass plate and peels off. [Substrate 2] Hydroxene 40 parts by weight, 60000 as a primer, 30 parts of toluene added to the product name "Auroren 250_MX parts" manufactured by maleic anhydride/acrylic acid modified paper-making chemistry (stock) '2-propanol i 作为 as a defoamer, a coating composition. The molecular weight of Auroren 250-MX is ~800. 〇Example 2 Protective thin electric treatment uses the composition to a thickness (a) The phase difference film and the undercoat layer are laminated on the opposite side of the laminated surface film of the retardation film formed of the polypropylene resin, and the corona discharge is applied at a cumulative irradiation amount of 15.9 kJ/m 2 . In the last 5 minutes, on the corona treatment surface, the Mayer rod (#14) was coated with the above primer 2 for coating, and dried on the retardation film at 8 (TC oven for 5 minutes). (b) Preparation of an elliptically polarizing plate An elliptically polarizing plate was produced in the same manner as in Example 1. (C) Measurement of Thickness of Elliptical Polarizing Plate - 37-201003249 Measurement was carried out in the same manner as in Example 1. The measurement results were shown. (d) The fixation test was carried out in the same manner as in Example 1. The measurement results indicated that (e) attached The peeling test of the glass plate was carried out in the same manner as in Example 1. The measurement result was stained [primer 3] as a primer, and the maleic anhydride/acrylic acid was changed to the product name of the paper-making chemical (stock). Auroren 3 5 0T part, 3 parts by weight of 2-propanol as an antifoaming agent was added to make a rent. The molecular weight of Auroren 350T was 60,000 to 80,000. Example 3 (a) Lamination of retardation film and undercoat layer On the opposite side of the lamination film of the retardation film made of the polypropylene resin, electric J was applied at a cumulative irradiation amount of 15.9 kJ/m 2 . Within 5 minutes after the corona discharge treatment, the corona treatment surface was (Mayer) rod (#3) was coated with the primer 10 for coating for 3 minutes in an oven for 3 minutes, and an undercoat layer of 0.8 μm on the retardation film. (b) An elliptically polarizing plate was prepared in Table 1. In Table 1, the olefin was used to form a ellipsic sheet in the same manner as in Example 1 except that the olefin was coated with a surface-protective thin discharge treatment and a thickness of -38 to 201003249 was used. The thickness of the elliptically polarizing plate was measured in the same manner as in Example 1. The measurement results are shown in Table i. (d) Fixing force test The measurement was performed in the same manner as in Example 1. The measurement results are shown in Table 1. (e) The peeling test for attaching a glass plate was carried out in the same manner as in Example 1. The measurement results are shown in Table 1. Coating agent 4] As a primer, 100 parts by weight of a product name "Auroren S-5 106-MX" manufactured by Sakamoto Paper Chemical Co., Ltd., which is a maleic anhydride/acrylic acid-modified olefin, is added as a defoaming agent. 3 parts by weight of 2-propanol was used as a coating composition. Auroren S-5106-MX has a molecular weight of 60,000 to 8,000. Example 4 (a) lamination of a retardation film and an undercoat layer on the opposite side of a laminated surface protective film of a retardation film made of a polypropylene-based resin, Corona discharge treatment was applied at a cumulative irradiation amount of 15.9 kJ/m2. Applying the above primer 4 coating composition '-39- 201003249 to '80°C' using the Mayer rod (#3) within 5 minutes after the corona discharge treatment The oven was dried for 3 minutes to form an undercoat layer having a thickness of 0.8 μm on the retardation film. (b) Preparation of elliptically polarizing plate An elliptically polarizing plate was produced in the same manner as in the first embodiment. (c) Measurement of Thickness of Elliptical Polarizing Plate The measurement was carried out in the same manner as in Example 1. The measurement results are shown in Table 1. (d) Fixing force test The measurement was carried out in the same manner as in Example 1. The measurement results are shown in Table 1. (e) Peel test for attaching a glass plate The measurement was carried out in the same manner as in Example 1. The measurement results are shown in Table 1. Comparative Example 1 (a) Preparation of retardation film without undercoat layer A retardation film made of polypropylene was subjected to corona discharge treatment with a cumulative irradiation amount of 1 5.9 kJ/m2 on the surface. The acrylic adhesive (P3 1 32 sold by Lintec) was attached to the corona-treated surface within 5 minutes after the corona discharge treatment. (b) Preparation of elliptically polarizing plate An elliptically polarizing plate was produced in the same manner as in the first embodiment. -40-201003249 (c) Measurement of Thickness of Elliptical Polarizing Plate The thickness of the elliptically polarizing plate was measured in the same manner as in Example 1. The results are shown in Table 1. (d) Fixing force test The fixing force was evaluated in the same manner as in Example 1. The results are shown in Table (e). Peel test for attaching a glass plate was carried out in the same manner as in Example 1, and the peeling property was evaluated. Table 1 Thickness (μιη) Adhesion from End & Peeling Amount (mm) Peelability Example 1 140.8 11.2 Good Example 2 14 1.0 11.2 Good Example 3 140.8 11.8 Good Example 4 140.8 10.6 Good Example 5 140.8 10.9 Good Comparative Example 1 140.0 20.1 Disadvantages The embodiments and examples of the present disclosure are illustrative of all points, but are not limited thereto. The scope of the present invention is defined by the scope of the claims. -41 - 201003249 Industrial Applicability According to the present invention, it is possible to provide a phase difference film of an adhesive layer which improves the adhesion between the phase difference film of the polypropylene resin and the pressure-sensitive adhesive layer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a phase difference film of an adhesive layer of the present invention. Fig. 2 (A) is a cross-sectional view showing a portion of the ellipsic polarizing plate of the present invention; (B) is a schematic view showing the axial angle of the polarizing plate. Fig. 3 (A) is a cross-sectional view showing an aspect of the elliptically polarizing plate of the present invention; and (B) is a view showing the axial angle of the polarizing plate. Fig. 4 is a schematic cross-sectional view showing a liquid crystal display device of the present invention. Fig. 5 is a schematic cross-sectional view showing a liquid crystal display device of the present invention. [Main component symbol description] 1 〇: retardation film with adhesive layer 1 2 : in-plane retardation phase axis 1 7 : in-plane retardation phase axis 2 〇: retardation film 2 2 : absorption axis 2 5 : 1 / 2 Wavelength plate 30: undercoat layer 4: adhesive layer - 42 - 201003249 5 〇: polarizing plate 52: elliptically polarizing plate 5 5 : elliptically polarizing plate 6 0 : liquid crystal cell 70 · · backlight - 43